Geochemical characterization of the Late Pleistocene loess-palaeosol sequence in Tyszowce (Sokal Plateau-Ridge, SE Poland)

Quaternary International xxx (xxxx) xxx–xxx

Contents lists available at ScienceDirect

Quaternary International journal homepage: www.elsevier.com/locate/quaint

Geochemical characterization of the Late Pleistocene loess-palaeosol sequence in Tyszowce (Sokal Plateau-Ridge, SE Poland) Jacek Skurzyńskia,∗, Zdzisław Jarya, Jerzy Raczyka, Piotr Moskab, Bartosz Korabiewskia, Kamila Ryznera, Marcin Krawczyka a b

University of Wroclaw, Institute of Geography and Regional Development, 1 Uniwersytecki Sqr, 50-137, Wroclaw, Poland Silesian University of Technology, Institute of Physics - Center for Science and Education, ul. Konarskiego 22B, 44-100, Gliwice, Poland

A R T I C LE I N FO

A B S T R A C T

Keywords: Loess Palaeosol Geochemistry Weathering indices SE Poland Late pleistocene

The Late Pleistocene loess-palaeosol sequence in Tyszowce (Sokal Plateau-Ridge, SE Poland) has been analysed for major elements (Si, Na, K, Mg, Ca, Fe, Mn, Al, Ti and P) in order to determine its chemical composition, stratigraphy and degree of chemical weathering. For the investigation, a total number of 85 loess and soil samples were tested. The vertical differentiation of chemical composition is strongly correlated with the variability of pedo- and lithostratigraphic units. The loess-palaeosol sequence in Tyszowce is geochemically distinct from other loess presented in the worldwide literature. The profile is generally enriched with silica while other chemical elements are relatively depleted. The contents of the major elements, except Si, are lower in relation to the Global Average Loess (GAL) composition. Weathering indices, such as Chemical Index of Alteration (CIA) or K/Al molar ratio and A-CN-K diagram, imply weak to moderate weathering of the source material.

1. Introduction Loess sediments in Poland are a part of the northern European loess belt, one of the most extensive loess areas in the world (e.g. Haase et al., 2007; Jary and Ciszek, 2013). Loess sediments in this area are spatially differentiated. This is connected mainly with the latitudinal extent of the Pleistocene extra-glacial zone (Tutkovsky, 1899; Jahn, 1950). Loess-palaeosol sequences in Poland have typical litho-pedological units of European loess (Jary and Ciszek, 2013). However, the pedolithological characteristics of Polish loess spatially differ from the west to the east. The lithological properties of the loess and palaeosols provide very good evidence of the variety of climatic and environmental conditions (e.g. Jersak, 1973; Maruszczak, 1991; Dwucet, 1999) over the last glacial-interglacial cycle. These features can be reconstructed based on the variety of proxy data. A number of studies have been conducted on loess deposits in Poland, providing a significant amount of information concerning their stratigraphy and palaeoclimatic conditions (e.g. Jary, 2009, 2010; Badura et al., 2013; Jary and Ciszek, 2013; Moska et al., 2011, 2017). Most papers focused on chronostratigraphy or basic lithological features, while little attention was paid to the geochemistry of aeolian deposits in Poland (e.g. Łukaszew and Mojski, 1968; Łącka et al., 2007; Łanczont et al., 2015a; b; Raczyk et al., 2015; Skurzyński et al., 2017).

∗

However, this issue should be broadly elaborated because, in the case of subaerial sediments, chemical weathering after deposition may play a more important role than it did in the source areas (Xiao et al., 2010; Varga et al., 2011). Under weathering conditions in the warm and moist climate, the element composition of a given parent material changes. Soluble and mobile elements are depleted and less soluble and immobile elements are relatively enriched (Buggle et al., 2011). As a consequence, the loess-palaesosol sequence differs in chemical composition even from one stratigraphic unit to another (Taylor et al., 1983; Pye and Johnson, 1988), thus it can be used as a lithostratigraphic criterion to verify the stratigraphic subdivisions (Ahmad and Chandra, 2013). This paper is focused on the major chemical elements of the Tyszowce loess-palaeosol sequence. The main purpose is to analyse in detail the geochemical characteristics of this section and to determine the weathering intensity. It is also important to provide new results concerning loess geochemistry in Poland for the worldwide database on the geochemical composition of loess-palaeosol sequences. 2. Regional setting and description of the profile The Tyszowce loess section (λ = 23°42′45″E, φ = 50°36′30″N) is located in the northern part of the Sokal Plateau-Ridge, which is the

Corresponding author. E-mail address: [email protected] (J. Skurzyński).

https://doi.org/10.1016/j.quaint.2018.04.023 Received 31 May 2017; Received in revised form 9 March 2018; Accepted 9 April 2018 1040-6182/ © 2018 Elsevier Ltd and INQUA. All rights reserved.

Please cite this article as: Skurzyński, J., Quaternary International (2018), https://doi.org/10.1016/j.quaint.2018.04.023

Quaternary International xxx (xxxx) xxx–xxx

J. Skurzyński et al.

Fig. 1. Location of the Tyszowce loess-palaeosol section on the map of loess distribution in Europe (A) and Poland (B) (after Mroczek, 2013, modified). PL means Poland, CZ – Czech Republic, SK - Slovakia, UA – Ukraine.

presence during the sedimentation of the L1LL2 loess. The L1SS1 unit (MIS 3) has been determined in Poland as the Komorniki soil (Jersak, 1973) or Gi/LMd soil according to Maruszczak (1991). The L1SS1 pedocomplex separates two main phases of Weichselian loess deposition. It consists of weak cambic horizon and 1–3 overlying tundra gley horizons, which have been deformed by cryoturbation and gelifluction processes. The L1SS1 palaeosol is covered by exceptionally thick L1LL1 loess, which is evidence of a very high rate of material deposition during the Upper Pleniweichselian (MIS 2). The L1LL1 unit is dominated by banded and laminated lithofacies. Homogeneous loess occurs very rarely. Banded loess in the lower part of the L1LL1 unit has been created as a result of simultaneous aeolian dust deposition and surface washout. In the middle and upper parts of the L1LL1 unit there are several sandy layers, suggesting short-term episodes of material transport from the nearby Huczwa River valley under severe climatic conditions. Tyszowce loess site is the unique place where two generations of ice-wedge casts within the L1LL1 unit have been found (Jary et al., 2014).

westernmost part of the Volhynia Upland (Maruszczak, 1972; Kondracki, 2002). The Sokal Plateau-Ridge is a latitudinal cretaceous hump with thick loess cover (Jahn, 1956). From the north and south the region is limited by distinct morphological edges to over 10 m high (Wojtanowicz and Buraczyński, 1978). The loess sequence in Tyszowce is located at the height of 226 m above sea level in the northern margin of loess cover, close to the Huczwa River, about 30 m above the modern valley bottom (Fig. 1). The loess deposits at an active brickyard locally reach a thickness of 20 m. The stratigraphy and palaeoenvironmental interpretation of neighbouring loess-palaeosol profiles in Tyszowce have been presented several times in Polish literature (e.g. Maruszczak, 1974; Buraczyński and Wojtanowicz, 1975; Wojtanowicz and Buraczyński, 1978; Jary, 2007). The profile discussed in this study was prepared during fieldwork in 2012 on the local culmination. The previously conducted research showed that the Late Pleistocene (Moska et al., 2017) loess-palaeosol sequence in Tyszowce probably contains one of the most detailed indirect records of climatic and environmental changes in Polish loess covers (Moska et al., 2017; Skurzyński et al., 2017). The 19-m loess-palaeosol sequence in Tyszowce consists of five units developed in the Late Pleistocene and Holocene: two polygenetic palaeosol complexes (S1 and L1SS1), two calcareous loess units (L1LL1 and L1LL2) and recent S0 soil (Fig. 2). To present the stratigraphy of the section, the labelling system elaborated by Kukla and An (1989) and adopted by Marković and co-authors (2008, 2015) has been used. The S1 pedocomplex is commonly correlated with marine isotope stage (MIS) 5 (Pisias et al., 1984; Martinson et al., 1987). In Polish loess stratigraphy it has been determined by Jersak (1973) as the Nietulisko I pedocomplex or Gi + GJ1 soils according to Maruszczak (1991). The S1 palaeosol in the studied section consists of two thick welded humic subhorizons of steppe soils (Early Weichselian) and a structural B horizon developed on a sandy substrate in the lower part (Eemian). The lower loess unit, i.e. L1LL2 (MIS 4), in Tyszowce is clearly banded and contains signs of gley processes and numerous humic intercalations. The lithological features of the L1LL2 loess indicate that this unit was formed as a result of aeolian deposition on the surface reworked by slope processes. The upper part of the L1LL2 loess has been transformed by processes connected with the formation of the L1SS1 palaeosol. There are ice-wedge casts in the L1LL2 loess unit in Tyszowce (Jary, 2007, 2009), which are evidence of permafrost

3. Methods The loess profile in Tyszowce was carefully cleaned and documented with respect to its sedimentology, palaeopedology and stratigraphy. The 19-m vertical sequence was sampled at close intervals (5 cm). In total, 380 samples were collected. For geochemical analysis, 85 samples were chosen - the number of samples was densified in the neighbourhood of lithological borders. The chemical composition was determined in accordance with the method introduced into the Polish loess literature by Raczyk (Raczyk et al., 2015). The selected bulk samples of loess and soil were dried in a laboratory dryer at 105 °C for 24 h. All samples were finely ground in agate mortar before calcination in the muffle furnace (1000 °C/1 h) to calculate the loss on ignition (LOI). From each sample, 250 mg of material was taken and mixed with flux (lithium borate). The mixture was melted in platinum crucible in the flame of a Bunsen burner at approx. 900 °C. The resulting melt was dissolved in 10% HCl and diluted with distilled water to 250 ml. Major element abundances, i.e. sodium (Na), potassium (K), magnesium (Mg), calcium (Ca), iron (Fe), manganese (Mn), aluminium (Al) and titanium (Ti), were determined by atomic absorption spectrometry (AAS) using a GBC Avanta Ʃ spectrometer. 2

Quaternary International xxx (xxxx) xxx–xxx

J. Skurzyński et al.

Phosphorus (P) was measured colourimetrically after mineralization of the sample in a microwave. Analytical uncertainties were ± 5% for Al, Fe, Ti, P, and ± 10% for Mn, Mg, Ca, Na, K. The resulting values of element concentrations were converted to oxides (excluding volatile components). Silica was not measured, assuming it to be a complement to 100%. This assumption was confirmed by the analysis and comparison of standards, i.e. loess certified reference materials ISE 934 and ISE 974, made by the Wepal company. The grain-size of the samples was determined by a laser grain-size analyser (Malvern Mastersizer, 2000), which has a measurement range of 0.02–2000 μm with a precision of ± 1%. The refractive and absorption indices used in the measurements were 1.544 and 0.1. Measurements were conducted after chemical pretreatment. The samples were first treated with H2O2 and 10% HCl to remove organic matter and carbonate, respectively. Finally, the samples were dispersed with a 0.5 N sodium metaphosphotate solution and ultrasonicated for 10 min before measuring (e.g. Song et al., 2014). 4. Results and discussions 4.1. General geochemical characteristic of the section The chemical composition of the loess-palaeosol sequence in Tyszowce is clearly differentiated in the depth profile. The major element composition of bulk samples (wt %) from Tyszowce is presented in Table 1. The samples contain a wide range of Si from 68.3 to 92.4%, with a relatively high mean value (80.1%). Si shows a negative correlation with all the major elements (Table 1), whose contents are relatively low. For example, a strong negative correlation between Si and K (R = −0.84) suggest a decrease in K-bearing minerals (e.g. illite or muscovite) while the content of quartz increases (Moosavirad et al., 2011). However, a positive correlation of Al with K (R = 0.80), Na (R = 0.87) and Mg (R = 0.19) suggests that the concentrations of the Kbearing minerals have a weak to moderate influence on the Al distribution in the profile (McLennan, 1993; Ahmad and Chandra, 2013). This probably also applies to Fe and Ti, which are strongly correlated with Al (R = 0.94 and 0.81, respectively). Ca and Mg are strong positively correlated with each other (R = 0.87) and LOI (R = 0.80, in both cases). This suggests that LOI is associated mainly with carbonate minerals. Na and K show similar trends in the depth profile (R = 0.87). The contents of Mn and P are minor and there is no interdependence with other chemical elements. The vertical differentiation of the chemical composition of the loesspalaeosol sequence in Tyszowce is strongly correlated with the variability of pedo- and lithostratigraphic units (Table 2, Fig. 3). In terms of the average chemical composition (Table 2), the high content of Si in the S0 and S1 soils is clearly marked. Both of these pedocomplexes are characterized by low amounts of Al, Mg and Ca, for example. This means that the content of mobile elements depleted during pedogenesis is low, as is the content of elements that are usually accumulated in soil units. The L1LL1, L1SS1 and L1LL2 units have many common features, e.g. similar average proportion of Si (Table 2). This suggests that the primary composition was quite homogeneous and was later modified by pedogenesis. The S0 soil is developed at the top of the L1LL1 loess. However, soil processes have changed the geochemical characteristics of the parent material quite significantly. This unit is characterized by the highest average P content in the profile (Table 2; Fig. 3). The genetic horizons of this soil are rather poorly differentiated - the whole unit is quite homogeneous. However, in the A horizon the LOI values were increased, probably due to the higher proportion of organic matter. In this horizon slightly less Fe and Na has been noticed. The geochemical composition of the L1LL1 loess differs significantly from the other units (Table 2). At the top of the L1LL1 loess a horizon of carbonate enrichment occurs - increases in the Ca and Mg amounts are

Fig. 2. Litho-pedostratigraphical units and results of OSL dating (Moska et al., 2017) of the Tyszowce loess-palaeosol section.

3

Quaternary International xxx (xxxx) xxx–xxx

J. Skurzyński et al.

Table 1 Major (wt %) elements concentrations of the loess-soil samples from Tyszowce. Total iron is expressed as Fe2O3. Major elements are recalculated on a volatile-free basis. Depth [m]

SiO2 (%)

Al2O3 (%)

Fe2O3 (%)

MnO (%)

MgO (%)

CaO (%)

Na2O (%)

K2O (%)

TiO2 (%)

P2O5 (%)

LOI (%)

0,05 0,10 0,35 0,55 0,70 1,00 1,40 1,70 1,90 2,10 2,40 2,70 3,00 3,25 3,65 4,00 4,35 4,60 4,90 5,00 5,10 5,35 5,70 6,00 6,25 6,65 7,05 7,15 7,40 7,60 7,85 8,15 8,40 8,80 8,95 9,10 9,30 9,55 9,80 10,00 10,35 10,45 10,65 10,90 11,10 11,35 11,55 11,75 11,85 11,95 12,05 12,25 12,55 12,95 13,10 13,35 13,70 13,90 14,05 14,25 14,60 14,90 15,10 15,30 15,50 15,65 15,80 16,00 16,25 16,50 16,75 16,85 17,00

86,16 86,78 86,44 85,23 86,02 76,55 83,87 80,20 80,40 88,97 82,89 84,62 81,98 80,98 82,48 81,43 87,23 80,79 79,93 83,75 81,60 82,75 80,32 77,22 78,84 77,84 79,79 77,15 79,03 79,13 79,28 79,42 77,04 78,67 77,49 77,88 79,68 74,95 77,65 78,02 77,35 78,70 76,19 74,06 76,19 75,90 77,44 79,83 77,29 79,99 74,60 75,73 76,86 77,82 77,26 77,71 72,53 68,26 76,74 73,92 73,69 80,21 78,61 79,63 75,68 78,61 75,37 76,97 77,22 74,08 75,46 75,04 78,52

6,97 6,53 7,04 7,40 6,84 7,23 5,29 5,94 6,26 3,61 5,80 4,58 6,11 6,15 5,91 6,49 4,20 6,80 6,81 5,45 6,52 6,10 7,09 7,81 7,07 8,13 7,47 7,78 7,50 7,12 7,32 7,06 7,87 7,44 7,85 7,79 7,60 8,44 8,19 7,76 8,09 8,66 9,46 9,85 9,40 9,57 9,36 7,98 9,23 7,74 9,53 8,90 9,05 9,38 9,50 9,31 9,64 10,64 10,26 10,64 10,76 10,42 11,72 11,32 10,57 9,87 10,76 10,48 10,35 10,91 10,76 11,26 10,50

2,29 2,18 2,28 2,37 2,33 2,04 1,61 1,77 1,75 1,07 1,54 1,10 1,48 1,58 1,51 1,70 1,13 1,80 1,80 1,48 1,68 1,64 1,73 2,10 1,96 2,19 1,91 2,13 1,99 1,97 2,00 1,88 2,08 2,06 2,18 1,97 2,07 2,22 2,23 2,33 2,53 2,51 2,55 2,97 2,66 2,71 2,61 2,32 2,64 2,18 2,65 2,80 2,65 2,65 2,60 2,72 2,99 2,93 2,95 3,15 3,12 3,15 3,55 3,24 3,34 2,87 3,20 3,17 3,23 3,60 3,41 3,11 3,13

0,07 0,05 0,05 0,05 0,05 0,05 0,04 0,04 0,05 0,05 0,04 0,03 0,04 0,05 0,05 0,05 0,04 0,05 0,05 0,04 0,05 0,05 0,04 0,05 0,05 0,05 0,05 0,07 0,04 0,06 0,05 0,05 0,05 0,05 0,05 0,06 0,06 0,05 0,06 0,06 0,06 0,05 0,07 0,07 0,05 0,04 0,05 0,04 0,04 0,07 0,05 0,05 0,07 0,04 0,06 0,05 0,07 0,05 0,05 0,06 0,10 0,06 0,04 0,03 0,03 0,04 0,04 0,04 0,04 0,04 0,04 0,04 0,04

0,45 0,47 0,44 0,50 0,53 1,40 1,07 1,28 1,22 0,85 1,15 0,86 1,43 1,39 1,67 1,36 1,00 1,46 1,43 1,19 1,34 1,36 1,47 2,15 1,65 1,77 1,65 2,00 1,82 1,83 1,70 1,68 1,96 1,80 1,83 1,80 1,49 2,18 1,63 1,55 1,74 1,49 1,53 1,59 1,46 1,56 1,42 1,28 1,37 1,39 1,75 1,45 1,42 1,37 1,38 1,38 1,81 1,72 1,42 1,57 0,98 0,69 0,79 0,73 1,21 1,08 1,18 1,14 1,07 1,18 1,24 1,19 0,97

0,84 0,81 0,60 1,12 0,87 9,61 5,50 8,00 7,34 3,59 5,73 6,57 6,06 6,89 5,38 5,82 4,19 5,91 6,85 5,37 5,76 5,14 6,13 7,04 7,09 6,28 5,67 7,31 6,10 6,53 6,17 6,57 7,32 6,45 6,94 7,04 5,72 8,37 6,64 6,92 6,63 4,89 6,46 7,62 6,14 6,41 5,44 4,86 5,63 5,13 7,58 7,34 6,07 4,99 5,43 4,89 9,31 12,46 4,74 6,70 7,53 2,01 1,88 1,67 5,63 3,98 5,59 4,30 4,26 6,47 5,35 5,87 3,44

0,73 0,69 0,69 0,76 0,75 0,72 0,65 0,71 0,72 0,53 0,77 0,64 0,75 0,78 0,78 0,82 0,63 0,83 0,80 0,76 0,85 0,85 0,87 0,89 0,89 0,98 0,90 0,88 0,92 0,87 0,92 0,87 0,94 0,92 0,93 0,87 0,97 0,96 0,93 0,87 0,92 1,02 1,00 0,97 1,04 1,01 0,98 0,98 0,99 0,90 0,93 0,93 0,96 0,99 0,94 0,92 0,89 0,93 0,94 0,99 0,97 0,82 0,83 0,83 0,83 0,87 0,90 0,90 0,88 0,85 0,88 0,82 0,83

1,79 1,78 1,77 1,81 1,85 1,69 1,45 1,44 1,61 0,90 1,48 1,11 1,55 1,61 1,58 1,69 1,11 1,69 1,67 1,41 1,55 1,47 1,71 2,02 1,80 2,05 1,84 1,97 1,89 1,80 1,85 1,77 2,00 1,89 2,01 1,88 1,72 2,10 1,97 1,77 1,95 1,98 2,00 2,13 2,31 2,05 1,96 1,98 2,05 1,84 2,15 2,01 2,12 2,01 2,08 2,24 2,00 2,24 2,14 2,21 2,08 1,87 1,82 1,78 1,91 1,88 2,12 2,14 2,09 2,02 2,03 1,87 1,75

0,61 0,60 0,63 0,64 0,66 0,59 0,48 0,53 0,56 0,40 0,54 0,44 0,55 0,52 0,57 0,59 0,45 0,60 0,59 0,50 0,59 0,57 0,57 0,65 0,59 0,67 0,66 0,66 0,63 0,62 0,63 0,63 0,67 0,65 0,64 0,65 0,62 0,65 0,64 0,64 0,65 0,63 0,67 0,67 0,69 0,67 0,66 0,65 0,67 0,69 0,67 0,72 0,70 0,67 0,66 0,70 0,66 0,67 0,68 0,65 0,69 0,67 0,68 0,68 0,70 0,72 0,74 0,75 0,79 0,77 0,76 0,74 0,74

0,10 0,12 0,08 0,10 0,11 0,12 0,05 0,08 0,08 0,04 0,06 0,04 0,05 0,06 0,06 0,07 0,04 0,06 0,06 0,05 0,06 0,06 0,07 0,07 0,06 0,06 0,06 0,07 0,07 0,07 0,07 0,06 0,07 0,06 0,07 0,06 0,07 0,08 0,07 0,07 0,08 0,08 0,07 0,07 0,07 0,07 0,08 0,07 0,08 0,08 0,09 0,08 0,08 0,08 0,08 0,08 0,10 0,10 0,09 0,09 0,07 0,09 0,08 0,08 0,10 0,09 0,09 0,10 0,07 0,07 0,08 0,07 0,07

5,20 5,15 4,03 3,97 3,69 9,02 5,22 7,71 7,23 3,93 6,00 5,82 6,34 6,90 6,06 6,52 4,29 6,44 7,13 5,76 6,28 6,06 6,80 8,03 7,31 6,96 6,70 13,16 6,89 7,24 6,91 7,23 7,96 7,32 7,80 7,63 7,49 8,69 7,23 7,78 7,81 6,77 7,69 8,77 6,86 7,87 6,88 5,88 6,71 6,09 8,13 7,67 7,24 6,53 6,81 6,56 9,87 8,58 6,89 8,29 5,83 6,55 6,81 7,01 7,93 6,46 7,61 6,92 6,70 8,25 7,90 8,39 6,72

(continued on next page) 4

Quaternary International xxx (xxxx) xxx–xxx

J. Skurzyński et al.

Table 1 (continued) Depth [m]

SiO2 (%)

Al2O3 (%)

Fe2O3 (%)

MnO (%)

MgO (%)

CaO (%)

Na2O (%)

K2O (%)

TiO2 (%)

P2O5 (%)

LOI (%)

17,10 17,20 17,30 17,45 17,65 17,80 17,95 18,05 18,35 18,50 18,85 19,00 Mean Min Max

82,62 80,26 85,40 85,59 85,93 86,37 87,79 88,59 88,98 92,44 91,26 91,65 80,13 68,26 92,44

9,24 11,11 7,49 8,01 7,81 7,19 6,35 5,93 5,92 3,72 4,53 4,27 7,99 3,61 11,72

2,48 3,20 2,03 2,24 2,19 2,37 2,06 1,83 2,35 1,69 1,66 1,57 2,31 1,07 3,60

0,04 0,03 0,03 0,03 0,03 0,05 0,04 0,04 0,02 0,01 0,03 0,02 0,05 0,01 0,10

0,65 0,65 0,55 0,52 0,46 0,43 0,41 0,41 0,49 0,52 0,44 0,43 1,24 0,41 2,18

1,90 1,16 1,52 0,68 0,58 0,55 0,37 0,38 0,36 0,42 0,34 0,39 4,98 0,34 12,46

0,68 0,81 0,59 0,55 0,62 0,61 0,57 0,55 0,39 0,27 0,38 0,37 0,82 0,27 1,04

1,64 1,94 1,62 1,63 1,61 1,62 1,63 1,54 1,03 0,66 0,94 0,92 1,78 0,66 2,31

0,71 0,79 0,75 0,70 0,73 0,76 0,70 0,67 0,41 0,26 0,40 0,34 0,63 0,26 0,79

0,05 0,07 0,03 0,04 0,04 0,05 0,08 0,07 0,05 0,02 0,03 0,03 0,07 0,02 0,12

5,52 5,69 4,74 4,00 4,07 4,10 2,65 2,38 3,38 3,42 2,12 1,91 6,50 1,91 13,16

the relatively high Ca content is characteristic for loess units. This indicates that this unit is a mixture of eroded soils and fresh loess deposits. The S1 pedocomplex is characterized by a very high average content of Si (88.4%) and the lowest average contents of the remaining chemical elements. A similar geochemical characteristic of the S1 unit was noticed in the Dankowice profile (SW Poland, Raczyk et al., 2015). The main litho-pedostratigraphic units of the loess-palaeosol sequence in Tyszowce differ from each other in terms of its chemical composition. The basic differences between the main loess and soil units are well expressed by changes in the value of molar relations e.g. Mg/Ca and K/Ca (Fig. 4). The Mg/Ca molar ratio increases in soils due to weaker Mg leaching, relative to Ca (Bokhorst et al., 2009). Mg is retained much more by clay minerals than Ca, due to significant differences in their ion beam size (Perel'man, 1977). The K/Ca ratio mainly reflects the strong dissolution of carbonates (Yang et al., 2004; Varga et al., 2011), thus it highlights the soil units (Fig. 4).

observed. The average contents of Al (7.74%) and Fe (2.15%) are significantly low in the profile scale, while the average Ca (6.43%) and Mg (1.51%) contents are the highest in the section (Table 2). In addition, the L1LL1 loess is also distinctly geochemically differentiated in the vertical profile. The uppermost parts of the unit are characterized by the lowest Al and Fe contents in the profile (Fig. 3). The contribution of these elements in the L1LL1 loess increases with depth and reaches its maximum just above the L1SS1 soil - in the horizon formed by deluvial processes. The Mn contents are variable in the lower part of the L1LL1 loess, and the transition to L1SS1 is underlined by a sharp decrease in the content of this element. In the top part of the L1LL1 loess, at a depth of 2.1, 2.7, 4.35 and 5.0 m, layers heavily enriched in the sand fraction have been found. Significant increases in Si content are observed in these samples, while the proportion of the remaining components are reduced (Fig. 3). The chemical composition of the L1SS1 soil is similar to the L1LL2 loess, in which the uppermost part was developed. L1SS1 is characterized by relatively high proportions of Al (11.01%) and Fe (3.32%), and significantly reduced Ca (2.8%) and Mg (0.85%) contents. The L1LL2 loess has the highest average Ti (0.75%) and K (1.95%) content and relatively high amounts of Al (10.5%) and Fe (3.14%). This unit, relative to the adjacent soil units, is clearly enriched in Ca (4.23%) and Mg (1.04%). The high proportion of Al and Fe may suggest a significant effect of postdepositional soil-weathering processes. However,

4.2. Chemical weathering degree As shown above, in the Tyszowce profile the soil units clearly differ from the loess. The alternation of loess and fossil soils is the basis for the stratigraphy of loess-palaeosol sequences (e.g.: Pecsi, 1995) and the intensity of pedogenic processes is highly related to the degree of

Table 2 Average chemical composition of the main litho-pedostratigraphic units of Tyszowce profile.

SiO2 (%) Al2O3 (%) Fe2O3 (%) MnO (%) MgO (%) CaO (%) Na2O (%) K2O (%) TiO2 (%) P2O5 (%) LOI (%)

S0

L1LL1

L1SS1

L1LL2

S1

86,13 85,23–86,78 6,96 6,53–7,40 2,29 2,18–2,37 0,06 0,05–0,07 0,48 0,44–0,53 0,85 0,60–1,12 0,72 0,69–0,76 1,80 1,77–1,85 0,63 0,60–0,66 0,10 0,08–0,12 4,41 3,69–9,02

78,71 68,26–88,97 7,74 3,61–10,76 2,15 1,07–3,15 0,05 0,03–0,10 1,51 0,85–2,18 6,43 3,59–12,46 0,88 0,53–1,04 1,83 0,90–2,31 0,62 0,40–0,72 0,07 0,04–0,12 7,14 3,93–13,16

78,53 75,68–80,21 11,01 10,42–11,72 3,32 3,15–3,55 0,04 0,03–0,06 0,85 0,69–1,21 2,8 1,67–5,63 0,83 0,82–0,83 1,84 1,78–1,91 0,68 0,67–0,70 0,09 0,08–0,10 7,07 6,46–7,93

77,41 74,08–82,62 10,52 9,24–11,26 3,14 2,48–3,60 0,04 0,03–0,04 1,04 0,65–1,24 4,23 1,16–6,47 0,84 0,68–0,90 1,95 1,64–2,14 0,75 0,71–0,79 0,08 0,05–0,10 7,02 5,52–8,39

88,40 85,40–92,44 6,12 3,72–8,01 2,00 1,57–2,37 0,03 0,01–0,05 0,46 0,41–0,55 0,56 0,34–1,52 0,49 0,27–0,62 1,32 0,66–1,63 0,57 0,26–0,76 0,04 0,02–0,08 3,28 1,91–4,74

5

Quaternary International xxx (xxxx) xxx–xxx

J. Skurzyński et al.

Fig. 3. Distribution of major elements contents (wt %) of Tyszowce profile. Dashed line means sandy layers; pale grey rectangles are horizons with signs of the gley processes. Main pedo-lithostratigraphic units are shown.

used to quantify the level of chemical weathering, defined by the following equation in molar proportions: CIA = [Al2O3/(Al2O3 + CaO * + Na2O + K2O)] * 100. CaO* represents Ca exclusively from the silicate minerals, and was determined by the method introduced by McLennan (1993). This is one of the most commonly used indicators for the reconstruction of palaeoclimatic and palaeoenvironmental conditions during the formation of loess-palaeosol sequences (Varga et al., 2011). It is assumed that the CIA in the range of 50–65 corresponds to weak chemical weathering under a cold and dry climate, and the values 65–85 represent warm and moist palaeoclimatic conditions (e.g.: Song et al., 2014). The variability of chemical weathering, expressed by the CIA index, is illustrated on the ternary A-CN-K diagram (Fig. 5; Nesbitt and Young, 1984). The duality of the profile is clearly highlighted. The CIA value of 65 is an acceptable limit, which separates weak and moderate stages of chemical weathering (e.g. Song et al., 2014). The S0 soil and the majority of the L1LL1 loess (up to 13.5 m in depth) were classified as weakly chemically weathered. Samples from the depth of 13.5–14.6 m (loess-soil sediments) are closer to the deeper, pedogenetically transformed part of the profile. The L1SS1 and L1LL2 units show a similar, relatively high degree of chemical weathering, reaching a maximum CIA value in the profile (above 70 in L1SS1). Two weathering trends of silicate minerals are indicated. The trend in the slightly chemically weathered part of the profile is subparallel to the CaO*+Na2O axis, and begins near the Upper Continental Crust (UCC; Taylor and McLennan, 1985) point. This suggests that the removal of Ca and Na (i.e. dissolving of plagioclases) is a major process of chemical weathering (Yang et al., 2004). In the more weathered part of the profile, the trend changes due to more intensive K removal. This is typical for the chemical weathering processes characterized by the removal of Na and Ca in the initial phase, removal of K in the intermediate phase and Si in the advanced phase (Nesbitt et al., 1980; Guan et al., 2016). In Tyszowce, the first phase concerns the L1LL1 loess and S0 soil, and the second phase - the S1, L1LL2 and L1SS1 units. The last phase in Tyszowce has not been found. This means that the parent material in the source area of the dust particles has only undergone weak weathering before erosion and

Fig. 4. Chemical proxy indicators of the loess-soil units of Tyszowce profile.

chemical weathering (e.g.: Kraus, 1999). Furthermore, although a palaeosol may be regarded as weathered loess, the loess units themselves are often bioturbated and weakly weathered after deposition, and may contain dust particles eroded and reworked from palaeosols (Kemp, 2001; Jeong et al., 2008) or older loess covers (Mroczek, 2013). This allows the chemical weathering indicators to be used to verify stratigraphic divisions. The CIA index (Nesbitt and Young, 1982) was

6

Quaternary International xxx (xxxx) xxx–xxx

J. Skurzyński et al.

Fig. 5. A-CN-K ternary diagram (Nesbitt and Young, 1984) of Tyszowce profile. CaO* (Ca in silicate minerals) was calculated based on the McLennan (1993) method. UCC – characteristic value for the upper continental crust (Taylor and McLennan, 1985). Dashed line – CIA value of 65. Solid grey line – the trend of the silicate minerals weathering. Presented oxides are in molar proportions.

Fig. 7. Scatter diagram of K2O/Al2O3 vs TiO2/Al2O3 molar ratios (Hao et al., 2010) for bulk samples from the Tyszowce loess-palaeosol sequence.

molar ratio (Cox et al., 1995), which in Tyszowce is firmly negatively correlated with CIA (R = −0.91). The K/Al values vary narrowly from 0.168 to 0.296 (average = 0.247). These values indicate the preponderance of clay minerals over K-bearing minerals (e.g. K-feldspars or micas; Cox et al., 1995). The K/Al molar ratio is sensitive to the soilforming processes, in contrast to the Ti/Al (e.g. Sheldon and Tabor, 2009) molar ratio. Both Ti and Al are thought to be immobile, because their solubility is very limited (Broecker and Peng, 1982) - the Ti/Al ratio should be constant even during post-depositional chemical weathering (Sheldon, 2006). For this reason, the plot of K/Al vs Ti/Al molar ratios (Hao et al., 2010) is very useful for identifying the provenance of sediments and may also be a good indicator of the heterogeneity or homogeneity of loess source areas (Hao et al., 2010; Peng et al., 2016). The trace index plot of Ti/Al vs K/Al (Fig. 7) shows that the samples from Tyszowce are significantly differentiated in the depth profile. However, the Ti/Al values have a positive correlation with K/Al (R = 0.71). This relation suggests that both Ti and Al contents can be influenced by post-depositional processes, which makes it impossible to deduce the source areas at this stage of research.

transportation (Jahn et al., 2001). The CIA index is often compiled with the Na/K molar ratio (e.g. Chen et al., 2008; Song et al., 2014). The values of this indicator are in inverse proportion with the weathering degree (e.g. Guan et al., 2016), because the weathering rate of Na-rich plagioclase is far greater than for potassium feldspar (Chen et al., 2008). However, the correlation between the CIA and Na/K molar ratios is not very strong (R = −0.64) in the Tyszowce profile. The Na/K ratio suggests greater weathering degrees of the S0 and S1 soils, compared to the CIA (Fig. 6). The chemical weathering degree is also well illustrated by the K/Al

4.3. Grain-size influence The grain-size composition of the loess-palaeosol sequence in Tyszowce is clearly differentiated in the depth profile (Fig. 8). There is a very strong positive correlation (R = 0.97) between the finest fractions i.e. < 4 μm and 4–8 μm. Fractions < 4 μm and 4–8 μm also are strongly correlated with 8–16 μm (R = 0.87 and R = 0.91, respectively). The proportion of these three granulometric fractions shows an increasing trend with depth. They are also strongly positively correlated with CIA (R = 0.73, 0.82 and 0.76, respectively). This is problematic because, according to Tsoar and Pye (1987), only dust particles finer than 20 μm can be transported in long-term suspension over a great altitudinal range and long distances. Use of the < 20 μm fraction should remove any geochemical contribution from coarse particles mainly derived from local loess deposition sites (Hao et al., 2010). The 16–31 μm fraction is the finest fraction where there is no interdependence with the CIA. This fraction is also correlated only with the 8–16 μm fraction (R = 0.42). In other cases the interdependence is not higher than

Fig. 6. Scatter diagram of CIA vs Na/K molar ratio for bulk samples from the Tyszowce loess-palaeosol sequence. 7

Quaternary International xxx (xxxx) xxx–xxx

J. Skurzyński et al.

Fig. 8. Distribution of grain-size (%) in Tyszowce profile. Dashed line means sandy layers; pale grey rectangles are horizons with signs of the gley processes. Main pedo-lithostratigraphic units are shown. Fig. 9. Scatter diagram of CIA vs sand (> 63 μm) of Tyszowce profile.

R = 0.25, with the exception of the > 63 μm fraction for which R = −0.83. However, the > 63 μm fraction (sand) comes from a very local source, and from the climatic point of view is connected only with short-term episodes of extremely harsh climate conditions (e.g. Moska et al., 2017). It seems that the 16–31 μm fraction is the most representative of the source areas for the Tyszowce loess. The A-CN-K diagram (Fig. 5) also reflects the grain-size differentiation (Buggle et al., 2008) - samples dominated by finer fractions are closer to the apex of the Al2O3 axis (Nesbitt et al., 1996). It should be noted that the S1 soil is outside of the chemical weathering trend. It is also relatively weakly weathered. In addition, the substrate of the S1 soil is characterized by a high content of sand fraction, especially in its lower part (Fig. 9). The effect of grain-size differentiation on CIA values was reported in the literature (e.g., Nesbitt and Young, 1982; Shao et al., 2012; Guan et al., 2016). Based on the example of fluvial sediments, Shao and coauthors (2012) showed that the CIA values decrease as the average particle size increases. In Tyszowce sandy material probably comes from the nearby Huczwa River valley. The lowest CIA values in the profile were recorded for samples at depths of 2.1, 2.7 and 4.35 m. All these samples, as well as samples from the depths of 18.35, 18.50, 18.85 and 19.00 m, are characterized by increased content of sand fraction. Taking into account the comparable contents of sand fraction in all these samples, it can be assumed that the CIA values for the S1 soil are underestimated. These values should be higher when restricting the grain-size to fractions less than 63 μm (e.g. Guan et al., 2016).

The results of mineralogical studies by Kuźniar (1912) and Tokarski (1917a, b) indicate, in turn, the importance of distant sources of loess dust (Jahn, 1950). Later research (Malicki, 1950; Jahn, 1956; Racinowski, 1976) was summed up by Maruszczak (1987), who supported the hypothesis of the local origin of loess dust. Comparing the Tyszowce profile to the selected loess localities described in the literature, it is possible to identify its distinct geochemical individuality (Table 3). The average share of Al is particularly low, comparable at most with French and British loess. The high average share of Si, higher than in China, Germany, India, Romania or Hungary, is comparable to France, the UK and USA. All of the measured elements, except Si and Ca, showed a significantly lower content than the corresponding value for the GAL. The same applies to UCC - however, in this case the content of Ti is also higher in Tyszowce. The most important comparison is with other geochemical data obtained for other Polish loess-palaeosol sequences, because the spatial variability of the chemical composition of Polish loess is poorly recognized. In most of the Polish loess-focused publications the chemical composition is limited to the results of analysis of selected chemical features i.e. CaCO3, humus and Fe2O3 contents (e.g. Jersak, 1973; Dolecki, 2002) and conducted in order to verify the stratigraphy. For individual profiles (Łukaszew and Mojski, 1968; Borowiec et al., 1977; Łanczont et al., Łanczont et al., 2015 a; b a; b; Raczyk et al., 2015; Kołodyńska-Gawrysiak et al., 2017; Skurzyński et al., 2017) the chemical composition was also analysed for other reasons. In those cases, the main objectives were found as the selected palaeoclimatic features (Łanczont et al., 2015b), the indigeneity of the parent material (Borowiec et al., 1977) or even the landform development (KołodyńskaGawrysiak et al., 2017). However, only a few of the publications cited above are suitable for spatial analysis. The loess profile nearest westward, in relation to Tyszowce, analysed for chemical composition in a suitable range, is located in Kraków Spadzista. For that profile, Łanczont et al. (2015b) presented the values of the CIA index, which are not higher than 70 - referring to the low degree of chemical weathering, similar to the profile in Tyszowce. However, the clear contrast with the results obtained for profiles located in SW Poland is particularly interesting, i.e. Dankowice (Raczyk et al., 2015) and Biały Kościół (Skurzyński et al., 2017). These profiles

4.4. Comparison with other loess localities As there is a lack of geochemical data on detrital sediments from this part of Europe, a comparison of data is made against the UCC, the GAL (Ujvari et al., 2008) and data on the chemical composition of selected loess localities. The lack of geochemical data concerning potential source areas is a common problem in loess research, e.g. Ahmad and Chandra (2013) reveal it for loessic sediments of the Kashmir Valley in India. This is particularly problematic in Poland, because the origin of loess dust for Polish loess has not been the subject of focused research so far. Two separate hypotheses are presented in the literature. Łoziński (1909) suggested that the transport of loess dust was relatively short. 8

Quaternary International xxx (xxxx) xxx–xxx

J. Skurzyński et al.

Table 3 Examples of chemical composition of loess from different localities. Locality a

Tyszowce (SE Poland) Dankowice (SW Poland)b Biały Kościół (SW Poland)c Romaniad Hungarye Germanyf Franceg Chinah UKi USAj Tajikistank Indial GAL - global average loessm UCC – Upper Continental Crustn

SiO2 (%)

Al2O3 (%)

Fe2O3 (%)

MnO (%)

MgO (%)

CaO (%)

Na2O (%)

K2O (%)

TiO2 (%)

P2O5 (%)

78.70 78.73 81.50 62.83 63.48 51.47 77.32 71.78 83.94 80.05 51.56 71.56 70.71 66.00

7.74 10.38 8.94 14.53 13.45 9.69 8.43 14.49 8.50 10.79 11.69 12.50 11.74 15.20

2.15 2.10 2.30 5.34 4.67 3.63 3.14 5.26 2.80 2.73 4.73 4.42 3.75 5.00

0.05 0.06 0.06 0.10 0.09 0.10 0.05 0.09 0.05 0.03 0.09 0.07 0.07 0.08

1.51 1.23 1.16 2.48 3.62 2.41 1.08 1.83 0.59 0.92 2.85 1.90 2.15 2.20

6.43 4.45 2.91 9.51 9.73 11.56 6.22 1.11 0.46 1.07 11.43 4.57 6.67 4.20

0.88 0.84 0.84 2.51 1.47 0.61 1.12 1.87 0.96 1.58 1.51 1.70 1.68 3.90

1.83 1.49 1.56 1.99 2.37 1.66 1.81 2.68 2.05 2.47 2.12 2.44 2.22 3.40

0.62 0.60 0.59 0.70 0.91 0.54 0.72 0.75 0.57 0.67 0.63 0.72 0.71 0.50

0.07 0.12 0.11 – 0.20 0.11 0.11 0.14 0.07 – 0.15 0.15 0.14 0.40

Note that for Tyszowce, Dankowice and Biały Kościół profiles the values are restricted to the L1LL1 loess units. a This study. b Raczyk et al., 2015. c Skurzyński et al., 2017. d Tugulan et al., 2016. e Ujvari et al., 2008. f Kuhn et al., 2013. g Lautridou et al., 1984. h Peng et al., 2016. i Gallet et al., 1998. j Taylor et al., 1983. k Li et al., 2016. l Tripathi and Rajamani 1999. m Ujvari et al., 2008. n Taylor and McLennan 1985.

chemical weathering (i.e. CIA = 85). This may suggest different environmental conditions of the loess cover development, represented by the analysed profiles. These differences, in limited way, are also visible in present climate conditions. The mean annual precipitation and temperature for Tyszowce are 577 mm and 7,6 °C, respectively. For Biały Kościół and Dankowice these values are 563 mm and 8,3 °C, respectively (climate-data.org, 1982–2012). Tyszowce is probably closer to the dust source area and deposition occurred in a more severe climate (more carbonates, fewer elements commonly associated with pedogenesis, e.g. Al and Fe). However, the disproportion between the thicknesses of the loess covers can also be important. A lower rate of dust deposition in the Biały Kościół and Dankowice could result in a more significant transformation of the deposited material due to longer exposure to changing weather conditions and infiltration of rainwater, in comparison to the Tyszowce profile. 5. Conclusions The chemical composition of the loess-palaeosol sequence in Tyszowce is strongly varied in the vertical profile, correlating with the variability of pedo- and lithostratigraphic units. This allows the use of chemical composition as a stratigraphical tool. However, the inference about source area heterogeneity is inapplicable. The L1LL1 loess is weakly weathered (CIA below 65) under cold and dry climatic conditions. This also means that the parent material in the source area of the dust particles has only undergone weak weathering before erosion and transportation. Lower parts of the profile are at the moderate stage of chemical weathering (CIA above 65). This implies that the S1 and L1SS1 pedocomplexes were created under relatively warm and moist climatic conditions – the aeolian sediments starting composition had been modified by pedogenesis. However, the CIA values in the upper part of L1LL1 and lower part of S1 are strongly influenced by the addition of sand. These values should be higher when

Fig. 10. Comparison of the chemical weathering degree between Tyszowce, Dankowice and Biały Kościół profiles. For description of the A-CN-K diagram please refer to Fig. 5.

have a similar average Si content (80.8 and 82.66%, respectively), with a significantly higher average of Al (10.56 and 9.38%) and lower Ca content (2.50 and 1.55%; Table 3). There is also a difference in the chemical weathering degree of whole loess-soil sequences (Fig. 10). The loess-palaeosol sequences in Dankowice and Biały Kościół are almost completely at the medium stage of chemical weathering. The most weathered parts of sequences nearly reach the lower limit of strong 9

Quaternary International xxx (xxxx) xxx–xxx

J. Skurzyński et al.

restricting the grain-size to the fractions less than 63 μm L1LL2 is calcareous, but relatively highly weathered. This is an effect of deluvial processes - relatively unweathered loess particles are mixed with material reworked from eroded soils. The loess-palaeosol sequence in Tyszowce is geochemically distinct from other loess presented in the worldwide literature. The contents of the major elements, except Si, are lower in relation to the GAL. There is also a contrast of the chemical weathering degree with loess of SW Poland (Dankowice and Biały Kościół profiles). The Tyszowce section is much less weathered. This suggests that the loess-palaeosol sequences of SW Poland have been developed under milder climatic conditions. This conclusion requires further studies, based on a greater number of loess-palaeosol sequences.

Loess Plateau of China: eolian dust provenance and paleosol evolution during the last 140 ka. Chem. Geol. 178, 71–94. Jary, Z., 2007. Record of climate changes in upper Pleistocene loess-soil sequences in Poland and western part of Ukraine. In: Rozprawy Naukowe Instytutu Geografii i Rozwoju Regionalnego Uniwersytetu Wrocławskiego 1 Wrocław (in Polish, with English Abstract). Jary, Z., 2009. Periglacial markers within the Late Pleistocene loess-palaeosol sequences in Poland and western part of Ukraine. Quat. Int. 198, 124–135. Jary, Z., 2010. Loess-soil sequences as a source of climatic proxies: an example from SW Poland. Geologija 52 (1–4), 40–45 (69-72). Jary, Z., Ciszek, D., 2013. Late Pleistocene loess-palaeosol sequences in Poland and western Ukraine. Quat. Int. 296, 37–50. Jary, Z., Mroczek, P., Moska, P., Ciszek, D., Raczyk, J., Skurzyński, J., Krawczyk, M., Korabiewski, B., Seul, C., 2014. Tyszowce loess section: the huge L1L1 loess accumulation and three generations of ice wedge casts. In: Jary, Z., Mroczek, P. (Eds.), Kukla LOESSFEST '14-7th Loess Seminar in Wrocław, International Conference on Loess Research in Memoriam of George Kukla, September 8-15 2014. Institute of Geography and Regional Development, University of Wrocław, pp. 68–69 Abstracts and field guide book. Jeong, G., Hillier, S., Kemp, R., 2008. Quantitative bulk and single-particle mineralogy of a thick Chinese loess-paleosol section: implications for loess provenance and weathering. Quat. Sci. Rev. 27, 1271–1287. Jersak, J., 1973. Lithology and stratigraphy of the loess on the southern Polish uplands. Acta Geographica Lodziensia 32 Łódź (in Polish, with English Abstract). Kemp, R.A., 2001. Pedogenic modification of loess: significance for palaeoclimatic reconstructions. Earth Sci. Rev. 54, 145–156. Kondracki, J., 2002. Geografia Regionalna Polski. PWN, Warszawa In Polish. Kołodyńska-Gawrysiak, R., Chodorowski, J., Mroczek, P., Plak, A., Zgłobicki, W., Kiebała, A., Trzciński, J., Standzikowski, K., 2017. The impact of natural and anthropogenic processes on the evolution of closed depressions in loess areas. In: A Multi-Proxy Case Study from Nałęczów Plateau, Eastern Poland. Catena 149. pp. 1–18. Kraus, M., 1999. Paleosols in clastic sedimentary rocks: their geologic applications. Earth Sci. Rev. 47, 41–70. Kuhn, P., Techmer, A., Weidenfeller, M., 2013. Lower to middle Weichselian pedogenesis and paleoclimate in Central Europe using combined micromorphology and geochemistry: the loess-paleosol sequence of Alsheim (Mainz Basin, Germany). Quat. Sci. Rev. 75, 43–58. Kukla, G., An, S., 1989. Loess stratigraphy in central China. Palaeogeogr. Palaeoclimatol. Palaeoecol. 72, 203–225. Kuźniar, C., 1912. Löss w beskidzie galicji zachodniej. Kosmos 37, 671–678 (in Polish). Lautridou, J.P., Somme, J., Jamagne, M., 1984. Sedimentological, mineralogical and geochemical characteristics of the loesses of North-West France. In: Pecsi, M. (Ed.), Lithology and Stratigraphy of Loess and Paleosols. Geographical Research Institute of the Hungarian Academy of Sciences, Budapest, pp. 121–132. Li, Y., Song, Y., Chen, X., Li, J., Mamadjanov, Y., Aminov, J., 2016. Geochemical composition of Tajikistan loess and its provenance implications. Palaeogeogr. Palaeoclimatol. Palaeoecol. 446, 186–194. Malicki, A., 1950. The origin and distribution of loess in central and eastern Poland. Annales Universitatis Mariae Curie-Skłodowska, sec. B 4/8, 195–228 (in Polish, with English Abstract). Marković, S., Bokhorst, M., Vanderberghe, J., McCoy, W., Oches, E., Hambach, U., 2008. Late Pleistocene loess-paleosol sequences in the Vojvodina region, north Serbia. J. Quat. Sci. 23, 73–84. Marković, S., Stevens, T., Kukla, G.J., Hambach, U., Fitzsimmons, K.E., Gibbard, P., Buggle, B., Zech, M., Guo, Z., Hao, Q., Wu, H., Ken O'Hara, D., Smalley, J., Ujvari, G., Sümegi, P., Timar-Gabor, A., Veres, D., Sirocko, F., Vasilijević, A., Jary, Z., Svensson, A., Jović, V., Lehmkuhl, F., Kovacs, J., Svircev, Z., 2015. Danube loess stratigraphy towards a pan-European loess stratigraphic model. Quat. Sci. Rev. 148, 228–258. Martinson, D.G., Pisias, N.G., Hays, J.D., Imbrie, J., Moore Jr., T.C., Shackleton, N.J., 1987. Age dating and the orbital theory of the ice ages: development of a high-resolution 0 to 300,000-year chronostratigraphy. Quat. Res. 27, 1–29. Maruszczak, H., 1972. Wyżyny lubelsko-wołyńskie. In: Klimaszewski, M. (Ed.), Geomorfologia Polski, T. 1, Warszawa, (in Polish). Maruszczak, H., 1974. Fossil soils and the sokal range loess stratigraphy. Annales Universitatis Mariae Curie-Skłodowska, sec. B 26, 27–66 (in Polish, with English Abstract). Maruszczak, H., 1987. Loesses in Poland, their stratigraphy and paleogeographical interpretation. Annales Universitatis Mariae Curie-Skłodowska, sec. B 41/2, 15–54. Maruszczak, H., 1991. Stratigraphical differentiation of Polish loesses. In: Maruszczak, H. (Ed.), Main Sections of Loesses in Poland. UMCS, Lublin, pp. 13–35 (in Polish, with English Abstract). McLennan, S., 1993. Weathering and global denudation. J. Geol. 101, 295–303. Moosavirad, S.M., Janardhana, M.R., Sethumadhav, M.S., Moghadam, M.R., Shankara, M., 2011. Geochemistry of lower jurassic shales of the shemshak formation, kerman province, Central Iran: provenance, source weathering and tectonic setting. Chemie der Erde 71, 279–288. Moska, P., Adamiec, G., Jary, Z., 2011. OSL dating and lithological characteristics of loess deposits from Biały Kościół. Geochronometria 38 (2), 162–171. Moska, P., Adamiec, G., Jary, Z., Bluszcz, A., 2017. OSL chronostratigraphy for loess deposits from Tyszowce – Poland. Geochronometria 44/1, 307–318. Mroczek, P., 2013. Recycled loesses – a micromorphological approach to the determination of local source areas of Weichselian loess. Quat. Int. 296, 241–250. Nesbitt, H.W., Young, G.M., 1982. Early proterozoic climate and plate motions inferred from major element chemistry of lutites. Nature 229, 715–717. Nesbitt, H.W., Young, G.M., 1984. Prediction of some weathering trends of plutonic and volcanic rocks based on thermodynamic and kinetic considerations. Geochimica et

Acknowledgments The research was performed under the National Science Centre project No. 2011/01/D/ST10/06049 entitled “Establishing the chronology of Late Pleistocene loess formation in Poland on the basis of high resolution luminescence dating and litho-pedological studies of selected loess-soil sequences” and the statutory founds of the University of Wroclaw. The authors are grateful for the field assistance from dr Przemysław Mroczek, dr Cyprian Seul and dr Dariusz Ciszek. We also thank the guest editor of this volume and two anonymous reviewers for improving our manuscript. References Ahmad, I., Chandra, R., 2013. Geochemistry of loess-paleosol sediments of Kashmir Valley, India: provenance and weathering. J. Asian Earth Sci. 66, 73–89. Badura, J., Jary, Z., Smalley, I., 2013. Sources of loess material for deposits in Poland and parts of Central Europe: the lost big river. Quat. Int. 296, 15–22. Bokhorst, M., Beets, C., Marković, S., Gerasimenko, N., Matviishina, Z., Frechen, M., 2009. Pedo-chemical climate proxies in Late Pleistocene Serbian-Ukrainian loess sequences. Quat. Int. 198, 113–123. Borowiec, J., Maruszczak, H., Racinowski, R., 1977. Regularities of the chemical and mineral composition differentiation as an index of autochtonism of Polish loess. Biul. Inst. Geol. 305, 69–82. Broecker, W., Peng, T., 1982. Tracers in the Sea. Eldigio Press, New York. Buggle, B., Glaser, B., Zoller, L., Hambach, U., Marković, S., Glaser, I., Gerasimenko, N., 2008. Geochemical characterization and origin of southeastern and eastern european loesses (Serbia, Romania, Ukraine). Quat. Sci. Rev. 27, 1058–1075. Buggle, B., Glaser, B., Hambach, U., Gerasimenko, N., Markowić, S., 2011. An evaluation of geochemical weathering indices in loess-paleosol studies. Quat. Int. 240, 12–21. Buraczyński, J., Wojtanowicz, J., 1975. New loess profiles on the sokal range. Ann. Univ. Mariae Curie-Skłodowska, Sec. B 28, 1–37 (in Polish, with English Abstract). Chen, Y., Li, X., Han, Z., Yang, S., Wang, Y., Yang, D., 2008. Chemical weathering intensity and element migration features of the Xiashu loess profile in Zhenjiang, Jiangsu Province. J. Geogr. Sci. 18, 341–352. Climate-dataorg, 1982 -2012. AmbiWeb GmbH. http://en.climate-data.org, Accessed date: 6 March 2018. Cox, R., Lowe, D., Cullers, R., 1995. The influence of sediment recycling and basement composition on evolution of mudrock chemistry in the southwestern United States. Geochim Cosmochim Acta 59/14, 2919–2940. Dolecki, L., 2002. Main Profiles of the Neopleistocene Loesses on the Horodło PlateauRidge and their Lithological-Stratigraphical Interpretation. UMCS, Lublin in Polish, with English Abstract. Dwucet, K., 1999. Lithogenesis of vistulian upper loess in Poland uplands and silesian lowlands. In: Prace Naukowe Uniwersytetu Śląskiego w Katowicach 1792, Katowice (in Polish, with English Abstract). Gallet, S., Jahn, B., Van VlietLanoe, B., Dia, A., Rossello, E., 1998. Loess geochemistry and its implications for particle origin and composition of the upper continental crust. Earth Planet Sci. Lett. 156, 157–172. Guan, H., Zhu, C., Zhu, T., Wu, L., Li, Y., 2016. Grain size, magnetic susceptibility and geochemical characteristics of the loess in the Chaohu lake basin: implications for the origin, paleoclimatic change and provenance. J. Asian Earth Sci. 117, 170–183. Haase, D., Fink, J., Haase, G., Ruske, R., Pecsi, M., Richter, H., Altermann, M., Jäger, K.D., 2007. Loess in Europe - its spatial distribution based on a european loess map, scale 1:2,500,000. Quat. Sci. Rev. 26, 1301–1312. Hao, Q., Guo, Z., Qiao, Y., Xu, B., Oldfield, F., 2010. Geochemical evidence for the provenance of middle Pleistocene loess deposits in southern China. Quat. Sci. Rev. 29, 3317–3326. Jahn, A., 1950. Loess, its origin and connection with the climate of the glacial epoch. Acta Geologica Polonica I (3), 257–310 (in Polish, with English Abstract). Jahn, A., 1956. Geomorphology and quaternary history of lublin plateau. In: Prace Instytutu Geograficznego PAN 7 Warszawa (in Polish, with English Abstract). Jahn, B., Gallet, S., Han, J., 2001. Geochemistry of the Xining, Xifeng and Jixian sections,

10

Quaternary International xxx (xxxx) xxx–xxx

J. Skurzyński et al.

Tokarski, J., 1917a. Less powiatu sokalskiego. Kosmos 40, 56–62 (in Polish). Tokarski, J., 1917b. O glinie nawianej Sokalszczyzny i Podola. Rozprawy Muzeum Dzieduszyckich 2, 167–182 (in Polish). Tripathi, J.K., Rajamani, V., 1999. Geochemistry of the loessic sediments on Delhi ridge, eastern Thar desert, Rajasthan: implications for exogenic processes. Chemical Geology 155, 265–278. Tsoar, H., Pye, K., 1987. Dust transport and the question of desert loess formation. Sedimentology 34, 139–153. Tugulan, L.C., Duliu, O.G., Bojar, A.V., Dumitras, D., Zinicovskaia, I., Culicov, O.A., Frontasyeva, M.V., 2016. On the geochemistry of the Late Quaternary loess deposits of Dobrogea (Romania). Quat. Int. 399, 100–110. Tutkovsky, P.A., 1899. K voprosu o sposobe obrazovaniya lessa. Zemlevedenie 1–2, 213–311 (in Russian). Ujvari, G., Varga, A., Balogh-Brunstad, Z., 2008. Origin, weathering, and geochemical composition of loess in southwestern Hungary. Quat. Res. 69, 421–437. Varga, A., Ujvari, G., Raucsik, B., 2011. Tectonic versus climatic control on the evolution of a loess-paleosol sequence at Beremend, Hungary: an integrated approach based on paleoecological, clay mineralogical, and geochemical data. Quat. Int. 240, 71–86. Wojtanowicz, J., Buraczyński, J., 1978. Materials to the absolute chronology of the loesses of grzęda sokalska. Annales Universitatis Mariae Curie-Skłodowska, sec. B 30/ 31 (3), 37–54 (in Polish, with English abstract). Xiao, S., Liu, W., Li, A., Yang, S., Lai, Z., 2010. Pervasive autocorrelation of the chemical index of alteration in sedimentary profiles and its palaeoenvironmental implications. Sedimentology 57/2, 670–676. Yang, S., Li, C., Yang, D., Li, X., 2004. Chemical weathering of the loess deposits in the lower Changjiang Valley, China, and paleoclimatic implications. Quat. Int. 117, 27–34. Łanczont, M., Madeyska, T., Bogucki, A., Mroczek, P., Hołub, B., Łącka, B., Fedorowicz, S., Nawrocki, J., Frankowski, Z., Standzikowski, K., 2015a. Środowisko abiotyczne paleolitycznej ekumeny strefy pery- i metakarpackiej. In: Łanczont, M., Madeyska, T. (Eds.), Paleolityczna Ekumena Strefy Pery- I Meta Karpackiej. UMCS, Lublin, pp. 55–457 (in Polish, with English Abstract). Łanczont, M., Madeyska, T., Mroczek, P., Komar, M., Łącka, B., Bogucki, A., Sobczyk, K., Wilczyński, J., 2015b. The loess-palaeosol sequence in the Upper Palaeolithic site at Kraków Spadzista – a palaeoenvironmental approach. Quat. Int. 365, 98–113. Łoziński, W., 1909. Über die mechanische Verwitterung der Sandsteine im gemässigten klima. Bulletin International de l'Academie des Sciences de Cracovie class des Sciences Mathematique et Naturalles 1, 1–25 (in German). Łukaszew, W., Mojski, J.E., 1968. Geochemical examinations of loess in the lublin Upland. Kwartalnik Geologiczny 12/4, 966–982 (in Polish, with English Abstract). Łącka, B., Łanczont, M., Madeyska, T., Boguckyj, A., 2007. Geochemical composition of Vistulian loess and micromorphology of interstadial palaeosols at the Kolodiv site (East Carpathian Foreland, Ukraine). Geol. Q. 51 (2), 127–146.

Cosmochimica Acta 48, 1523–1534. Nesbitt, H.W., Markovics, G., Price, R.C., 1980. Chemical processes affecting alkalis and alkaline earths during continental weathering. Geochimica et Cosmochimica Acta 44 (11), 1659–1666. Nesbitt, H.W., Young, G.M., McLennan, S.M., Keays, R., 1996. Effects of chemical weathering and sorting on the petrogenesis of siliciclastic sediments, with implications for provenance studies. J. Geol. 104, 525–542. Pecsi, M., 1995. The role of principles and methods in loess-paleosol investigations. Geo. J. 36, 117–131. Peng, S., Hao, Q., Wang, L., Ding, M., Zhang, W., Wang, Y., Guo, Z., 2016. Geochemical and grain-size evidence for the provenance of loess deposits in the Central Shandong Mountains region, northern China. Quat. Res. 85, 290–298. Perel’man, A., 1977. Geochemistry of Elements in the Supergene Zone. Keterpress Enterprises, Jurusalem. Pisias, N.G., Martinson, D.G., Moore Jr., T.C., Shackelton, N.J., Prell, W., Hays, J., Boden, G., 1984. High resolution stratigraphic correlation of benthic oxygen isotopic records spanning the last 300,000 years. Mar. Geol. 56, 119–136. Pye, K., Johnson, R., 1988. Stratigraphy, geochemistry, and thermoluminescence ages of Lower Mississippi Valley loess. Earth Surf. Process. Landforms 13, 103–124. Racinowski, R., 1976. Uwagi o składzie minerałów ciężkich lessów lubelskich i przemyskich. Biuletyn Instytutu Geologicznego 297, 227–247 (in Polish, with English Abstract). Raczyk, J., Jary, Z., Korabiewski, B., 2015. Geochemical properties of the late Pleistocene loess-soil sequence in Dankowice (Niemcza-Strzelin hills). La. Landf. Anal. 29, 49–61. Shao, J., Yang, S., Li, C., 2012. Chemical indices (CIA and WIP) as proxies for integrated chemical weathering in China: inferences from analysis of fluvial sediments. Sediment. Geol. 265–266, 110–120. Sheldon, N.D., 2006. Abrupt chemical weathering increase across the Permian-Triassic boundary. Palaeogeogr. Palaeoclimatol. Palaeoecol. 231, 315–321. Sheldon, N.D., Tabor, N.J., 2009. Quantitative paleoenvironmental and paleoclimatic reconstruction using paleosols. Earth Sci. Rev. 95, 1–52. Skurzyński, J., Jary, Z., Raczyk, J., Moska, P., Krawczyk, M., 2017. The stratigraphic and spatial aspects of the differentiation of the chemical composition of the Late Pleistocene loess-palaeosol sequences in Poland – a case study of the Tyszowce and Biały Kościół profiles. Acta Geographica Lodziensia 106, 87–103 (in Polish, with English Abstract). Song, Y., Chen, X., Qian, L., Li, C., Li, Y., Li, X., 2014. Distribution and composition of loess sediments in the ili basin, central asia. Quat. Int. 334–335, 61–73. Taylor, S.R., McLennan, S.M., 1985. The Continental Crust: its Composition and Evolution. Blackwell, London. Taylor, S.R., Mclennan, S.M., McCulloch, M.T., 1983. Geochemistry of loess, continental crustal composition and crustal model ages. Geochimica et Cosmochimica Acta 47 1987–1905.

11