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On the geochemistry of the Late Quaternary

loess deposits of Dobrogea (Romania)

Article in Quaternary International · August 2015

DOI: 10.1016/j.quaint.2015.06.062

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Contents lists available at ScienceDirect

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

On the geochemistry of the Late Quaternary loess deposits of

Dobrogea (Romania)
L.C. Tugulan a, 1, O.G. Duliu b, f, *, Ana-Voica Bojar c, d, Delia Dumitras e, Inga Zinicovskaia f, g,
Otilia A. Culicov f, h, Marina V. Frontasyeva f
a
University of Bucharest, Doctoral School on Physics, P.O. Box MG-11, RO-077125 Magurele, Ilfov, Romania
b
University of Bucharest, Department of Structure of Matter, Earth and Atmospheric Physics and Astrophysics, P.O. Box MG-11, RO-077125 Magurele,
Ilfov, Romania
c
University of Salzburg, Department of Geology and Geodynamics, Hellbrunnerstrasse 34, 5020 Salzburg, Austria
d
Mineralogy, Studienzentrum Naturkunde, Weinzo €ttlstraße 16, 8045 Graz, Austria
e
National Geological Museum, 2 Pavel Dimitrievici Kiseleff aven., 011345 Bucharest, Romania
f
Joint Institute for Nuclear Research, Frank Neutron Physics Laboratory, 6 Joliot Curie str., 141980 Dubna, Russian Federation
g
Institute of Chemistry, Academy of Sciences of Moldova, 3 Academiei str., MD-2028 Chisinau, Republic of Moldova
h
National Institute for R&D in Electrical Engineering ICPE-CA, 313 Splaiul Unirii, Romania

a r t i c l e i n f o a b s t r a c t

Article history: Ten samples of loess and palaeosols collected from the CostinestieDobrogea (Romania) loess deposit and
Available online xxx covering a time span of about 690 ± 90 ka were analyzed by X-ray diffraction, Instrumental Neutron
Activation Analysis and X-ray Fluorescence in order to determine the origin as well as the climatic
Keywords: conditions during loess deposition. The presence of illite and calcite suggests reduced weathering,
Loess confirmed by climate proxies. Chemical Index of Alteration (54.6e64.0), Chemical Index of Weathering
Palaeosol
(65.7e71.7) and Rb/Sr (0.26e0.47) were lower than the neighboring Hungarian loess, but closer to the
Dobrogea
average loess. The content of 28 trace elements, including 10 REE, confirmed an average rock compo-
Palaeoclimate
Geochemistry
sition close to the Upper Continental Crust. The elevated content of Cr and Ni indicated the presence of a
Mineralogy certain amount of felsic rock material. Zr and Hf whose content was more than twice that of the Upper
Continental Crust indicate significant sediment sorting. The low values of climatic proxies as well as the
absence of any statistical significant difference between loess and palaeosol material confirmed rather
limited weathering during the formation of the south-eastern Dobrogea loess deposits.
© 2015 Elsevier Ltd and INQUA. All rights reserved.

1. Introduction
Loess is an aeolian sediment consisting of fine grains of quartz,
calcite, feldspars, smectite/chlorite and mica group from a diversity
of source lithologies. Thoroughly mixed by various transport
mechanisms, loess has an average composition of Earth's superfi-
cial crust (Taylor and McLennan, 1991; Schnetger, 1992; Gallet
et al., 1998; McLennan, 2001). Loess, which covers about 10% of
the earth surface (McLennan, 1993, Smalley and Leach, 1978), has
been identified in both hemispheres, the most widespread
* Corresponding author. University of Bucharest, Department of Structure of
Matter, Earth and Atmospheric Physics and Astrophysics, P.O. Box MG-11, RO-
077125 Magurele, Ilfov, Romania.
E-mail address: o.duliu@upcmail.ro (O.G. Duliu).
1
Present address: Horis Hulubei National Institute of Physics and Nuclear En-
gineering, P.O. Box MG-06, RO-077125 Magurele, Ilfov, Romania.
accumulations being found in China where the loess deposits are
up to 140 m thick (Catt, 1986). Generally, such deposits consist of
an alternation of loess layers separated by palaeosol strata formed
during shorter interglacials.
Long term exposure of rocks to atmospheric factors can be
related to physical and chemical weathering (Bland and Rolls,
1998). While physical weathering breaks down rocks into clasts,
chemical weathering, mainly under the action of acid rain water,
progressively transforms less thermodynamically stable minerals
such as feldspars into more thermodynamically stable ones in the
given environment, such as iron oxy-hydrates or clay minerals
(Bjørlykke, 2010; Buggle et al., 2011).
During this process, Naþ, Kþ and Ca2þ are lost, determining the
concentrations of Al3þ and Si4þ in the residue. Therefore, the con-
centration of Al3þ and Si4þ together with the mobile elements Ca,
Na and K can be used to quantify weathering (Wronkiewicz and

http://dx.doi.org/10.1016/j.quaint.2015.06.062
1040-6182/© 2015 Elsevier Ltd and INQUA. All rights reserved.

Please cite this article in press as: Tugulan, L.C., et al., On the geochemistry of the Late Quaternary loess deposits of Dobrogea (Romania),
Quaternary International (2015), http://dx.doi.org/10.1016/j.quaint.2015.06.062
2 L.C. Tugulan et al. / Quaternary International xxx (2015) 1e11

Fig. 1. The general map of Romania showing the main loess deposits (light-brown colour) and the Costinesti location (45 550 05.2500 N, 28 370 56.0500 E) (A). A general photographic
image of Costinesti loess cliff corresponding to collection points LII, SII, LIII, S III, L IV, L V and L VI (B) as well as the diagram of the stratigraphic column (C) are reproduced too. The
collecting points S I, and S IV were located in two other sections. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this
article.)

Condie, 1987; Goldberg and Humayun, 2010). These processes are
also present in the case of loess deposits whose geochemistry and
mineralogy represent a valuable record of the palaeoclimatic cycles
(Kohfeld and Tegen, 2007). In order to decipher weathering activity,
various climate proxies such as grain size (Markovi c et al. 2007),
stable isotopic signature d18O (Li et al. 2007) or d13C and d15N
(Schatz et al., 2010), magnetic susceptibility (Markovi
c et al., 2009;
Nie et al., 2013), chemical index of alteration (CIA) (Nesbitt and
Young, 1982), chemical index of weathering (CIW) (Harnois,
1988), and detailed mineralogical and geochemical investigations
were conducted (Markovi c et al. 2006; Schellenberger and Veit,
2006; Bokhorst et al., 2009).
The CIA remains one of the most suitable chemical weathering
indices as it provides a quantitative estimation of the degree of
silicate hydrolysis by monitoring the content of major oxides Na2O,
Al2O3, K2O, and CaO. Depending on the rock type as well as on the
degree of weathering, CIA can vary from 30 to 55 in the case of fresh
basalt, granite or granodiorite, to 75 in the case of illite and
muscovite rich deposits, and reaches a maximum value of 100 in
kaolinite or gibbsite (Nesbitt and Young, 1982; Fedo et al., 1995;
Bahlburg and Dobrzinski, 2011). CIA values ranging between 50
and 70 indicate weak weathering, characteristic for a cold and arid
climate. When it varies between 70 and 85, CIA shows a moderate
degree of weathering specific to a warm and humid climate, while
values over 85 characterize a high degree of chemical weathering
(Nesbitt and Young, 1982; Taylor and McLennan, 1991).
The same elements which define CIA can be used, by means of
ternary diagrams Al2O3eCa*O þ Na2OeK2O (AeCNeK), to repre-
sent the weathering of the parent rock as well as to characterize the
loess lithology (Johnsson, 1993; Yang et al., 2004; Li and Yang,
2010). Furthermore, some trace elements such as Sc, Zr, REE, Hf,
and Th, which show relative low mobility during deposition
together with Cr and Ni, can be used as indicators of loess origin
(Nesbit, 1979; Taylor and McLennan, 1991; McLennan et al., 1993;

Please cite this article in press as: Tugulan, L.C., et al., On the geochemistry of the Late Quaternary loess deposits of Dobrogea (Romania),
Quaternary International (2015), http://dx.doi.org/10.1016/j.quaint.2015.06.062
 L.C. Tugulan et al. / Quaternary International xxx (2015) 1e11 3

Nesbitt and Young, 1996; Újva ri et al. 2008, 2014; Wang et al., 2012;
Xie et al., 2014).
In Romania, loess occupies about one third of territory (Fig. 1),
the most important deposits being located in Dobrogea and in the
Romanian Plain. At Hagieni, loess deposits reach a maximum
thickness of 55 m (Jipa, 2013). Previous investigations of the loess
deposits from Romania were summarized by Radan (2012).
To obtain more data regarding the environmental condition
during the formation of Dobrogea loess, a sequence of loess and
palaeosols of about 19 m deposited on Sarmatian limestones in the
vicinity of Costinesti village (Fig. 1) was sampled for mineralogical
and geochemical investigations. The content of nine major ele-
ments: Si, Ti, Al, Fe, Mn, Mg, Ca, Na and K as oxides together with 28
trace elements including Sc, V, Cr, Ni, ten REE as well as Hf and Th
was determined by X ray Fluorescence (XRF) and Instrumental
Neutron Activation Analysis (INAA). The results indicate the pa-
leoclimatic conditions during the last 650 ± 90 ka, the age of the
lowermost palaeosol layer (Ghenea and Radan, 1993) as well as the
nature of South-eastern Dobrogea loess deposits in the context of
neighboring loess deposits (Újva ri et al., 2008, 2014).
2. South-eastern Dobrogea loess: Costinesti
The aeolian deposits of southern Dobrogea present some fea-
tures considered typical for loess, such as the absence of bedding
deposited above the Sarmatian limestones (Conea, 1970). Palaeosol
layers PSI and PSII are chernozems, while PSIII to PS VI consist of
forest soil.
The upper layers of loess, L I, LII and LIII were attributed to MIS 2
to MIS 6 (Constantin et al. 2014), the intermediary L IV to MIS 10,
and the basal horizons consisting of altered loess L VI correspond to
MIS 16 (Conea, 1970; Constantin et al. 2014). More recent paleo-
magnetic and optical stimulated luminescence data attributed
palaeosol PS I to MIS 5e (Constantin et al. 2014), while the other
palaeosols PS II, PS III, PS IV, and PS V could be attributed to MIS 7,
MIS 9, MIS 11, MIS 13 and 15 respectively (Fig. 1). According to
Ghenea and Radan (1993) the estimated the age of the lowermost
palaeosol layer PS VI was 650 ± 90 ka, which corresponds to MIS 17
(Fig. 1).
3. Analytical methods and materials
For this study, we selected six loess and four palaeosol samples
covering the entire investigated sequence. The uppermost point
was chosen at a depth of 4 m and the lowermost at a depth of 19 m,
10 cm above the Sarmatian limestone (Fig. 1, Table 1). Although the
modern soil is a pasture without any sign of tilling, we have not
considered it as its geochemistry could be significantly affected by
pollution.

Table 1
The sampling depth as well as some general characteristics of the investigated loess and palaeosol samples (Tugulan and Duliu, 2014).

Sample Depth (m) Summary description Sample Depth (m) Summary description

SI 4.5 Palaeosol L IV 10.1 Loess

light-brown dark red-brown
LI 5.1 Loess S III 10.4 Palaeosol
brown dark brown
L II 8.2 Loess LV 10.9 Loess
brown red-brown
L III 9.1 Loess S IV 11.8 Palaeosol
dark red-brown red-brown
S II 9.5 Palaeosol SV 19.1 Palaeosol
brown red-brown

Table 2
Semi-quantitative X ray diffraction data of Costinesti loess and palaeosol samples.

14 Å (smectite and chlorite) 10 Å (mica group) Quartz Calcite K-Feldspar Plagioclase-albite

SI * * *** ** * **
LI * * *** ** * **
L II * * *** * * **
L III * * *** *** * **
S II * * *** *** * **
L IV * * *** *** * **
S III * * *** *** * **
LV * * *** * * **
S IV * * *** *** * **
SV * * *** *** * **

*** Mineral is main component. ** Mineral is secondary component. * Mineral is present in small amounts.

and high porosity estimated to 45e50% (Ghenea and Radan, 1993).
Previous studies indicated the Costinesti loess deposit located in
the south-eastern part of Dobrogea, in the vicinity of the Black Sea
(Fig. 1), as one of the most representative for this region (Jipa,
2013). Moreover, the Costinesti cliff loess, with a thickness of
19e20 m, displays a relatively well expressed alternation of loess
and palaeosols, a characteristic feature of most loess deposits
(Haase and Richter, 1957; Conea, 1970; Constantin et al. 2014)
(Fig. 1).
Six loess horizons (LIeLVI) interbedded with six palaeosol
levels (PSIePSVI) overlie the Lower Pleistocene reddish clay
From each point, about 2 kg of soil was collected by using 30 cm
metallic cores (Table 1) (Tugulan and Duliu, 2014). About 0.5 kg of
fresh material was dried to constant weight and divided into four
aliquots, two for XRF investigations, one for XRD and the last one
for INAA measurements. To avoid any possible contamination, we
have used only the material from the tips of cores.
3.1. XRD analysis
The mineralogical composition of loess and palaeosol samples,
previously ground and sieved on a 40 mm (about 300 mesh) sieve,

Please cite this article in press as: Tugulan, L.C., et al., On the geochemistry of the Late Quaternary loess deposits of Dobrogea (Romania),
Quaternary International (2015), http://dx.doi.org/10.1016/j.quaint.2015.06.062
4 L.C. Tugulan et al. / Quaternary International xxx (2015) 1e11

was determined using an 8 Bruker D8 Advance powder diffrac- the mobile cations Naþ, Kþ and Ca2þ, as oxides, in molar pro-
tometer provided with a Kristalloflex K780 Cu anode X-ray tube. portions, following the equation:
XRD spectra were processed by means of Eva Diffrac software and
interpreted by using the Crystallography Open Database (2014). Al2 O3
CIA ¼ $100 (1)
Al2 O3 þ Na2 O þ K2 O þ Ca* O
3.2. XRF analysis
where: Ca*O represents the residual calcium contained by silicate
XRF was used to determine the content of nine major rock minerals after carbonates were removed by acid treatment.
forming elements, Na, Mg, Al, Si, K, Ca, Ti, Mn and Fe, as well as In our case, the Ca*O content was systematically higher than
those of Rb and Sr in both HCL treated and untreated samples. To Na2O (see Table 3). Therefore, to calculate the CIA we have
remove carbonates, each sample was treated for 15 days with a considered the McLennan (1993) approach by using the equation
solution of HCl (10% wt) and oxygenated water (10% wt). Then, the ri et al. 2008). The final results
CaO* ¼ Na2O (Gallet et al. 1998; Újva
solid residue was rinsed with distillate water, dried to constant are reproduced in Table 3.

Table 3
The content of major elements oxides (wt %) before and after HCl leaching (*) as well as of the Rb and Sr (ppm) of the Costinesti samples. For comparison the content of the
same elements in average Hungarian loess (AH) (Újvari et al., 2008), average loess (Újv
ari et al., 2008), Upper Continental Crust (UCC) (Rudnic and Gao, 2003), North American
Shale Composite (NASC) (Gromet et al. 1984) and Post Archean Average Australian Shale (PAAS) (Taylor and McLennan, 1991) are given as well.

Element Sample

SI LI L II L III S II L IV S II LV S IV SV Average ± St. Dv. AH AL UCC NASC PAAS

SiO2 61.96 65.00 64.83 67.37 59.40 61.89 65.88 60.22 61.37 60.33 62.83 ± 2.73 63.48 70.71 66.62 64.08 62.80
SiO2* 67.11 75.23 66.90 75.28 67.11 74.41 76.01 68.51 67.30 73.54 71.14 ± 4.03
TIO2 0.71 0.71 0.71 0.80 0.61 0.67 0.71 0.59 0.74 0.74 0.7 ± 0.06 0.91 0.71 0.65 0.70 1.00
TIO2* 0.88 0.92 0.83 0.98 0.81 0.92 0.91 0.79 0.93 1.02 0.90 ± 0.07
Al2O3 14.62 14.37 11.64 16.17 13.43 15.26 14.61 12.60 15.52 17.08 14.53 ± 1.63 13.45 11.74 15.40 16.90 18.9
Al2O3* 13.80 10.68 13.11 12.23 13.57 10.86 10.54 12.96 13.95 11.99 12.37 ± 1.31
FeO 5.08 4.94 5.44 6.11 4.91 5.01 5.36 4.31 5.46 6.82 5.34 ± 0.7 4.67 3.75 5.04 5.09 6.50
FeO* 5.72 2.42 5.25 2.47 5.86 2.82 2.84 5.53 6.62 4.45 4.40 ± 1.61
MnO 0.10 0.09 0.09 0.11 0.08 0.09 0.10 0.08 0.11 0.12 0.1 ± 0.01 0.09 0.07 0.10 0.06 0.11
MnO* 0.04 0.03 0.04 0.02 0.04 0.02 0.03 0.04 0.04 0.02 0.03 ± 0.01
MgO 2.34 2.78 3.05 2.19 2.46 2.32 2.11 2.26 2.72 2.55 2.48 ± 0.3 3.62 2.15 2.48 2.86 2.20
MgO* 1.97 0.38 1.94 0.34 1.75 0.55 0.72 1.75 1.87 1.04 1.23 ± 0.69
CaO 10.58 7.09 8.86 2.92 14.92 10.35 7.28 15.65 9.59 7.89 9.51 ± 3.74 9.73 6.67 3.59 3.63 1.30
CaO* 6.12 5.58 7.30 4.43 6.56 6.23 4.76 6.03 5.44 4.58 5.70 ± 0.93
Na2O 2.40 2.64 3.19 2.22 2.43 2.41 2.08 2.33 2.74 2.61 2.51 ± 0.31 1.47 1.68 3.27 1.14 1.20
Na2O* 1.79 1.9 2.08 1.74 1.86 1.95 1.71 1.87 1.67 1.47 1.23 ± 0.69
K2O 2.20 2.19 2.18 2.11 1.77 2.00 1.87 1.96 1.76 1.86 1.99 ± 0.17 2.37 2.22 2.80 3.97 3.70
K2O* 2.56 2.44 2.54 2.52 2.44 2.24 2.48 2.53 2.18 1.91 2.38 ± 0.21
Rb 83 93 87 104 67 84 107 71 89 95 88 ± 13 103 78 84 125 160
Sr 234 275 307 220 261 263 193 250 305 251 256 ± 35 183 210 320 142 200
CIA 61.5 54.6 57.8 59.2 60.8 55.2 56.0 59.4 64.0 63.5 59.2 ± 3.3 64.6 59.8 48.6 67.8 70.5
CIW 70.1 58.3 65.7 68.1 68.9 62.9 65.2 67.8 71.7 71.2 67.0 ± 4.1 73.6 68.0 54.2 81.8 82.7
Rb/Sr 0.35 0.34 0.28 0.47 0.26 0.32 0.55 0.28 0.29 0.38 0.35 ± 0.09 0.56 0.37 0.27 0.88 0.80

weight, ground in a ball mill and sieved on a 100 mm (about
140 mesh) sieve. The same procedure was also used in the case of
raw, untreated material. Finally, two 3.4 cm diameter pellets were
prepared for each sample by hydraulic pressing at 20 t force for two
minutes.
The XRF measurements were performed by an EX-6600 SDD
Xenemetrix spectrometric system equipped with an EG 60X-ray
generator (Pmax ¼ 300 W, Vmax ¼ 60 kV, Imax ¼ 4.9 mA) and a
25 mm2 Silicon Drift Detector on-line with a built-in a multichannel
analyzer. XRF spectra were analyzed by the nEXT 2.0.q.6 pro-
prietary software. The DC 73372, DC 73307 (China National Analysis
Center for Iron and Steel) and SL-1 (International Atomic Agency
Energy) reference materials were used for efficiency calibration,
and the accuracy was checked by using the TILL-1 (Natural Re-
sources Canada) reference sample. Accordingly, the overall uncer-
tainty regarding the content of major elements was less than 5%.
3.3. CIA, CIW and Rb/Sr ratio
CIA, according to Nesbitt and Young (1982), is defined as the
ratio between the content of immobile aluminum oxide Al2O3 and
To avoid possible misinterpretations due to the absorption of Kþ
ions by clay minerals, Harnois (1988) proposed the use of the chemical
index of weathering (CIW) which differs by the absence, in eq. (1), of
K2O. Moreover, the relative higher mobility of Sr with respect to Rb
makes the Rb/Sr ratio (Dypvik and Harris, 2001; Xu et al., 2010),
another descriptor of the post-depositional weathering of loess se-
quences (Zhang et al. 2013). In view of these and for a better
description of loess and palaeosol weathering, both CIA and CIW as
well as Rb/Sr ratios were calculated and reproduced in Table 3.
3.4. INNA analysis
The content of 28 elements was determined by neutron acti-
vation analysis at the pulsed fast reactor IBR-2 (Flerov Neutron
Physics Laboratory, Joint Institute for Nuclear Research, Dubna,
Russian Federation). The description of the irradiation channels and
the pneumatic transport system REGATA of the IBR 2 can be found
in Frontasyeva and Pavlov (2000). An amount of 100 mg of material
was used for irradiation.
To determine short lived isotopes, the samples were irradiated
for 1 min and, after a decay of 5 min, measured for 10 min. In case of
long lived isotopes samples were irradiated for 60 h, repacked and

Please cite this article in press as: Tugulan, L.C., et al., On the geochemistry of the Late Quaternary loess deposits of Dobrogea (Romania),
Quaternary International (2015), http://dx.doi.org/10.1016/j.quaint.2015.06.062
 L.C. Tugulan et al. / Quaternary International xxx (2015) 1e11 5

measured, using high purity germanium detectors, twice, after 5e6
days and 11e12 days of decay. The data acquisition was 45 and
90 min long, respectively.
Element contents were determined on the basis of certified
reference materials: 2709 NIST (San Joaquin Soil), 2710 NIST
(Montana Soil I), 2711 NIST (Montana Soil II) and 1633b NIST (Coal
fly ash). The NAA data processing and determination of element
concentrations were performed using the software developed in
FLNP JINR (Dmitriev and Pavlov, 2013).
Finally, cluster analysis (Davies, 2002), AeCNeK (Nesbitt and
Young, 1984) and SceLaeTh ternary diagrams as well as different
2D plots including the REE-chondrite normalized diagram were
used to analyze the elemental composition of loess and palaeosol
samples. All statistical analysis were performed by StatSoft™ Sta-
tistica 11.
4. Results and discussion
4.1. Mineralogy
The results of XRD analysis of bulk material show that both loess
and palaeosol sequences consist mainly of six dominant mineral
fractions: quartz, calcite, plagioclase-albite, K-feldspars, smectite/
chlorite and mica group. The relative abundances of minerals for
the different sampled layers are given in Table 2.
The mineral composition of analyzed samples is in good
agreement with the existent data regarding loess mineralogy, while
the presence of calcium carbonate, chlorite and mica suggests weak
to moderate weathering, corresponding to the so-called S1 stage
(Terhorst et al. 2012). The same data points to the absence of any
significant difference between loess and palaeosols through the
entire column.
4.2. Major elements
The content of all nine major elements as oxides, in both un-
treated and HCl treated samples, is reproduced in Table 3, while the
content of untreated ones is illustrated in Fig. 2A spidergram.
Average loess, Hungarian average loess (Újvari et al., 2008) as well
as the UCC (Rudnic and Gao, 2003) were plot on the same figure for
comparison. We have chosen Hungarian loess as the closest one to
our location for which the major elements data are available. The
average loess was selected as it present a general view of the world
loess deposit while the UCC was preferred as it describes the
average composition of the continental crust, the main source of
loess deposits.
All Costinesti samples showed, except for CaO and to a lesser
extent Na2O and K2O, contents similar to UCC. The SiO2, Al2O3 and
MgO contents are slightly lower while TiO2 and FeO slightly over-
pass the UCC. Most probably, the reduced content of sodium and
potassium oxides could be attributed to a lower resistance of
feldspars to weathering.
Due to the reduced number of samples, the compositional
variation described by the coefficient of variation (CV), the standard
deviation to the mean ratio varied between 4.7% for SiO2 to 39.4%
for CaO. In the case of the other seven elements, CV was more
steady, by taking values between 8.7% (TiO2 and Na2O) and 13.0%
(FeO and Na2O) (Table 3). The high variability of the CaO content
could most probably be attributed to the presence, at different
levels, of small calcareous concretions, frequently found in the
Costinesti loess deposit (Fig. 1).
As Table 3 data show, SiO2, Al2O3 and, to a lesser extent CaO,
represent the dominant components of both loess and palaeosols
with a total content between 85 and 88%. These data are very close
to both Hungarian and average loess as well as to UCC, but exceed
both NASC and PAAS contents.
The cluster analysis showed that all nine major elements form
two clusters (Fig. 2B), one consisting only of calcium oxide while the
other one contains the other elements grouped in three sub-clusters.
By taking into account the mineral composition of the unleached
loess and palaeosol samples as determined by XRD, the first cluster
could be mainly attributed to calcium carbonate, while the other one,
by taking into account the presence of silicon and aluminum oxides,
could be attributed to feldspars and clay minerals. The average
content of calcium oxide is about the same that of Hungarian loess,
but significant higher than those of average loess. The alkaline metal
oxides Na2O and especially K2O show lower concentrations with
respect to UCC, also reported by Újv ari et al. (2014) in the case of
Hungarian loess.
The correlation analysis was performed in the Q mode (corre-
lation between samples from the point of view of element con-
tents) and R mode (correlation between element from the point of

Fig. 2. Two diagrams illustrating the content (±1 s) of major elements (as oxides) normalized to UCC (Rudnic and Gao, 2003) (A) as well as the existing correlation between the
major elements of Costinesti samples (B). On the last diagram, the presence of two different clusters, one consisting of CaO and one consisting of all other oxides could be remarked.
The inset reproduces the corresponding table of the correlation coefficients. All evidenced correlations are significant at p < 0.05 (95%).

Please cite this article in press as: Tugulan, L.C., et al., On the geochemistry of the Late Quaternary loess deposits of Dobrogea (Romania),
Quaternary International (2015), http://dx.doi.org/10.1016/j.quaint.2015.06.062
6 L.C. Tugulan et al. / Quaternary International xxx (2015) 1e11
Fig. 3. Two bi-plots proving the moderated weathering process of the Costinesti loess deposit. For a better comparison on Na2O/K2O ratio versus CIA (Song et al., 2014) graph (A)
and CNeKeA ternary plot (Nesbitt and Young, 1984) (B), the points corresponding to the neighboring Mircea Voda and Hungarian loess as well as to some characteristics minerals
ri et al., 2008, 2014; Buggle et al. 2011).
and rocks presenting different degrees of weathering are plotted too (Újva
view of their distribution within samples). In the first case, the
correlation coefficients, for loess and palaeosols, varied between
0.9333 and 1.0 at p < 0.01, indicative of chemical homogeneity of
the Costinesti sample for major elements. In the case of R mode,
only a few major components showed moderate to significant
correlations (Fig. 2B). The positive correlation between TiO2 and
SiO2 and between TiO2 and Al2O3 suggest a possible association of
the titanium minerals with the coarse-grained fraction of the loess,
as previously reported for Hungarian loess by Újv ari et al. (2008). At
the same time, calcium correlates negatively with silicon,
aluminum, and iron, confirming the existing dissimilarities be-
tween the distribution of carbonates and the other minerals which
compose the Costinesti loess deposit. After acid leaching, the CaO
content was reduced by about 40%, and its CV fell to 16.3%, most
probably due to the remaining smectite and plagioclase feldspars.
The content of major elements from the acid leached samples
allowed us to calculate both CIA and CIW. The CIA values varied
between 54.6 and 64 with an average value of 59.2 ± 3.3, lower
than the neighboring Hungarian loess, but very close to the average
loess as defined by Újva ri et al. (2008) (Table 3). With respect to
UCC (Rudnic and Gao, 2003) with CIA 48.6, Costinesti samples had
slightly higher values, but significantly lower than those of NASC
Fig. 4. A Spidergram illustrating the content (±1 s) of Costinesti trace elements
normalized to UCC (Rudnic and Gao, 2003).
Please cite this article in press as: Tugulan, L.C., et al., On the geochemistry of the Late Quaternary loess deposits of Dobrogea (Romania),
Quaternary International (2015), http://dx.doi.org/10.1016/j.quaint.2015.06.062
(CIA 67.8) (Gromet et al. 1984) and PAAS (CIA 70.5) (Taylor and
McLennan, 1991).
A linear representation of the CIA values versus depth shows,
within experimental uncertainties, an almost constant value, sug-
gesting a steady and relative moderate chemical weathering, also
supported by the biplot of Na2O/K2O molar ratio versus CIA (Song
et al., 2014) (Fig. 3A). All Costinesti samples form a group corre-
sponding to the same degree of weathering. As CIW differs by CIA
only in the K2O content, both proxies indicate the same weathering
trend (see Table 3), indicated by a correlation coefficient of
0.9876 at p < 0.01. The Rb/Sr ratios of 0.35 ± 0.09 are lower than
Hungarian average loess but comparable with those of the average
loess (Újvari et al., 2008) and slightly higher than UCC (Table 3),
sustaining the hypothesis of moderate weathering.
The same elements which define CIA were used, by means of
ternary diagrams Al2O3eCa*O þ Na2OeK2O (AeCNeK), to repre-
sent the weathering of the parent rock as well as to characterize the
loess lithology (Nesbitt and Young, 1984, 1989; Johnsson, 1993;
Yang et al., 2004; Li and Yang, 2010) (Fig. 3B). On this diagram,
the points corresponding to Costinesti samples are located on the
same weathering trend, beginning from a point whose composition
is very close to the UCC (Rudnic and Gao, 2003), parallel to the
AeCN line. Additionally on this trend, whose maximum CIA value
for Costinesti samples is 64, there are no significant differences
between loess and palaeosols.
This suggests that the original material of Costinesti samples
initially had a mineral composition relatively close to the UCC, but
that, during weathering, although relatively weak, K2O and CaO
were partially leached from the silicates. At the same time, the
absence of a sizable difference between loess and palaeosols
showed that, in the interglacial periods, the weathering process
was not significant.
4.3. Trace elements
The content of 26 trace elements, including 10 REE as deter-
mined by INAA is reproduced in Table 4 and illustrated by a spi-
dergram normalized to UCC (Rudnic and Gao, 2003) in Fig. 4. Except
for Zr and Hf, and to a lesser extent Cr and Ni, the average content of
all the elements is close to UCC (Rudnic and Gao, 2003), PAAS
(Taylor and McLennan, 1991) and NASC (Gromet et al. 1984), indi-
cating a primary continental origin of the loess material. It was
difficult to recognize any significant difference, within the experi-
mental uncertainties, between loess and palaeosol trace element
distribution.
 L.C. Tugulan et al. / Quaternary International xxx (2015) 1e11 7

Table 4
The content of trace elements (ppm) of the Costinesti loess and palaeosol samples. For comparison the content of the same elements in Upper Continental Crust (UCC) (Rudnic
and Gao, 2003), North American Shale Composite (NASC) (Gromet et al. 1984) and Post Archean Average Australian Shale (PAAS) (Taylor and McLennan, 1991) are given.

Element Sample

SI LI L II L III S II L IV S III LV S VI SV Average ± St. Dv. UCC NASC PAAS

Sc 9.9 10.3 9.9 11.3 9.2 10.1 11.0 8.0 10.2 10.8 10.1 ± 0.9 14 14.9 16
V 95 95 94 91 81 94 98 78 91 107 92 ± 7.8 97 130 150
Cr 122 126 119 132 108 124 134 107 122 124 122 ± 8.4 92 125 110
Co 14 15 15 18 14 15 16 12 16 19 15 ± 2 17.3 25.7 23
Ni 60 59 55 67 55 60 63 45 55 66 58 ± 6 47 58 55
Zn 74 125 79 82 69 69 82 59 79 84 80 ± 17 67 nd 85
As 1.3 1.2 1.3 1.5 1.2 1.4 1.5 1.1 1.4 1.5 1.3 ± 0.1 4.7 28.4 nd
Zr 461 496 477 497 420 453 542 414 460 394 461 ± 42 193 200 210
Mo 0.8 0.9 0.9 1.1 0.9 0.9 0.9 0.7 0.9 0.8 0.9 ± 0.1 1.1 nd nd
Cs 4.6 4.7 4.6 5.4 4.5 5.0 5.4 4.0 4.9 5.4 4.8 ± 0.5 4.9 5.2 15
Ba 552 549 534 539 450 547 648 525 504 404 525 ± 62 624 636 650
La 33.0 31.8 29.7 36.0 29.9 32.2 35.2 27.8 31.9 32.5 32.0 ± 2.3 31 31 38
Ce 64.1 63.3 57.2 69.4 55.0 62.9 68.4 52.8 60.5 60.4 61.4 ± 5.1 63 66.7 80
Nd 33.5 29.4 26.0 29.7 28.3 29.0 35.0 30.0 31.1 26.2 29.8 ± 2.7 27 27.4 32
Sm 4.5 4.4 4.1 4.8 4.0 4.3 4.9 3.8 4.3 4.3 4.3 ± 0.3 4.7 5.6 5.6
Eu 1.0 0.8 0.9 1.0 0.9 0.9 0.9 0.8 0.9 0.9 0.9 ± 0.1 1.0 1.2 1.1
Gd 5.7 4.2 2.8 5.1 4.0 4.6 5.3 3.9 4.4 4.1 4.4 ± 0.8 4.0 nd 4.7
Tb 0.6 0.6 0.6 0.6 0.5 0.6 0.6 0.5 0.6 0.5 0.6 ± 0.0 0.5 0.85 0.77
Tm 0.3 0.3 0.2 0.3 0.2 0.2 0.3 0.2 0.2 0.2 0.2 ± 0.0 0.3 nd 0.4
Yb 2.0 2.1 1.9 2.1 1.6 1.8 2.0 1.6 1.8 1.7 1.9 ± 0.2 2.0 3.1 2.8
Lu 0.5 0.4 0.4 0.4 0.4 0.0 0.5 0.4 0.3 0.4 0.4 ± 0.1 0.31 0.46 0.43
Hf 15.7 15.8 15.0 16.0 12.4 13.9 16.1 12.7 14.0 11.7 14.3 ± 1.5 5.3 6.3 5
Tl 1.5 1.5 1.4 1.6 1.3 1.4 1.6 1.2 1.4 1.4 1.4 ± 0.1 0.9 1.1 nd
W 2.7 2.8 2.8 3.1 2.8 2.7 3.0 2.6 2.8 2.7 2.8 ± 0.1 1.9 nd nd
Th 11.7 11.2 10.8 12.8 10.3 11.7 13.3 10.0 11.7 11.8 11.6 ± 1.0 10.5 12.3 14.6
U 3.1 3.5 3.5 3.3 2.9 3.0 3.3 2.9 2.9 2.9 3.1 ± 0.3 2.7 2.7 3.1
La/Th 2.82 2.82 2.74 2.81 2.90 2.74 2.65 2.79 2.72 2.75 2.78 ± 0.07 2.95 2.52 2.60
La/Yb 16.9 15.3 15.6 17.0 18.3 17.5 17.3 17.8 17.9 19.2 17.3 ± 1.1 13.6 10 13.57
Eu/Eu* 0.59 0.56 0.80 0.61 0.65 0.61 0.56 0.61 0.64 0.64 0.63 ± 0.06 0.66 0.65

Fig. 5. The Ba/Sr vs. Rb/Sr bi-plot (A) as well as the ternary SceLaeTh (B) illustrating in a comparative manner the position of the Costinesti samples with respect to average
sedimentary rocks UCC (Rudnic and Gao, 2003), NASC (Gromet et al. 1984), PAAS (Taylor and McLennan, 1991), average Hungarian loess (Újva ri et al. 2008), average loess (Újva
ri
et al. 2008) and Western Carpathian granite (Broska et al., 2004).

A biplot of the Ba/Sr ratio versus Rb/Sr ratio (Fig. 5A) showed a
linear dependency between them, characterized by a correlation
coefficient of 0.9676 at p < 0.01 as well as a trend from UCC to PAAS,
similar with those reported by Újva ri et al. (2008) for Hungarian
Loess. The average values of these ratios, in the case of Costinesti
loess and palaeosol samples, are closer to average loess then to the
average Hungarian loess. Moreover, the position on this graph of
the average Western Carpathian granite (Broska et al. 2004) also
suggests the presence of some igneous rock material. The ternary
diagram of the insoluble elements SceLaeTh reproduced in Fig. 5B
showed that all Costinesti samples form a single cluster together
with corresponding points of UCC, NASC and PASS, in perfect
agreement with the continental origin of loess and palaeosol
deposits.
The relatively increased content of Cr and Ni could attest to the
presence of some felsic lithology among the other sources of loess
material. The Na2O/Al2O3 vs. K2O/Al2O3 (Garrels and Mackenzie,
1971) and TiO2 vs. Ni (Floyd et al., 1989) bi-plots reproduced in
Fig. 6A and B show that the Costinesti loess and palaeosols are at
the limit between igneous rocks, which could be an explanation of
this finding. The same trend was noticed in the case of Th/Ni vs. Zr/
Ni and Th/V vs. Zr/V (Újva ri et al. 2008) biplots (Fig. 6C and D),
where all points corresponding to Costinesti samples presented the
same location with respect to the floodplain sediments and to the

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8 L.C. Tugulan et al. / Quaternary International xxx (2015) 1e11

Fig. 6. Four diagrams: Na2O/Al2O3 vs. K2O/Al2O3 (Garrels and Mackenzie, 1971) (A), TiO2 vs. Ni (Floyd et al., 1989), Th/Ni vs. Zr/Ni (C) and Th/V vs. Zr/V (D) (Újvari et al. 2008), used to
discriminate the position of Costinesti loess and palaeosol with respect to average sedimentary rocks UCC (Rudnic and Gao, 2003), NASC (Gromet et al. 1984), PAAS (Taylor and
McLennan, 1991), average Hungarian loess (Újva ri et al. 2008), average loess (Újvari et al. 2008) suggesting the presence of certain felsic rock material.

basaltegranite tendency, slightly displaced towards felsic volcanic
rocks.
The same conclusion is sustained by comparing the La/Sc, Th/Sc,
Cr/Th as well as the Eu/Eu* ratios of the Costinesti samples with the
corresponding values for sediments deriving from felsic and mafic
sources (Amstrong-Altrin et al., 2004) as well as with the UCC
(Rudnic and Gao, 2003). The results reproduced in Table 5 show
that Costinesti samples have, especially in the case of La/Sc, Th/Sc
and to a lesser extent in the case of CR/Th, an intermediate position
between UCC and sediments derived from felsic sources.
diagram of the insoluble elements SceLaeTh (Fig. 5B) shows that
all Costinesti samples form a single cluster together with corre-
sponding points of average rocks represented by the UCC, NASC,
and PASS.
The XRD data documented the presence of zircon in all the
Costinesti samples, which can explain the higher content of both Zr
and Hf. Zircon incorporates Hf during crystallization, so that zircon
contains 1e4% Hf, in agreement with the present data showing a
Hf/Zr ratio of 3.1 ± 0.1%, very close to those of UCC and NASC (3.1
and 3.2% respectively), but higher than PAAS (2.4%). Sc, Zr, REE, Hf

Table 5
The average values ±1 s of the La/Sc, Th/Sc, Cr/Th and Eu/Eu* ratios of the Costinesti samples with respect to similar ratios in the case of sediments derived from mafic and felsic
rocks (Amstrong-Altrin et al. 2004) as well as in the case of UCC (Rudnic and Gao, 2003).

Elemental ratio Sediments from mafic sources Sediments from felsic sources Costinesti samples UCC

La/Sc 0.43e0.86 2.50e16.3 3.19 ± 0.15 0.21

Th/Sc 0.05e0.22 0.84e20.5 1.15 ± 0.05 0.75
Cr/Sc 25.00e500.00 4.00e15.00 10.54 ± 0.39 8.76
Eu/Eu* 0.71e0.95 0.40e0.94 0.63 ± 0.06 0.72

The presence of a certain amount of felsic rock material in
Costinesti loess could be an explanation of the increased content of
Cr previously reported for Danube Delta lacustrine sediments
(Dinescu et al., 1998, 2004). However, this does not alter the relative
similarities between Costinesti samples and the UCC. A ternary
and Th, due to their relative low mobility represent good indicators
of the sedimentation processes. Both Th/Sc versus Zr/Sc (McLennan
et al. 1993) (Fig. 7A) and La/Th versus Hf (Floyd and Leveridge, 1987)
(Fig. 7B) biplots suggest the existence of significant sedimentary
sorting.

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 L.C. Tugulan et al. / Quaternary International xxx (2015) 1e11 9

Fig. 7. Two diagrams illustrating the Zr enrichment (high Zr/Sc ratio) due to sediment recycling (A) by means of a Th/Sc versus Zr/Sc plot (McLennan et al., 1993) as well as the
presence of recycled components (B) by means of a La/Th versus Hf plot (Floyd and Leveridge, 1987) for all Costinesti samples. Similar data for UCC (Rudnic and Gao, 2003), NASC
(Gromet et al., 1984) and PAAS (Taylor and McLennan, 1991) are illustrated too.

Fig. 8. Two diagrams depicting some characteristic distribution of the REE in Costinesti loess and palaeosol samples. The La versus Th plot (Taylor and McLennan, 1991) (A) and the
chondrite normalized REE plot (B). Similar data for UCC (Rudnic and Gao, 2003), NASC (Gromet et al., 1984) and PAAS (Taylor and McLennan, 1991) are illustrated too. Chondrite
normalized values taken from Taylor and McLennan (1991).

The REE represent a group of 15 elements with very similar
chemical properties and whose content offers information con-
cerning the origin and evolution of rocks (McLennan, 1989). The
biplot La vs. Th (Fig. 8A) shows a direct correlation characterized by
La/Th ratio of 2.78 ± 0.09, very close to all three average sedi-
mentary rocks: UCC (2.80), NASC (2.52) and PAAS (2.60).
The distribution on a chondrite normalized diagram (Fig. 8B)
shows a typical pattern for the continental crust, very similar to
those of UCC, NASC, and PAAS. According to the data reproduced in
Table 4, all Costinesti samples present almost the same La/Yb ratio
of 17.3 ± 1.1, slightly higher than those of UCC and PAAS but
significantly higher than NASC.
Another parameter which characterize the REE distribution
consists of the Eu/Eu* ratio (Eu stands for chondrite normalized
content while Eu* is equal to the geometric mean of the product of
Sm and Gd contents normalized to chondrite, i.e. Eu* ¼ (SmN*GdN)½
which define the Eu anomaly). In the case of Costinesti samples, the
Eu/Eu* ratio has an average value of 0.63 ± 0.06 close to those of
UCC (Rudnic and Gao, 2003) and PAAS (Taylor and McLennan, 1991).
Eu as Eu2þ ions substitute for Sr ions in plagioclases, and has the
tendency to be enriched in the Lower Continental Crust and
consequently to be depleted in the rock which finally formed the
UCC (McLennan, 1989). A negative Eu anomaly indicates the pres-
ence of a sedimentary material close to the UCC (Duliu, 2011), as in
the case of Costinesti loess and palaeosols. Hence, the distribution
of trace elements in the loess and palaeosol samples from Costinesti
shows, within experimental uncertainties, no differences between
loess and palaeosol, confirming the same source of sedimentary
material, whose composition, close to the average continental one,
shows the influence of some material of felsic rock origin.
5. Conclusions
The XRD, XRF and INAA data of ten loess and palaeosol samples
collected from Costinesti, Southern Dobrogea, provided informa-
tion concerning the weathering conditions and the provenance of
material from this formation. The Costinesti loess deposit, devel-
oped during the last four glacial cycles, consists mainly of quartz,
calcite, plagioclase-albite, K-feldspars, smectite/chlorite and a 10 Å
mica group. Three different climatic proxies: CIA, CIW and Rb/Sr
ratios, indicated limited weathering during loess deposition,
further confirmed by the presence of both calcite and clay minerals.
The average contents of 28 trace elements was, with the
exception of Cr, Ni, Zr and Hf, very close to those of the average

Please cite this article in press as: Tugulan, L.C., et al., On the geochemistry of the Late Quaternary loess deposits of Dobrogea (Romania),
Quaternary International (2015), http://dx.doi.org/10.1016/j.quaint.2015.06.062
10 L.C. Tugulan et al. / Quaternary International xxx (2015) 1e11
rocks UCC, NASC and PAAS. A more detailed analysis including the
distribution of low mobility elements Sc, Zr, REE, Hf, and Th sug-
gests the presence in the Costinesti loess and palaeosols, together
with the continental material, of a certain amount of felsic com-
ponents, thus explaining the observed increased content of Cr and
Ni. The REE distribution showed a typical upper continental pattern
with an Eu negative anomaly.
Acknowledgements
L.C.T. wishes to acknowledge that this work was done during his
Ph.D. studies at the Doctoral School of Physics of the University of
Bucharest. The INAA analysis was performed at the Frank Neutron
Physics Laboratory of the Joint Institute of Nuclear Research (JINR)
e Dubna, Russian Federation within the Protocol No. 4322-4-14/16
between JINR and the University of Bucharest. We would also wish
to thank an anonymous reviewer for his thoughtful examination of
the manuscript and for his remarks and suggestions and to Mrs
Mariana Marinescu for her help in revising the final version of the
manuscript.
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