GeolCarp_Vol68_No3_248

GEOLOGICA CARPATHICA

, JUNE 2017, 68, 3, 248 – 268

doi: 10.1515/geoca-2017-0018

www.geologicacarpathica.com

Geochemistry, environmental and provenance study of

the Middle Miocene Leitha limestones (Central Paratethys)

AHMED ALI

1, 2, 

and MICHAEL WAGREICH

Geology Department, Faculty of Science, Minia University, 61519 Menia, Egypt;



ahmad.ali@mu.edu.eg

Department of Geodynamics and Sedimentology, Centre for Earth Sciences, University of Vienna, 1090 Vienna, Austria

(Manuscript received July 20, 2016; accepted in revised form March 15, 2017)

Abstract: Mineralogical, major, minor, REE and trace element analyses of rock samples were performed on Middle

Miocene limestones (Leitha limestones, Badenian) collected from four localities from Austria (Mannersdorf, Wöllersdorf,

Kummer and Rosenberg quarries) and the Fertőrákos quarry in Hungary. Impure to pure limestones (i.e. limited by Al

contents above or below 0.43 wt. %) were tested to evaluate the applicability of various geochemical proxies and indices

in regard to provenance and palaeoenvironmental interpretations. Pure and impure limestones from Mannersdorf and

Wöllersdorf (southern Vienna Basin) show signs of detrital input (REEs = 27.6 ± 9.8 ppm, Ce anomaly = 0.95 ± 0.1 and the

presence of quartz, muscovite and clay minerals in impure limestones) and diagenetic influence (low contents of, e.g.,

Sr = 221 ± 49 ppm, Na is not detected, Ba = 15.6 ± 8.8 ppm in pure limestones). Thus, in both limestones the reconstruction

of original sedimentary palaeoenvironments by geochemistry is hampered. The Kummer and Fertőrákos (Eisenstadt–

Sopron Basin) comprise pure limestones (e.g., averages Sr = 571 ± 139 ppm, Na = 213 ± 56 ppm, Ba = 21 ± 4 ppm,

REEs = 16 ± 3 ppm and Ce anomaly = 0.62 ± 0.05 and composed predominantly of calcite) exhibiting negligible diagenesis.

Deposition under a shallow-water, well oxygenated to intermittent dysoxic marine environment can be reconstructed.

Pure to impure limestones at Rosenberg–Retznei (Styrian Basin) are affected to some extent by detrital input and

volcano-siliciclastic admixture. The Leitha limestones at Rosenberg have the least diagenetic influence among the studied

localities (i.e. averages Sr = 1271 ± 261 ppm, Na = 315 ± 195 ppm, Ba = 32 ± 15 ppm, REEs = 9.8 ± 4.2 ppm and Ce anomaly =

0.77 ± 0.1 and consist of calcite, minor dolomite and quartz). The siliciclastic sources are characterized by immobile

elemental ratios (i.e. La/Sc and Th/Co) which apply not only for the siliciclastics, but also for marls and impure limestones.

At Mannersdorf the detrital input source varies between intermediate to silicic igneous rocks, while in Kummer and

Rosenberg the source is solely silicic igneous rocks. The Chemical Index of Alteration (CIA) is only applicable in the

shale-contaminated impure limestones. CIA values of the Leitha limestones from Mannersdorf indicate a gradual

transition from warm to temperate palaeoclimate within the limestone succession of the Badenian.

Keywords: Central Paratethys, Neogene, Leitha limestones, geochemistry, provenance.

Introduction

Sedimentary geochemistry, especially the distribution of rare

earth elements (REEs) provides valuable information about

marine depositional environments and sediment provenance.

It is used in the assessment of the pathways of terrigenous and

biogenic fluxes from the source to the sediments (Piper 1974;

Elderfield & Greaves 1982; Haley et al. 2004; Anderson et al.

2007; Johannesson et al. 2014; Garbelli et al. 2016). Absolute

element concentrations, relative abundance, patterns of the

REEs and Ce and Eu anomalies provide guiding tools and can

be used as proxies for various environmental parameters,

widely applied in sedimentological studies (e.g., Elderfield

1988; Piepgras & Jacobsen 1992; Nozaki 2001; Bau et al.

2010). The absolute and relative concentrations of these ele-

ments in sediments help us to recognize, classify and unravel

(1) the detrital input but also input from hydrothermal systems

and related alterations; (2) the interaction with the biogeo-

chemical cycle involving removal of elements from water

bodies by adsorption and oxidation on particle surfaces and

deeper regeneration within the sedimentary column; and

(3) the effects of advective transport through rocks (Elderfield

1988; Kocsis et al. 2010; Azmy et al. 2011). REEs are charac-

terized by largely similar behaviour in sediments, based on the

chemical similarity as a result of the progressive filling of

the inner 4f electrons orbital with increasing atomic number

(de Baar et al. 1985; Nozaki 2001; Kim et al. 2012).

REEs patterns can be used to distinguish between different

depositional environments. Based on the model proposed by

Haley et al. (2004) three pattern types can be distinguished:

(1) the linear pattern type which shows a constant, but mode-

rate increase in the Post-Archean Australian Shale (PAAS)-

normalized REEs across the series, from lower to higher

atomic numbers. In this pattern type REEs are released mainly

from the degradation of particulate organic matter (POC). This

pattern is distinctive for oxygen levels, namely oxic and

suboxic environments; (2) HREE-enrichment pattern (higher

(H) atomic number REEs enriched) in which the POC source

plays an important role in carrying REEs; (3) MREE bulge

pattern (enrichment in middle (M) REEs) which is strongly

related to high Fe-concentrations. This correlation is inter-

preted as a result of the dissolution of a surficial, REE-

enriched solid Fe-phase which becomes the source for these

REEs.

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Further sediment geochemical interpretations can be per-

formed using cerium and europium. All lanthanide elements

are generally positively trivalent charged (i.e.

), but Ce and

Eu also exist in

and

states, respectively. The oxidation of

(loss of electron) and production of Ce

takes place

trough reaction with seawater and results in the formation of

cerium dioxide (CeO

) which is highly insoluble in seawater.

This criterion makes Ce a practical index for interpreting

primary redox conditions in seawater using carbonates

(Elderfield 1988; Bau 1991; Bau & Möller 1992; Bau &

Dulski 1999; Hongo & Nozaki 2001; Dubinin 2004; Craddock

et al. 2010; Schmidt et al. 2010). The reduction of Eu

to Eu

which has the ability to replace Ca

in feldspars, especially in

plagioclase, is favourable in sites with submarine hydrother-

mal activity (Elderfield 1988) representing a secondary signi-

ficant REEs source (e.g., Michard et al. 1983; Hinkley &

Tatsumoto 1987; Campbell et al. 1988). There, the REEs are

scavenged quickly from the hydrothermal fluids, especially

Eu which is removed faster than its neighbour elements, and

thus produces a positive Eu anomaly (Olivarez & Owen 1991).

In this study we analysed the mineralogy and geochemistry

of Neogene limestones (Middle Miocene, Badenian Leitha

limestones) at several localities in Austria and Hungary. This

work deals mainly with sediment geochemistry regarding

major, minor and REEs of these limestones transitional from

impure to pure carbonate lithologies (distinguished by Al

contents below or above 0.43), to get information about sedi-

ment provenance, hinterland and depositional environments.

Provenance and environmental sediment geochemistry signals

are distinguished and evaluated for significance in a relatively

straightforward carbonate setting of the Central Paratethys Sea

to test the applicability of various methods in sediment geo-

chemistry on shallow-water carbonates in general.

Geological settings

The Vienna Basin was formed mainly as a pull-apart basin

along strike-slip and normal faults due to transtension along

the junction of the Eastern Alps and Western Carpathians

(Royden 1985; Wessely 2006). Subsidence took place during

the late Early to Middle Miocene, and led to faulting along the

basin margins. Subsidence rates strongly varied during basin

development with increasing rates during the early Badenian

in the southern part of the basin (Wessely 1983; Lankreijer et

al. 1995; Wagreich & Schmid 2002; Lee & Wagreich 2017).

Islands, shoals, and small carbonate platforms were wide-

spread in the Vienna Basin during the Middle Miocene (Dullo

1983; Riegl & Piller 2000; Schmid et al. 2001; Kováč et al.

2007; Harzhauser & Piller 2010). The Leitha Mountains

(southern part of Vienna Basin), type area of the Leitha lime-

stones, represented a shallow carbonate platform with exten-

sive carbonate production (Schmid et al. 2001; Strauss et al.

2006). According to Riegl & Piller (2000) these Leitha lime-

stones were deposited in a gently sloping, shallow subtidal

environment.

The Eisenstadt-Sopron Basin formed a small satellite basin

of the Vienna Basin to the southeast, similar in many respects

also to the larger Styrian Basin (e.g., Ebner & Sachsenhofer

1995) in the south of Austria, both at the junction to the

Pannonian Basin system, and having similar Leitha limestones

deposits in shoaling parts of the basins. The Styrian Basin

opened in the Early Miocene during the final stage of the

Alpine orogeny (Ebner & Sachsenhofer 1995), and was

divi ded by the N–S Middle Styrian Hills into the Eastern and

Western Styrian subbasins (Kröll 1988). Basin subsidence

during the Karpatian was a result of extensional tectonics and

led to marine flooding (Ebner & Sachsenhofer 1995); eruptive

volcanism accompanying the tectonic activity continued in the

Badenian (Balogh et al. 1994; Slapansky et al. 1999; Seghedi

& Downes 2011).

Middle Miocene shallow-water limestones in Central Europe

are termed the Leitha limestones, a classical name that was

already used during the 19

century (e.g., Suess 1860). Lateron,

the stratigraphic unit was defined by Papp & Steininger in

more detail (in Papp et al. 1978), although this definition does

not conform to modern stratigraphic codes (Hedberg 1976;

Salvador 1994; Steininger & Piller 1999) — as a consequence

the term is not defined formally, and we use the term Leitha

limestone as an informal name throughout the following paper.

Leitha limestone thus refers to Middle Miocene shallow-water

carbonate units composed mainly of corallinacean algae and

subordinate coral-bearing strata. The latter were defined origi-

nally as being reefs (Papp et al. 1978; Dullo 1983; Tollmann

1985), but later investigations (Piller & Kleemann 1991; Piller

et al. 1996, 1997; Riegl & Piller 2000) confirmed that these

carbonates are not reefal deposits sensu stricto but rather coral

carpets such as at the type locality in the Leitha Mountains of

eastern Austria (Riegl & Piller 2000).

The unit is dated mainly to the Badenian (regional Central

Paratethys Middle Miocene stage) which is equivalent to

the Langhian–early Serravallian stages (Piller et al. 2007;

Hohenegger et al. 2014). The existence of the lost Paratethys

Sea was already proposed by Laskarev (1924) due to its diffe-

rent biogeographic entity compared to the Mediterranean

Neogene. The Paratethys was subdivided into three palaeo-

geographic and geotectonic units, the Western, Central and

Eastern Paratethys, respectively. The Eastern Alpine- Carpathian

Foreland basins, from Lower Austria to Moldavia, the study

area of the Vienna, Eisenstadt and Styrian basins in Austria,

and the adjacent large Pannonian Basin System were included

into the Central Paratethys (Piller et al. 2007).

Although a huge amount of palaeontological data is avai lable

for these Miocene limestones (e.g. Riegl & Piller 2000;

Schmid et al. 2001), the exact chronostratigraphic position of

individual units of Leitha limestones remains hard to unravel.

In general, mostly a middle to late Badenian (Langhian to

early Serravalian) age was deciphered more recently (e.g.,

Reuter et al. 2012; Wiedl et al. 2012, 2013, 2014; Hohenegger

et al. 2014). Numerical ages for the Badenian are rare; tuffs

intercalated with Leitha limestones in the Styrian basin at

Retznei quarry were dated using

Ar/

Ar method on biotite,

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and yielded an age of 14.21± 0.07 Ma, together with three

sanidine crystals of 14.34 ± 0.12 Ma (Handler et al. 2006).

Hohenegger et al. (2009) and Hohenegger & Wagreich (2012),

using cyclostratigraphy and astrochronology on combined

outcrops and core data of the Badenian type locality in the

southern Vienna Basin, dated the middle Badenian to 14.22 to

13.98 Ma (see also Hohenegger et al. 2014). Strauss et al.

(2006) used 3D seismic reflection data, well-drill data, surface

outcrops and refined biostratigraphy in the interpretation of

sequence stratigraphic framework for the southern and central

Vienna Basin. Three Badenian 3

order depositional cycles,

also recognized in the Styrian Basin (Schreilechner & Sachsen-

hofer 2007), are correlated with the TB2.3., TB2.4. and TB2.5.

cycles from the global sea-level charts of Haq et al. (1987)

with most Leitha limestones corresponding to the TB2.4 and

TB2.5 sequences, starting at 14.8 Ma and 13.6 Ma, respecti-

vely (Hohenegger et al. 2014).

Sedimentary facies of Leitha limestones were investigated

from many localities in Austria such as the type-locality at

Fenk quarry (Grosshoeflein, Leitha Mts., Burgenland province,

Austria, Fig. 1), where a sequence of ten coral intervals was

observed (Riegl & Piller 2000). According to the authors these

coral intervals represent a sequence of coral carpets and non-

frame building coral communities.

Studied areas

Mannersdorf quarry (samples are denoted by M14/n, where

n is sample number) is an active quarry of the Lafarge Zement-

werke GmbH close to the village Mannersdorf in Lower

Austria (Fig. 1), in the SW marginal part of the Vienna Basin.

The quarry is located in the NE marginal part of the Leitha

Mountains (Fig. 1) extends in NE–SW direction, and the

mining activity continues in a SW direction. The Leitha lime-

stones overlie mainly Middle Triassic dolostone and in some

parts there is a deepening upward (transgressive) succession

preserved, represented by basal breccias — gravel/conglo-

merate–sandstone–limestone (Fig. 2). In the NE part of the

quarry a gravel layer underlies the limestones, described by

Wiedl et al. (2012) as well rounded, poorly sorted, and com-

posed of granite, quartz and dolostone pebbles and fine quartz

sand. Detailed stratigraphy and facies description were given

by Wiedl et al. (2012); the facies types determined by these

authors will be also used in our study. Besides cross-bedded

gravel facies, basal breccia facies and rhodolith facies, the

bioclastic corallinacean facies include seven subfacies (i.e.

Acervulina-rhodolite, Mollusc, Amphistegina, Bryozoan, Coral

debris, Pholadomya and Pinna subfacies) (Wiedl et al. 2012).

The abandoned Wöllersdorf quarry area (samples are deno-

ted by WÖ/n) is situated on the western margin of the Vienna

Basin (Fig. 1). Here, Miocene sediments transgress mainly

Triassic carbonates of the Northern Calcareous Alps. Several

metres of Leitha limestones yield abundant Corallinacea, and

molluscs (Wessely 2006). Mainly algal rudstones, grainstones

and packstones were described from this area (Rohatsch

2005).

The Kummer quarry (samples are denoted by SK/n) is located

2 km to the East of St. Margarethen village in Burgenland,

Austria (Fig. 2), within the Eisenstadt–Sopron Basin. The basin

is surrounded by the Leitha Mountains to the North,

Fertőrákos–Ruster Hügelland to the East, the Sopron Hills to

Fig. 1. a — General map of Austria with Leitha mountains location; b — geological map of the Leitha mountains and the southern Vienna

Basin, including Leitha limestones distribution (after Strauss et al. 2006).

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the South and Rosalia mountains to the West. The Leitha lime-

stones overly Neogene gravels and Austroalpine basement

rocks. In the current paper we are following the sedimentology

and stratigraphy of the quarry provided by Schmid et al.

(2001) who defined three sedimentary facies (i.e. coralli-

nacean debris facies, laminated marl facies and rudstones

facies) from the quarry (Fig. 2).

Fertőrákos quarry (samples are denoted by F/n) is located to

the south of Kummer quarry in Hungary and has a largely

similar geological setting and stratigraphy as Kummer quarry,

being also part of the Eisenstadt–Sopron Basin (Fig. 2).

Rosenberg quarry (samples are denoted by RR/n) (40 km

south of Graz, Fig. 3) is part of the Retznei cement quarries

of the Lafarge Zementwerke GmbH in the Styrian Basin.

The Leitha limestones in the area are correlated with the

second Badenian transgression into the Central Paratethys

which corresponds to TB 2.4 of the global sea level of Haq et

al. 1987; see also Strauss et al. (2006). The stratigraphy of the

studied locality shows a mixture of carbonates with silici-

volcaniclastic sediments which were investigated and facies

types were determined by Reuter et al. (2012). Four deposi-

tional units and six facies types (reef facies, inter-reef facies,

coralline algal debris facies, rhodolith-Porites facies, quartz

sand-Planostegina facies and coral carpet facies) are reported

from the mixed silici-volcaniclastic succession at the

Rosenberg quarry (Reuter et al. 2012).

Methods

In total, 91 sediment samples were collected. The 41 sam-

ples from Mannersdorf include eight clastic samples for deci-

phering siliciclastic background values (i.e. one sand, one

conglomerate, one sandstone and five intercalated clay sam-

ples) and 33 samples represent various Leitha limestones

facies types. Six Leitha limestone samples were collected at

the Wöllersdorf quarry. A total of thirty samples were taken

from Kummer quarry near St. Margarethen village including

twenty-three limestone samples, four marly facies and three

clastic samples. Eleven samples were collected at Rosenberg

quarry, two from the lower siliciclastics, four samples represent

limestones, one tuff sample and four upper siliciclastics

samples. Only three limestone samples were taken from the

Fertőrákos locality. Limestone samples include both pure and

impure limestones featuring visible siliciclastic contamination.

Rock samples were cut into 5×5 cm slabs for thin sections,

while all samples were powdered for X-Ray Diffraction

(XRD) and whole rock geochemical analyses. The thin sec-

tions were investigated microscopically and photomicro-

graphs were taken by Leica microscope (Leica DM2700P)

with Leica camera (Leica MC170 HD) connected to computer

software (LAS v4.4.0). For XRD analysis the powdered sam-

ples were analysed with a Panalytical PW 3040/60 X’Pert

PRO diffractometer (CuKα radiation, 40 kV, 40 mA, step size

0.0167, 5 s per step). The X-ray diffraction patterns were inter-

preted using the Panalytical software “X´Pert High score plus”

at the University of Vienna, Austria. SEM pictures were taken

using a FEI Scanning Electron Microscope at the University

of Vienna, Austria. The apparatus is equipped with secondary

electron detectors for operation at high vacuum and low

vacuum, as well as a back scattered electron detector and an

energy dispersive X-ray detection unit (EDAX Apollo XV).

The chemical bulk rock analyses including major oxides,

some minor elements (see Tables 1, 2 & 3) and loss on

ignition (LOI) were detected by ICP-emission spectroscopy

Acme

Labs (Acme Analytical Laboratories Ltd.,

www. acmelab.com; now Bureau Veritas Mineral Labs) in

Vancouver (Canada). For the analysis of trace elements (REE

Fig. 2. Simplified geological map of the Eisenstadt–Sopron Basin,

SE Vienna Basin and westernmost Pannonian Basin with location of

Kummer and Fertőrákos quarries (after Schmid et al. 2001).

Fig. 3. Geological map of the Styrian Basin with location of the studied

Rosenberg quarry near Retznei village (after Reuter et al. 2012).

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and base metals) ICP-mass spectroscopy was used

(www.acmelab.com). Standard deviations are mainly in the

range of 0.1 to 1 % (for further details see Neuhuber et al.

2016). In addition, three samples of cements and individual

shells (cement from M14/43, oyster shell from SK/28 and

pectinid shell from SK/19) were selected for chemical analy-

ses to be compared to the whole rock chemical analyses of the

same samples.

The PAAS-normalized REEs patterns were obtained by

dividing the measured elements by the same elements of

Taylor & McLennan (1985). The PAAS value of REEs are as

follows La = 38, Ce = 80, Pr = 8.9, Nd = 32, Sm = 5.6, Eu = 1.1,

Gd = 4.7, Tb = 0.77, Dy = 4.4, Ho = 1, Er = 2.9, Tm = 0.4, Yb = 2.8

and Lu = 0.43 ppm (Taylor & McLennan 1985). Ce anomaly

was quantified after the normalization of the neighbouring

elements La and Pr throughout the equation (De Baar et al.

1983): Ce/Ce* = 2CeN/(La+Pr)N, and the Eu anomaly was

evaluated using the equation: Eu/Eu* = EuN/√SmN*GdN,

where the subscript N refers to normalized value to PAAS.

Sr/Ca ratio was calculated after the conversion of CaO wt. %

into Ca ppm by the equation (CaO wt. % * 0.7147) * 10000 =

Ca ppm) to each sample then Ca was divided by Sr and expres-

sed in a reverse manner where the numerator represents Sr and

equals 1 and denominator represents the result of the division.

These calculations were summed and averaged to all lime-

stone samples.

Many indices were proposed to evaluate the chemical

weathering such as chemical index of alteration (CIA) = [Al

(Al

+ CaO* + Na

O + K

O)] × 100, chemical index of

weathe ring (CIW) = [Al

/ (Al

+ CaO + Na

O)] × 100 or

CIW` = [Al

/ (Al

+ Na

O)] × 100, where CaO* represents

the calcium content derived from silicates (Nesbitt & Young

1982; Harnois 1988; Chittleborough 1991; Cullers 2000).

The CIA is applied here to determine the degree of chemical

weathering in which CaO* is set equal to Na

O because of the

high content of calcite in all samples (McLennan et al. 1993).

Mn* values were calculated by the equation [(Mn*=

Log (Mn

sample

/ Mn

shale

) / (Fe

sample

/ Fe

shale

) according to Wedepohl

(1978) average Mn

shale

value is 600 ppm and average Fe

shale

value is 46150 ppm].

Results

Mineralogy

The bulk mineralogy of limestone samples from Manners-

dorf examined by SEM, optical microscopy and XRD allowed

the discrimination of four categories. The mineral composi-

tion of these categories is: (1) only calcite (pure limestone,

Fig. 4a, b); (2) calcite and a small amount of quartz (also pure

limestones); (3) calcite and a small amount of quartz and dolo-

mite and (4) calcite, quartz and clay minerals (impure lime-

stone, Fig. 4c, d). Besides that, the optical microscopy and

Scanning Electron Microscopy (SEM) examination of the

samples proved the presence of muscovite (Fig. 4a), clay

minerals and feldspars with variable amounts in all studied

limestones facies and sometimes pyrite and barite.

In this regard the Leitha limestones lithofacies are treated

here separated in two main groups: (1) visibly “pure” lime-

stones with minor amounts of detrital materials only con-

firmed by SEM and in some cases by optical microscopy,

(2) “impure” limestones with variable to abundant amounts of

the detritus revealed by XRD.

Samples from Wöllersdorf are subdivided into two groups

according to the mineralogical composition, namely: (1) litho-

facies mainly consisting of calcite, quartz and muscovite and

(2) lithofacies composed of calcite, dolomite and quartz, both

lithofacies are considered here as impure limestones. Lime-

stones from the Kummer quarry display two main lithofacies:

(1) limestones composed mainly of calcite and minor quartz

abundance (pure limestones, Fig. 4e, f), and (2) marly

facies composed of calcite with quartz and clay minerals.

The Fertőrákos limestone samples are similar to the Kummer

pure limestones with mainly calcite and quartz as mineral

components.

The Rosenberg Leitha limestones comprise calcite, dolo-

mite and quartz, dolomite is significantly more abundant

(higher intensity peak in XRD chart, sample RR/7) in the

sample directly in contact with the tuff layer, the mineralogy

of the latter layer is quartz, calcite, muscovite, albite, orthoclase

and gypsum.

Geochemistry

Major elements

The average chemical compositions of the Mannersdorf

samples are shown in Table 1. In pure Leitha limestones sam-

ples the major oxide is CaO average of 54.98 wt. % (n=25).

In contrast the lithofacies with higher clay mineral contents

(impure limestones) show a gentle variation in the major

oxides in which the average CaO content is lower with value

of 51.56 wt. % (n=6) while average Al

content is 1.19 wt. %.

At Wöllersdorf, the two Leitha limestones lithofacies which

are impure limestones exhibit different chemical characte ris-

tics (Table 2) in which the major oxides compositions in the

calcite lithofacies are dominated by CaO with an average

value of 53.2 wt. % (n=3) and MgO average value is

0.64 wt. %. The limestones lithofacies with dolomite have

average values of CaO = 47.3 wt. % and MgO = 5.7 wt. % (n=3).

At Kummer, the pure limestone lithofacies dominated by

calcite have a CaO average value of 54.4 wt. % (n=23) and an

average Al

= 0.14 wt. %. Marly lithofacies have a lower

CaO average of 46.1 wt. % (n=4), average SiO

of 8.7 wt. %,

average Al

of 3.2 wt. %, average Fe

of 0.9 wt. %, while

MgO; K

O have average values of 0.8 and 0.6 wt. %, respec-

tively. Fertőrákos Leitha limestones samples do not show dif-

ferences from Kummer samples, showing that they are pure

(Table 2) with a CaO average of 53.97 wt. % (n=3).

The Rosenberg Leitha limestones samples (n=4) show dif-

ferences in chemical compositions with respect to their strati-

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graphic position within the Leitha limestone interval. Two

samples were collected from the lower and upper parts of

the main limestone bank (Reutel et al. 2012), in contact to

underlaying and overlaying siliciclastics, and two samples

from the middle portion of the bank (Table 3). In the former

ones the average CaO is 51.46 wt. % and Al

average is

0.75 wt. %. The latter samples have higher CaO with average

of 55.12 wt. % and lower Al

average of 0.06 wt. %.

The tuff layer (sample RR/6) has the lowest SiO

content

among the sampled siliciclastics with 16.93 wt. % and the

highest content of MgO with 8.31 wt. %. The CaO, Al

and K

O contents are 29.91, 5.73, 3.57 and 1.26 wt. %,

respectively.

Minor elements

Minor element contents in the Mannersdorf samples are low

in the limestone facies compared to the siliciclastics (Table 1).

The only exception is strontium (Sr) which has a significantly

higher content in the limestone facies. The average Sr content

in the different limestone facies varies from pure (221 ppm,

n= 25) to impure limestones (224 ppm, n=6) at Mannersdorf,

recording Sr/Ca ratios with an average of 1/1845. Interes-

tingly, the arsenic (As) content in siliciclastic samples is

variable and ranges from low (9.6 ppm) to high (136.6 ppm)

contents. In contrast As content in the limestones is conside-

rably lower.

Rock type

Underlying clastics

n=3

Intercalated clastics

n= 5

Pure limestone

dominated by calcite

n= 8

Pure limestone with

minor quartz

n= 17

Impure limestone with

clay minerals

n= 6

Limestone with minor

dolomite

n=2

SiO

54.46 ± 11.6

47.2 ± 21.8

0.34 ± 0.21

1 ± 0.43

3.68 ± 1.56

0.86 ± 0.26

5.05 ± 2.99

13.92 ± 5.11

0.1 ± 0.07

0.31 ± 0.14

1.19 ± 0.58

0.24 ± 0.07

1.65 ± 0.1

4.71 ± 2.24

0.06 ± 0.04

0.13 ± 0.06

0.57 ± 0.15

0.1 ± 0.01

MgO

0.4 ± 0.2

1.18 ± 0.52

0.34 ± 0.02

0.31 ± 0.1

0.47 ± 0.12

0.94 ± 0.52

CaO

18.69 ± 7.8

12.76 ± 16.3

55.47 ± 0.8

54.76 ± 0.53

51.56 ± 1.23

54.2 ± 0.28

0.19 ± 0.22

0.28 ± 0.34

–

0.02

–

0.81 ± 0.52

2.25 ± 1.05

0.02 ± 0.01

0.05 ± 0.03

0.21 ± 0.11

0.03 ± 0.01

MnO

0.02 ± 0.01

0.05 ± 0.04

–

0.05 ± 0.03

0.01

LOI

18.27 ± 6.89

16.3 ± 11.7

43.59 ± 0.66

43.34 ± 0.27

42.1 ± 1.1

43.5 ± 0.14

24.37 ± 6.57

80.6 ± 39.97

1.88 ± 0.95

2.65 ± 1.24

10.55 ± 6.54

3.55 ± 1.91

2.63 ± 0.35

10.12 ± 6.63

0.47 ± 0.26

0.61 ± 0.38

1.6 ± 0.85

–

69.2 ± 25.9

–

111.8 ± 31.6

101± 35.4

–

5.7 ± 9.1

–

46.3 ± 13.2

114.6 ± 45.3

9 ± 3.2

15.7 ± 2.7

23.17 ± 6.24

18.5 ± 3.53

367.2 ± 424.6

138.2 ± 55.8

279. 6 ± 40.9

208.4 ± 22.45

195.4 ± 59.3

170. 5 ± 37.3

35.37 ± 30.17

103 ± 56.65

0.79 ± 0.53

2.2 ± 1.06

7.9 ± 4.49

1.8 ± 0.57

12.2 ± 15.77

12.9 ± 7.99

0.18 ± 0.1

0.29 ± 0.18

1.27 ± 0.53

0.35 ± 0.07

222 ± 141

610 ± 371

10.5 ± 2.67

18 ± 9.69

220.5 ± 323.4

119.5 ± 135.1

3.67 ± 0.7

13.66 ± 5.7

0.51 ± 0.2

0.76 ± 0.37

2.23 ± 0.5

0.6 ± 0.14

99.7 ± 37.7

175.3 ± 82.5

3.35 ± 0.65

4.68 ± 1.69

17.75 ± 7.75

10.15 ± 0.35

4.9 ± 1.5

25.68 ± 10.3

0.9 ± 0.15

1.61 ± 0.38

14.83 ± 19. 55

2.1 ± 0.28

4.17 ± 2.28

12.36 ± 5.21

–

0.2 ± 0.07

0.62 ± 0.53

–

2.53 ± 0.75

4.74 ± 2.08

0.1 ± 0.5

0.15 ± 0.08

0.47 ± 0.23

0.1

1.8 ± 1.28

11.74 ± 5.44

0.2 ± 0.07

0.35 ± 0.2

0.98 ± 0.46

0.2

1.3 ± 0.36

9.78 ± 7.33

1.18 ± 0.43

2.86 ± 1.5

4.6 ± 2.6

3.5 ± 0.28

6.9 ± 4.78

27.7 ± 15.31

0.98 ± 0.29

1.62 ± 0.52

4.57 ± 1.22

0.95 ± 0.21

13.53 ± 10.77

54.4 ± 27.77

1.33 ±0.36

2.45 ± 0.81

9.02 ± 2.46

1.45 ± 0.07

1.53 ± 1.26

6.71 ± 3.29

0.13 ± 0.04

0.29 ± 0.1

1.05 ± 0.31

0.19 ± 0.02

6.13 ± 5.24

27.1 ± 12.53

0.65 ± 0.23

1.19 ± 0.4

4.58 ± 1.48

0.75 0.35

1.1 ± 1.01

5.53 ± 2.47

0.11 ± 0.05

0.21 ± 0.07

1 ± 0.48

0.16 ± 0.04

0.36 ± 0.26

1.12 ± 0.51

0.03 ± 0.02

0.05 ± 0.02

0.33 ± 0.2

0.06 ± 0.01

1.24 ± 0.8

5.17 ± 2.16

0.13 ± 0.02

0.24 ± 0.07

1.7 ± 1.47

0.28 ± 0.01

0.2 ± 0.12

0.8 ± 0.37

0.02 ± 0.01

0.04 ± 0.01

0.3 ± 0.3

0.05 ± 0.01

1.11 ± 0.59

4.48 ± 1.89

0.12 ± 0.04

0.22 ± 0.05

1.88 ± 2.03

0.32

0.21 ± 0.07

0.91 ± 0.39

0.03 ± 0.01

0.05 ± 0.01

0.43 ± 0.5

0.07 ± 0.01

0.57 ± 0.18

2.4 ± 1.13

0.1 ± 0.04

0.14 ± 0.04

1.24 ± 1.5

0.2 ± 0.06

0.09 ± 0.03

0.33 ± 0.18

0.02 ± 0.01

0.18 ± 0.23

0.03

0.6 6 ± 0.17

2.13 ± 1.13

0.08 ± 0.04

0.12 ± 0.03

1.16 ± 1.52

0.17 ± 0.01

0.11 ± 0.03

0.33 ± 0.17

0.02 ± 0.01

0.2 ± 0.25

0.03

Ce/Ce*

0.94 ± 0.04

0.93 ± 0.02

0. 84 ± 0.18

0.91 ± 0.07

0. 95 ± 0.08

0.92

Eu/Eu*

1.38 ± 0.16

0.98 ± 0.1

1.56 ± 0.76

1.05 ± 0.22

1.16 ± 0.17

1.13 ± 0.09

ΣREEs

33.74 ± 24.76

139.1 ± 68.9

3.59 ± 0.93

6.65 ± 1.98

27.61 ± 9.79

4.7 ± 0.18

(La/Yb)

0.74 ± 0.42

0.94 ± 0.07

0.92 ± 0.39

0.99 ± 0.2

0.65 ± 0.41

0.42 ± 0.08

Y/Ho

23.24 ± 1.2

28.5 ± 1.8

30.6 ± 9.4

36.7 ± 11.6

33.2 ± 7.4

30.2 ± 2.1

* oxides in wt. %, elements in ppm and (–) indicates not detected

Table 1: Average chemical compositions* and standard deviations of Mannersdorf Leitha limestones facies types and siliciclastics.

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In the Wöllersdorf samples the minor element concentra-

tions are still low without major variations between the two

lithofacies and similar to those from Mannersdorf quarry,

except for Sr which is lower in the lithofacies containing

dolomite with an average value of 141.5 ppm, with Sr/Ca ratio

of 1/2412, and the other lithofacies has an average value of

253 ppm and Sr/Ca ratio of 1/1506.

In general minor elements in the Kummer samples are again

low except for Sr. Unlike the Mannersdorf and Wöllersdorf

samples, Sr content is higher in the Leitha limestones litho-

facies with an average of 571 ppm (n=23). The Sr/Ca ratio in

this locality also differs significantly from Mannersdorf and

Wöllersdorf, with average value of 1/716. The average

value in the intercalated marly facies is 360 ppm. The Sr

content at Fertőrákos averages 629 ppm and Sr/Ca ratio of

1/613.

The Rosenberg samples show high Sr contents compared to

the other localities not only in the Leitha limestones but also in

surrounding siliciclastics. The average content in limestones

(both pure and impure, n=4) equals 1271 ppm with Sr/Ca ratio

average of 1/301, while Sr in the tuff layer has a value of

1074.1 ppm.

Rock type

Wöllersdorf impure

limestones with

clays

n=3

Wöllersdorf impure

limestones with

dolomite

n=3

Kummer pure

limestones

n= 23

Kummer marls

n= 4

Kummer

siliciclastics

n=3

Fertőrákos pure

limestones

n= 3

SiO

2.38 ± 1.46

2.96 ± 1.45

0.61 ± 0.2

8.7 ± 1.53

26.73 ± 9.02

1.78 ± 0.44

0.75 ± 0.41

0.52 ± 0.13

0.14 ± 0.06

3.18 ± 0.48

9.12 ± 2.59

0.27 ± 0.08

0.21 ± 0.1

0.22 ± 0.05

0.28 ± 0.17

0.9 ± 0.2

3.26 ± 2.06

0.09 ± 0.01

MgO

0.64 ± 0.01

4.7 ± 2.9

0.61 ± 0.06

0.75 ± 0.12

1.69 ± 0.3

0.57 ± 0.03

CaO

53.21 ± 1.31

47.26 ± 4.38

54.35 ± 0.45

46.11 ± 1.18

27.81 ± 9.11

53.97 ± 0.31

0.01

0.03 ± 0.01

0.04 ± 0.01

0.1 ± 0.02

0.08 ± 0.03

0.13 ± 0.07

0.1 ± 0.03

0.03 ± 0.01

0.56 ± 0.07

1.61 ± 0.46

0.0.3 ± 0.01

MnO

–

0.06 ± 0.05

0.13 ± 0.14

0.02 ± 0.01

0.05 ± 0.02

LOI

42.47 ± 0.78

43.1 ± 0.21

43.75 ± 0.24

39.3 ± 1.12

28.8 ± 5.68

42.97 ± 0.23

1.43 ± 0.29

1.7 ± 0.7

1.7 ± 1.3

3 ± 2.76

159.8 ± 260.4

0.77 ± 0.06

0.53 ± 0.25

0.4 ± 0.14

0.42 ± 0.25

0.98 ± 0.32

6.97 ± 5.58

0.25 ±0.15

2.93 ± 1.27

4.03 ± 0.32

1.99 ± 1.45

3.08 ± 1.08

46.87 ± 43.89

0.83 ± 0.4

–

25.66 ± 6.55

68.42 ±23.7

–

011 ± 0.03

0.07 ± 0.01

11.33 ± 5.17

30.75 ± 2.36

94.67 ± 40.51

15.33 ± 5.77

253.2 ± 15.5

141.5 ± 24.6

570. 7 ± 139

196.6 ± 53.4

359.8 ± 113.1

629 ± 45

5.97 ± 2.82

3.93 ± 1.03

1.31 ± 0.53

29.63 ± 3.18

91.33 ± 30.33

1.57 ± 0.35

0.43 ± 0.23

0.33 ± 0.16

0.21 ± 0.17

3.98 ± 0.62

14.13 ± 5.69

0.23 ± 0.06

18 ± 7.8

9 ± 1

20.57 ± 4.07

70.25 ± 3.3

170.3 ± 47.4

17.33 ± 0.58

0.9 ± 0.2

1.1 ± 0.26

1 ± 0.33

1.8 ± 0.39

9.1 ± 6.97

0.7

16.93 ± 7.03

22.63 ± 13.75

3.71 ± 2.65

50.8 ± 58.4

59.8 ± 17.15

6.4 ± 4.9

2.6 ± 0.72

2.77 ± 0.59

6.15 ± 1.15

7.7 ± 1.2

18.57 ± 5.74

6.2 ± 0.4

0.8 ± 0.46

0.37 ± 0.21

0.25 ± 0.07

2.2 ± 0.59

6.6 ± 1.9

–

0.47 ± 0.21

0.6 ± 0.36

0.15 ± 0.08

1.4 ± 1.41

1.7 ± 0.52

–

0.6 ± 0.26

0.67 ± 0.12

0.44 ± 0.16

2.5 ± 0.45

7.53 ± 2.48

0.43 ± 0.06

1.63 ± 0.78

1.7 ± 0.44

1.97 ± 0.47

2.18 ± 1.06

3.9 ± 1.51

1.3 ± 0.26

2.4 ± 1.13

2.7 ± 0.5

3.76 ± 0.73

8.33 ± 0.92

22.53 ± 7.19

3.33 ± 0.25

4.57 ± 2.63

4.8 ± 0.87

4.46 ± 1.01

14.43 ± 1.96

43.17 ± 15.74

4.1 ± 0.4

0.54 ± 0.27

0.59 ± 0.12

0.72 ± 0.14

1.78 ± 0.25

5.03 ± 1.59

0.69 ± 0.05

2.17 ± 1.16

2.37 ± 0.58

3.18 ± 0.63

7.08 ± 1.24

19.23 ± 6.19

3 ± 0.1

0.44 ± 0.24

0.5 ± 0.15

0.65 ± 0.14

1.35 ± 0.28

3.72 ± 1.07

0.62 ± 0.08

0.09 ± 0.06

0.1 ± 0.03

0.16 ± 0.3

0.31 ± 0.05

0.83 ± 0.29

0.17± 0.02

0.43 ± 0.16

0.54 ± 0.07

0.82 ± 0.14

1.33 ± 0.26

3.6 ± 1.3

0.83 ± 0.08

0.07 ± 0.03

0.08 ± 0.02

0.13 ± 0.02

0.21 ± 0.03

0.55 ± 0.19

0.12 ± 0.01

0.44 ± 0.19

0.45 ± 0.11

0.79 ± 0.15

1.2 ± 0.21

3.08 ± 1.03

0.81 ± 0.09

0.08 ± 0.03

0.09 ± 0.02

0.16 ± 0.02

0.22 ± 0.03

0.59 ± 0.22

0.16 ± 0.03

0.23 ± 0.08

0.27 ± 0.06

0.47 ± 0.08

0.67 ± 0.12

1.67 ± 0.52

0.46 ± 0.05

0.03 ± 0.01

0.04 ± 0.01

0.06 ± 0.01

0.095 ± 0.01

0.23 ± 0.08

0.06 ± 0.01

0.2 ± 0.09

0.23 ± 0.08

0.38 ± 0.07

0.58 ± 0.07

1.51 ± 0.45

0.38 ± 0.09

0.04 ± 0.01

0.06 ± 0.01

0.1 ± 0.01

0.22 ± 0.06

0.06 ± 0.01

Ce/Ce*

0.9 ± 0.08

0.87 ± 0.07

0.62 ± 0.05

0.86 ± 0.02

0.92 ± 0.04

0.62 ± 0.01

Eu/Eu*

0.88 ± 0.26

0.91 ± 0.19

1.02 ± 0.09

1.08 ± 0.1

1.05 ± 0.04

1.09 ± 0.17

ΣREEs

11.72 ± 6.07

12.8 ± 2.5

15.79 ± 2.91

37.67 ± 5.24

106 ± 35.9

14.8 ± 0.98

(La/Yb)

0.88 ± 0.04

0.9 ± 0.14

0.74 ± 0.1

1.06 ± 0.03

1.1 ± 0.04

0.66 ± 0.13

Y/Ho

33 ± 1.7

31 ± 2.2

38.56 ± 3.05

34.6 ± 2.8

31.7 ± 2

39 ± 4.7

* oxides in wt. %, elements in ppm and (–) indicates not detected

Table 2: Average chemical compositions* and standard deviations of Wöllersdorf, Kummer and Fertőrákos Leitha limestones facies types and

Kummer siliciclastics.

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REEs patterns

In the Mannersdorf samples the overall concentration of the

REEs in the carbonate facies in general is lower and varying

due to the clay content compared to the intercalated clastics

with contents higher than 110 ppm. The average ƩREEs is

5.7 ppm (n=25) in the absence of clays (pure limestones)

while this average is enhanced due to the presence of clays to

27.6 ppm (n=6). The total REEs value is strongly positive

correlated to Al

wt. % (r=0.95), as well as Zr (r = 0.92);

on the other hand, it is negatively correlated to CaO wt. %

(r = − 0.84). PAAS normalized REEs patterns of the inter-

calated clastics are flattened and show average shale patterns

(Fig. 5a). PAAS (Taylor & McLennan 1985) normalized REEs

patterns of limestones facies from Mannersdorf are almost flat

with negative Ce anomaly in pure limestones (Fig. 5b, c)

but this anomaly is less pronounced in impure limestones

(Fig. 5d). The LREEs/HRREs ratio is marked by the (La/Yb)

ratio which has an average value around 1 (i.e. 0.97, n=30),

apart from some samples which exhibit HREEs enrichment

with an average value of 0.45 (n=9).

The total REEs content in Wöllersdorf samples averages

12.3 ppm (n=6). The PAAS normalized RREs patterns are

nearly flat (Fig. 6a) with low LRREs/HRREs ratio indicated

by (La/Yb)

ratio ranging from 0.74 to 0.99 with an average

of 0.86.

Table 3: Average chemical compositions* and standard deviations of Rosenberg Leitha limestones facies types and siliciclastics.

Rock type

Rosenberg lower

siliciclastics

n=2

Rosenberg pure

limestones

n=2

Rosenberg impure

limestones

n=2

Rosenberg tuff layer

Rosenberg upper

siliciclastics

n= 4

SiO

25 ± 0.23

0.25 ± 0.04

2.24 ± 0.22

16.93

41.42 ± 7.47

4.78 ± 1.71

0.06 ± 0.04

0.75 ± 0.07

5.73

8.93 ± 4.08

3.06 ± 0.35

0.06 ± 0.03

0.35 ± 0.01

3.57

3.88 ± 1.34

MgO

2.42 ± 0.04

0.64 ± 0.07

1.81 ± 0.93

8.31

4.17 ± 1.32

CaO

32.96 ± 6.33

55.1 ± 0.54

51.4 ± 1.3

29.91

17.86 ± 9.05

0.63 ± 0.23

0.02

0.07 ± 0.01

0.44

0.99 ± 0.18

1.17 ± 0.36

0.02 ± 0.01

0.16 ± 0.03

1.26

1.91 ± 0.86

MnO

0.04

–

0.01

0.02

0.09 ± 0.07

LOI

28.95 ± 4.45

43.6 ± 0.42

42.85 ± 0.07

32.7

19.85 ± 5.6

5.05 ± 1.63

1.3 ± 0.42

1.85 ± 0.5

68.8

6.25 ± 2.92

7.1 ± 2.97

0.65 ± 0.07

1.15 ± 0.35

4.6

10.1 ± 5.52

20.95 ± 5.02

0.5-

3.2 ± 1.13

47.28 ± 26.64

75.26 ± 9.68

–

123.2

148.8 ± 22.6

39.5 ± 9.19

–

15 ± 1.4

78 ± 38

750 ± 110

1378 ± 229

1164 ± 325

1074.1

518 ± 360

43.1 ± 12.3

0.8 ± 0.28

7.1 ± 0.42

48.5

73.1 ± 38.5

2.5 ± 0.28

0.2

0.6

4.63 ± 2.59

187.5 ± 105.4

20.5 ± 2.12

43.5 ± 13.4

206

285.3 ± 113

6.75 ± 3.6

0.95 ± 0.07

1.3 ± 0.28

25.7

7.45 ± 4.26

68.4 ± 11.6

1.3 ± 0.28

8.85 ± 0.21

78.4

137.1 ± 56.1

13.95 ± 6.01

2.65 ± 0.07

2.95 ± 0.21

19.8

20.9 ± 7.2

5.75 ± 2.62

–

0.65 ± 0.07

6.7

9.1 ± 4.24

1.75 ± 0.35

–

0.2

3.73 ± 1.43

4.1 ± 1.9

–

0.7 ± 0.14

7.4

6.08 ± 3

2.6 ± 1.6

1.2 ± 0.71

2.25 ± 1.77

9.5

3.28 ± 1.23

14.95 ± 6.15

1.4 ± 0.28

3.05 ± 0.21

18.2

22 ±9.01

29.5 ± 12.73

1.85 ± 0.07

5.05 ± 0.07

37.3

43.38 ± 18.36

3.28 ± 1.36

0.27 ± 0.02

0.63

4.64

5.11 ± 2.29

12.75 ± 6.01

1.15 ± 0.07

2.45 ± 0.49

18.7

19.3 ± 9

2.58 ± 1.36

0.22 ± 0.01

0.48 ± 0.08

3.79

3.99 ± 1.83

0.62 ± 0.28

0.08

0.12 ± 0.02

0.86

0.86 ± 0.35

2.64 ± 1.3

0.26

0.49 ± 0.04

3.7

3.67 ± 1.51

0.41 ± 0.18

0.06 ± 0.01

0.08 ± 0.01

0.57

0.6 ± 0.28

2.34 ± 1.2

0.29 ± 0.01

0.45 ± 0.01

3.16

3.55 ± 1.31

0.47 ± 0.18

0.07 ± 0.01

0.1 ± 0.01

0.62

0.7 ± 0.24

1.31 ± 0.64

0.22 ± 0.01

0.27 ± 0.02

1.63

2.09 ± 0.74

0.18 ± 0.08

0.03 ± 0.01

0.05 ± 0.01

0.21

0.3 ± 0.11

1.21 ± 0.57

0.19 ± 0.04

0.22 ± 0.01

1.41

1.96 ± 0.74

0.2 ± 0.08

0.02

0.04 ± 0.01

0.22

0.29 ± 0.1

Ce/Ce*

0.96 ± 0.02

0.7 ± 0.08

0.84 ± 0.04

0.93

0.94 ± 0.01

Eu/Eu*

1.13 ± 0.05

1.58 ± 0.03

1.13 ± 0.35

1.07

1.06 ± 0.04

ΣREEs

72.42 ± 32.14

6.09 ± 0.33

13.44 ± 0.29

95.01

107.8 ± 45.6

(La/Yb)

0.93 ± 0.13

0.54 ± 0.01

1.04 ± 0.04

0.95

0.83 ± 0.17

Y/Ho

29.4 ± 1.3

39 ± 8.8

31 ± 0.08

29.8 ± 1.99

* oxides in wt. %, elements in ppm and (–) indicates not detected

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Pure limestone facies from Kummer have PAAS normalized

REEs patterns which resemble seawater patterns with negative

Ce anomaly and HREEs/LREEs enrichment (Fig. 6b). The total

REEs content in this facies has an average of 15.8 ppm (n=23),

this content has very weak negative correlation with Zr

(r = − 0.05), weak positive correlation with Al

with r =0.27

and weak negative correlation with CaO with r = − 0.21. The

(La/Yb)

ratio average of this facies is 0.74. The pattern shape

in the marly facies is characterized by MREEs enrichment

(Fig. 6c) and the REEs content is higher than in the limestones

facies with average values of 37.7 ppm, as well as the (La/Yb)

ratio average of 1.1. The clastic facies has a flat pattern

(Fig. 6c) with the highest concentration among the facies in

Kummer, with average REEs content of 106 ppm and (La/Yb)

ratio average of 1.1. Fertőrákos pure limestones exhibit

a simi lar REEs pattern to those from Kummer (Fig. 6d)

with average content of 14.8 ppm and (La/Yb)

ratio average

of 0.66.

The Rosenberg limestones show two REEs patterns: (1) for

two samples in contact with siliciclastics there is a flat pattern

with average 13.4 ppm and (La/Yb)

ratio average of 1.04 and

a seawater like REEs pattern with pronounced Ce anomaly

and REEs average content of 6.09 ppm and HREEs enrich-

ment indicated by (La/Yb)

ratio average of 0.54 (Fig. 7a);

(2) the REEs patterns of the underlying and overlying layers

and the intercalated tuff layer are flat with MREEs enrich-

ments and (La/Yb)

ratio average of 0.9 (Fig. 7b).

Ce anomaly

In Mannersdorf the values of the anomaly in the various

rock types are approximately the same, the average value in

pure and impure limestones is 0.9 (n= 33). Samples from

Wöllersdorf have Ce/Ce* values close to those of the Manners-

dorf average of 0.88. The Kummer pure limestones facies has

an average Ce anomaly of 0.62, while the marly facies has

a higher average of 0.86 and the highest average value is

recorded in the intercalated clastics where it reaches 0.92.

The average Ce anomaly in limestones from Fertőrákos is also

0.62. Pure limestones from Rosenberg quarry have average Ce

anomaly value of 0.7 (n= 2) while the average value of the

impure facies is 0.84 (n=2).

Fig. 5. PAAS-normalized REEs pattern of various rock types from Mannersdorf: a — clastic samples including lower siliciclastics and inter-

calated ones; b — pure limestone samples composed mainly of calcite; c — pure limestones composed of calcite and quartz; d — impure Leitha

limestones with muscovite and clays.

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from the Rosenberg quarry have averages of 1.6 and 1.13,

respectively.

Y/Ho ratio

The average Y

mol

/Ho

mol

ratio of pure and impure limestones

from Mannersdorf are approximately the same 34 and 33,

respectively. In Wöllersdorf the limestone lithofacies contai-

ning dolomite has an average value of 31 which is lower than

the average value in the lithofacies dominated by calcite with

clays where it equals 33. In the Kummer pure limestones

facies the average value is 39 and in the marly facies the ratio’s

average is 35. The limestones from Fertőrákos have exactly

the similar ratios as the Kummer limestones. At Rosenberg

the Y/Ho ratio averages 35 (31– 45) in both pure and impure

limestone facies.

Discussion

Factors controlling mineralogy

The Leitha limestones studied here have slightly different

mineralogical compositions according to the sampling locality

and its regional substratum geology. Samples from Manners-

dorf and Wöllersdorf show the effect of intermittent silici-

clastic input during limestone deposition as indicated by the

presence of quartz and clay minerals, as well as the effect of

diagenesis which led to the formation of dolomite. Various

types of pure to impure limestones can be recognized in all the

studied localities. Major impurities are quartz, clay minerals

and other phyllosilicates, and feldspar (e.g. microcline),

reworked and incorporated from adjacent basement complexes

and derived from riverine input. The source of pyrite and

barite in some samples may be related to the degradation of

organic matter during the early stages of diagenesis which

provides sulphur for the formation of such minerals in oxic to

suboxic environments (Schieber 2011; Arndt et al. 2013).

In pure limestones from Kummer and Fertőrákos, the pre-

dominance of calcite and the sole abundance of clastic mine-

rals (e.g., quartz and clay minerals) are also related to the role

of erosion and reworking of pre-existing limestones in subaerial

and shallow water conditions,

as a result of reduced marine

conditions and/or lowered sea level. This scenario is based on

the deposition of sands, gravels and hydrodynamically con-

trolled “detritic” Leitha limestones by Gilbert-type deltas in

the Eisenstadt-Sopron Basin (Rostá 1993; Wiedl et al. 2014).

Limestones from Rosenberg show detrital input signals espe-

cially in the impure limestone samples collected near the con-

tact with underlying and overlying siliciclastics. Magmatic

activity certainly played a role in affecting carbonate sedimen-

tation in the studied area (Reuter et al. 2012). Mineralogically,

dolomite formation in those limestones is related to the pre-

sence of intervening tuff layers, which are originally rich in

Mg, acting as the primary source for dolomitization during

early diagenesis.

Geochemistry

Major elements

Generally, CaO wt. % in the studied limestones varies in

reverse relation to SiO

and Al

which clearly indicates the

effect of siliciclastic input and thus detrital dilution of carbo-

nates during deposition. Al

is used as a proxy for clay

content in limestones (Nothdurft et al. 2004), and the average

contents of 1.2 wt. % in impure limestones from Mannersdorf

confirms their classification as shale-contaminated (average

value for siliciclastic-contaminated carbonates is 0.42 wt. %,

Veizer 1983). The same feature applies at Wöllersdorf with

wt. % average of 0.63. On the other hand, pure lime-

stones from Kummer and Fertőrákos do not show any signifi-

cant siliciclastic contamination as indicated by Al

contents

below 0.37 wt. %. At Rosenberg, the two samples in contact

with the underlying and overlying siliciclastics have Al

contents of 0.7 and 0.8 wt. %, respectively, giving an indica-

tion of the contamination, while the two limestone samples

further away from the contact and in the middle of the outcrop

do not show a similar trend and can be classified as pure lime-

stones with an Al

wt. % average of 0.06.

Minor elements

The Leitha limestones exhibit a significant variation in Sr

content, with a general increase towards the South of the

studied Austrian basins (Fig. 8). Although Sr values are lower

than the average global carbonate value (610 ppm, Mielke

1979), the Sr content in the different limestone facies at

Mannersdorf is the highest among the various rock types in

that area with an average of 231 ppm. The Sr/Ca ratio in

carbonates is used as a proxy to track the variations in sea-

water Sr/Ca ratio (e.g., Ullmann et al. 2016) and the diagenesis

(e.g., Ando et al. 2006). The Sr/Ca ratio with an average of

1/1845 in all the Leitha limestones samples is higher than the

mean value given by Kulp et al. (1952) which should be less

than 1/1000 in most types of limestone. The lowest content is

recorded in Mannersdorf and Wöllersdorf with a maximum

value of 352 ppm. The Sr is favoured to be incorporated into

aragonite rather than calcite, but this Sr is lost during diage-

netic transformation of the metastable aragonite into the stable

calcite (Morse & Mackenzie 1990).

Two main causes of low Sr content in limestones from

Mannersdorf and Wöllersdorf are proposed here. First, the main

constituents of these limestones are corallincean red algae and

foraminifers which are, mineralogically, high-Mg calcites

(Scholle & Ulmer-Scholle 2003), more prone to low Sr con-

tents. Second, the release of Sr to pore water during recrystalli-

zation of calcite (Baker & Bloomer 1988) reduces the Sr content

of the deposits. Although, additional diagenetic studies should

be carried out on these localities, we favour the second explana-

tion because Leitha limestones with largely similar composi-

tion, for instance, from the Kummer quarry have higher Sr con-

tents with slight upward increase due to diagenesis (Fig. 9).

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The highest Sr content is recorded in samples from the Styr-

ian basin (i.e. Rosenberg samples) not only in the limestones,

but also in the siliciclastics except for two samples. This basin

suffered volcanism with a wide spectrum of magmatic rocks

during the Neogene to Quaternary evolution of the Carpathi-

an-Pannonian region (Harangi et al. 2006; Seghedi & Downes

2011, Ali & Ntaflos 2013). Volcanic activity may have played

a role in a higher primary Sr content of regional Badenian wa-

ter masses, and thus may be preserved in limestones from the

Rosenberg quarry. Scleractinian corals (e.g. Porites and Tar-

bellastraea, Riegl & Piller 2000) which are aragonitic (Schol-

le & Ulmer-Scholle 2003) could also account for parts of the

higher Sr content.

REEs patterns

The total REEs contents in the pure and impure samples

from Mannersdorf and impure samples from Wöllersdorf and

their strong positive correlation with terrigenous proxies such

as Al

and Zr (Fig. 10) indicates the influence of the detrital

input during sedimentation on the total REEs content. Zr is

used as a terrigenous input proxy due to its resistance to

weathering and alteration processes (Taylor & McLennan

1985) besides its low abundance in seawater (Boswell & El-

derfield 1988) and the single valency state prevents the effect

of the changing redox conditions during deposition (Calvert et

al. 1996). The stratigraphic distribution of the REEs content at

Mannersdorf does not show a clear relationship between the

facies type and REEs concentration (Fig. 10). The PAAS nor-

malized REEs patterns of all the Leitha limestones facies are

flat in shape and display a non-seawater like pattern due to the

effect of clay admixture. These flat patterns are similar to the

patterns of shales which represent the original source of the

REEs in the ocean (Elderfield 1988). There is no strong cor-

relation between REEs content and detrital proxies such as

and Zr (r=0.27 and −0.05, respectively) in Kummer

pure limestones samples supporting the idea that these sam-

ples are not contaminated by siliciclastics and retain the (orig-

inal) seawater signal better. The REEs contents in the studied

facies types do not vary and have a limited range (Fig. 11).

Also, REEs patterns in these samples and at Fertőrákos show

seawater-like shale normalized REEs patterns, characterized

by HREEs enrichment shown by the low (La/Yb)

ratio (ave-

rage 0.74 for 23 samples), a negative Ce anomaly (average =

0.6) , and a high (Y/Ho)

mol

ratio (average = 39). These patterns

are interpreted as preserving the primary sedimentary environ-

mental signal of marine water under oxic conditions (Haley et

al. 2004).

Both REEs pattern types exist in the Rosenberg samples,

where impure samples in contact with the underlying and

overlying siliciclastic and contaminated with shale have flat

non-seawater like patterns with (La/Yb)

of average 1.04

(n=2), higher REEs content (average 13.4 ppm), lower (Y/Ho)

mol

ratio of average 31 and Ce anomaly of 0.84. On the other hand,

the pure limestones samples are significantly different,

displaying seawater-like patterns with HREEs enrichment

with (La/Yb)

of average 0.54 (n=2), lower REEs content of

average 6.1 ppm, higher (Y/Ho)

mol

ratio of average 39 and Ce

anomaly of 0.7. The latter two samples suggest deposition of

Fig. 8. Sr content of Leitha limestones from all localities, showing

increasing values in Eisenstadt-Sopron (Kummer and Fertőrákos) and

Styrian (Rosenberg) basins compared to the Vienna Basin (Manners-

dorf and Wöllersdorf).

Fig. 9. Stratigraphic distributions of Sr content in the Kummer quarry

with an increase upward, while Y/Ho ratio is almost the same in all

samples (colours of facies after Schmid et al. 2001).

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the Rosenberg limestones under oxic conditions whereas more

impure samples indicate a masking of the primary environ-

mental (seawater) signal by siliciclastic contamination.

To test for the REEs elements pattern source three single-

component samples were selected (cement, oyster shell, and

pectinid shell) to be compared to the whole rock chemical

analyses of the same parental samples. The cement fraction

(sample M14/43) does not show a diverging total REEs con-

tent compared to the whole rock sample (5.28 vs. 5.73 ppm,

respectively) but the Ce anomaly is different with a lower value

of 0.62 in the cement fraction compared to 0.86. The REEs

pattern in the cement fraction is more similar to the seawater-

like pattern than the sample itself, with HREEs enrichment

(i.e. (La/Yb)

value of 0.2), this ratio is 0.52 in the sample

(Fig. 12a) and higher Y/Ho ratio of 27 and 23 for the whole

sample. These relations give a hint of oxic marine conditions

and cement precipitation from seawater trapped in pores

during early diagenesis.

In samples from Kummer the total REEs content is lower in

the biogenic fractions compared to the whole rock sample

(3.22 and 2.78 ppm vs. 12.96 and 13.8 ppm in the whole rock

samples). The REEs patterns in the whole rock samples are

better defined than in the biogenic material (Fig. 12b) which

can be explained by the lack of some

elements such as Dy and Tm and the

low elements contents of these frac-

tions. The Ce anomaly is lower in the

oyster shell (0.5 vs. 0.65 in the whole

rock sample), a reverse situation to

the pectinid shell where it is higher

than the whole sample (0.59 vs. 0.52,

respectively). Also, the Y/Ho ratio

shows no clear trend from the shells

versus the whole rock samples.

Ce anomaly

The Ce anomalies in limestones

from Mannersdorf and Wöllersdorf

are close to 1, and thus differ from

seawater values (0.1– 0.4). This can be

explained by (1) the minor presence

of clay minerals (from detrital input)

in the pure and impure samples which

is identified in all samples based on

XRD analysis but to some extent by

using SEM; (2) the release of LREEs

due to the degradation of the organic

matter including Ce in the few centi-

metres depth of the sediment column

below the sea floor. Haley et al (2004)

showed that in oxic environments the

remineralization of organic coatings

results in a balancing of the Ce ano-

maly to the value of the source mate-

rial. Moreover, the presence of pyrite

and barite supports such a conclusion by postulating that the

organic matter was the source for sulphur (Schieber 2011;

Arndt et al. 2013). The Ce anomaly record is different at

Kummer and Fertőrákos, displaying considerably lower values

(average 0.62) than at Mannersdorf and Wöllersdorf. This

indicates primary seawater values and conforms to an inter-

pretation of an oxic depositional environment, characterized

by the lack of detectable detrital input which may have been

removed during reworking and redeposition of the predomi-

nating detrital limestones from these localities. At Rosenberg,

two ranges of Ce anomalies exist which indicate significant

detrital input in impure limestones resulting in higher values

whereas the lower values in pure limestones record primary

oxic conditions.

Y/Ho ratio

The ratio of yttrium (Y) versus holmium (Ho) in the studied

limestones samples is nearly similar in all the studied locali-

ties. The values are slightly higher in samples exhibiting low

or no siliciclastic input (≥ 35 in relatively pure limestones)

compared to samples with siliciclastic admixture (29 –35 in

impure limestones). The values indicate in general deposition

Fig. 10. Stratigraphic distributions of Al

, REEs and Zr at Mannersdorf with strong correlation

between the three parameters (colours of facies after Wiedl et al. 2012).

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under oxic conditions. Due to the simi-

larity in ionic radii of Y and Ho the ex-

pected oceanic distributions are closely

similar (Zhang et al. 1994; Bau et al.

1995). Nevertheless, their different geo-

chemical behaviour results in strong

frac tionation between the two elements.

The former authors deduced that the Y/Ho

ratios in seawater are approximately

two times higher than the chondritic and

shale ratios. The ratio is also affected

by redox conditions where it decreases

from 102 in oxic to 67 in anoxic waters

as a consequence of preferential sorp-

tion of Ho with respect to Y on Fe- and

Mn-oxyhydroxide particles that even-

tually dissolve under anoxic conditions

(Bau et al. 1997). The fractionation

takes place predominately in the ocean

(Nozaki et al. 1997).

Interpretation of controlling factors

The evidence derived from the

mineralogical compositions and the

above mentioned geochemical proxies

account for the influence of several

factors controlling the sediment geo-

chemistry, notably the trace elements

and RREs. In principle the following

main factors govern the composition of

the Miocene limestones: (1) detrital

admixture from siliciclastics and volcaniclastics, (2) palaeo-

environmental signals from primary seawater composition

and redox states, (3) diagenetic overprint. Detritally-contami-

nated limestones show clear devia tions from the normal sea-

water conditions while the purer limestones point more clearly

to the primary depositional environments if not strongly affec-

ted by diagenesis and later alteration.

Diagenetic evolution

There are significant differences in the diagenetic evolution

between the studied localities. Chemical elements such as Sr,

Na and Ba can be used as indices for the magnitude of diage-

netic overprint, because these elements are generally incorpo-

rated during deposition and redistributed during diagenesis

Fig. 11. Stratigraphic distributions of Al

, REEs and Zr at Kummer with weak positive correla-

tion between REEs and Al

and no correlation between REEs and Zr (colours of facies after

Schmid et al. 2001).

Fig. 12. a — REEs patterns of sample M14/43 from Mannersdorf compared to cement fraction (M14/43Ce) of the same sample, b — REEs

patterns of the biotic fractions (oyster, pectinid shell) compared to the whole samples from Kummer.

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(e.g., Land & Hoops 1973; Brand & Veizer 1980; Morrison &

Brand 1986; Nothdurft et al. 2004; Webb et al. 2009). Here,

the enrichment and/or depletion of these elements are used

only to evaluate the relative degree of diagenesis in the studied

limestones.

Intensive meteoric diagenesis, as expected and demonstra-

ted for these carbonate platforms (Dullo 1983) leads to deple-

tion in elements such as Sr, Na and Ba. The overall Sr content

varies considerably, with low amounts in all limestone sam-

ples from Mannersdorf and Wöllersdorf (averages 221 ppm in

Mannersdorf and 197 ppm in Wöllersdorf), and increasing

from Kummer and Fertőrákos (average 570 ppm) to Rosen-

berg (average 1271 ppm) as shown in Figure 8. This trend

indicates in general that Mannersdorf and Wöllersdorf lime-

stones suffered more intensive diagenesis compared to the

other localities. A similar trend in Na and Ba supports this

idea. Mannersdorf and Wöllersdorf show the lowest values of

these elements (Na not detected in most of the samples, ave-

rage Ba of 15.6 ppm), followed Kummer and Fertőrákos

(average 212.9 ppm Na, average 20.6 ppm Ba) and with the

highest values at Rosenberg (average 315.3 ppm Na, average

43.5 ppm Ba). The above mentioned values for Na and Ba are

derived only from pure limestone samples without visible con-

tamination by detrital input to avoid mixing with the signal

coming from clay minerals. The minimal diagenetic overprint

on limestones from the Rosenberg quarry was previously also

reported on the basis of stable isotopes studies on shell mate-

rial (Bojar et al. 2004). REEs patterns are in accordance with

this interpretation, indicating stronger diagenetic overprint

influencing the palaeoenvironmental signal considerably at

Mannersdorf and Wöllersdorf, whereas at Kummer and Rosen-

berg localities, the original seawater signal is largely preserved.

Provenance

Geological setting and relations to basement rocks at the

studied localities gives the opportunity to evaluate the applica-

bility of various elemental ratios to deduce the possible sources

of siliciclastic input during shallow-water carbonate deposi-

tion. The distributions of immobile elements are used to inter-

pret sediment sources and hinterland geology, for example, La

and Th are enriched in acidic rocks, while Sc, Cr and Co are

enriched in basic rocks (McLennan et al. 1983, 1990; Cullers

2000; Madhavaraju et al. 2010). The resulting elemental ratios

are more affected by the composition of source rocks rather

than the depositional environment (Cullers 1988, 1994).

La/Sc, La/Co, Th/Sc, Th/Co and Th/Cr elemental ratios are

used to evaluate and classify the detrital input sources. Ele-

mental ratios of limestone samples from Mannersdorf and

Kummer containing considerable amounts of detrital materials

and siliciclastic samples from the former localities and Rosen-

berg are shown in Table 4. The Mannersdorf samples exhibit

a wide range of elemental ratios indicating intermediate to

silicic igneous rock sources, while the Kummer and Rosen-

berg samples plot in the range of silicic rocks (Figs. 13, 14).

This conforms to the mainly silicic source material present in

the Austroalpine basement units of the surrounding Alpine

units (e.g., Schuster & Nowotny 2015), namely (meta) grani-

tes, gneisses and mica schists.

Palaeoenvironments

Considering pure (with respect to detrital contamination)

and diagenetically relatively unaltered limestones, Ce and Eu

anomalies can be used as proxies to infer palaeoenvironments,

essentially indicating the redox state during limestone deposi-

tion. In addition, the Mn* values of the Leitha limestone

samples are overall positive indicating deposition under oxic

conditions. On the other hand, some siliciclastic samples from

the three localities show negative Mn* values which point to

(more) reducing depositional environments, in accordance

with intermittently low-oxygen depositional sites and dysoxia

events inferred for certain parts of the Leitha limestone

platforms (Schmid et al. 2001).

Weathering

Weathering indices, related to source rock weathering, were

evaluated here to test the applicability of these methods and to

evaluate the transfer of the weathering signal from the source

to the carbonates. The relative proportions of mobile element

oxides (CaO, Na

O and K

O) to immobile element oxides

Table 4: Range of elemental ratios of Mannersdorf, Kummer and Rosenberg compared to felsic rocks, mafic rocks and PAAS.

Mannersdorf impure

Leitha limestones

n=4

Mannersdorf

siliciclastics

n=8

Kummer

marls

n=4

Kummer

siliciclastics

n=3

Rosenberg

siliciclastics

n=7

Felsic rocks

Mafic rocks

PAAS

La/Sc

0.49–4.4

0.62–3.21

2.87–3.85

2.93–2.95

2.13–3.86

2.5–16.3

0.43–0.86

2.4

La/Co

1.13–3.72

1.12–3.69

6.82–8.63

2.3–5.21

1.9–3.96

1.8–13.8

0.14–0.38

1.65

Th/Sc

0.07–1.2

0.35–1.82

0.87–1.1

0.86–1.03

0.53–1.23

0.84–20.5

0.05–0.22

0.90

Th/Co

0.17–0.94

0.27–1.91

2–4.2

0.78–1.82

0.54–1.61

0.67–19.4

0.04–1.4

0.63

Th/Cr

0.06–0.12

0.07–0.15

0.09–0.11

0.11

0.02–0.07

0.13–2.7

0.018–0.046

0.13

Cr/Th

8–17

7–186

9–11

15–47

4.0–15.0

25–500

7.53

Mn*

0.77–1.06

−0.72–0.21

0.92–1.47

−0.52–0.09

−0.32–0.84

CIA

71.4–72.9

74.7–91.1

83.1–84

83.2–83.6

64.2–72.8

CIW`

93.7–99.1

92.6–99.5

98.8–98.9

84.6–92.9

Cullers (1994, 2000); Cullers & Podkovyrov (2000); Cullers et al. (1988)

Taylor & McLennan (1985)

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(Al

) were used to determine the degree of chemical weathe-

ring, in our study related to weathering of the siliciclastic

admixture in impure limestones; pure limestones cannot be

used for these methods because of the low contents of the

respective elements.

The Mannersdorf impure and Kummer marly limestones

and siliciclastics show uniform, moderate to high degrees of

chemical weathering with CIA values ranging from 71 to 91

(Table 4). Using the A-CN-K (Al

– CaO*+ Na

O –K

ternary plot (Fig. 15), these values approach the muscovite

and illite fields which have CIA values of 75 and 75 to 85,

respectively (Nesbitt & Young 1982). Such values resulted

from the transformation of feldspars (from felsic source rocks

of the Austroalpine basement) into clay minerals along the

transport path and finally deposited in limestones or as inter-

calated layers. In comparison, the Rosenberg samples show

lower values (64–73, Fig. 15) with a low degree of chemical

weathering indicating most probably the influence of the

primarily volcano-siliciclastic input in the Styrian basin with

short transport distance und thus minor weathering. The CIW`

shows a similar trend to CIA among the studied samples

(Table 4). In contrast to impure limestones, the application of

the CIA index in pure limestones (i.e. low Al

content below

0.42 wt. %, for example, in the Kummer limestones) proves

impractical because the obtained values are attributed to low

contents of both mobile and immobile oxides rather than a par-

ticular mineralogy.

Provenance versus palaeoenvironmental signals

Geochemical data from varying sites of Central Paratethys

Middle Miocene carbonate platform limestones allow a testing

of signals according to provenance and/or palaeo-environ-

mental significance. Samples investigated range from pure

limestones (Al

< 0.42 wt. %, CaCO

99 wt. %) to impure

limestones (Al

> 0.42 wt. %, CaCO

< 80 wt.

%, impurities

from quartz, pyrite and evaporites) to siliciclastics (sands,

clays) present as interlayers and below and/or above the lime-

stones. Signals can thus be separated accordingly into those

stemming from siliciclastic admixture, and so mainly influen-

ced by provenance signals carried by the (minor) siliciclastic

fraction, and palaeoenvironmental signals representing origi-

nal sea-water composition — although this signal may also be

indirectly influenced by the surrounding geology via disso-

lution and locally deviating water chemistry within the basins

investigated.

As expected, the provenance signal is the main influence on

various parameters as deduced from similar values going from

impure to more pure limestones. Still, classical provenance

indicators like immobile elemental ratios, CIA and CIW` are

Fig. 13. Th/Co vs La/Sc plot of impure Leitha limestones samples

containing detrital materials and siliciclastic samples from Manners-

dorf (intermediate to silicic), Kummer and Rosenberg (silicic)

quarries (after Cullers 2002).

Fig. 14. La–Th–Sc ternary plot of impure Leitha limestones samples

containing detrital materials and siliciclastic samples from Manners-

dorf (intermediate to silicic), Kummer and Rosenberg (silicic)

quarries (after Cullers 2002).

Fig. 15. A-CN-K ternary plot with the chemical index of alteration

(CIA) of impure limestones, marls and siliciclastics of Mannersdorf,

Kummer and Rosenberg quarries, mineral fields are represented by

kaolinite (Ka), chlorite (Chl), illite (Il), muscovite (Mu), smectite

(Sm), plagioclase (Pl) and K-feldspars (Kfs).

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applicable and interpretable even in impure limestones such as

those from Mannersdorf, which contain considerable amounts

of Al

up to 2.5 wt. % and marly samples from the Kummer

quarry. The high values of the CIA indicate enhanced chemical

weathering in the hinterland due to warm and humid

palaeo climate, and thus compatible with increased detrital

input into the basins (Nesbitt & Young 1982; Zhao &

Zheng 2014).

Furthermore, the stratigraphic evolution at Mannersdorf

with a significant gradual decline in the detrital content (e.g.,

, Fig. 10) upwards coincides with the regional palaeo-

climatic changes in the Central Paratethys region in which

a tropical (Wiedl et al. 2012) to warm-temperate climate

(Mid-Miocene Climatic Optimum) was followed by gradual

temperature decline (Ivanov et al. 2002; Hohenegger et al.

2009; Kováčová et al. 2009). Provenance signals are derived

clearly as a function of the presence of detrital-siliciclastic

material which, by itself, is also a function of weathering,

palaeoclimate and palaeohydrology. The alternative explana-

tion of enhanced detrital input due to tectonic subsidence and

hinterland uplift is unlikely because of the significant decrease

in tectonic activity during the middle to late Badenian (Lee &

Wagreich 2017).

In contrast, only pure limestones with Al

below 0.23 wt. %

give reliable information about their specific depositional

environment and environmental conditions in general. Thus,

palaeo-environmental signals are relatively hard to decipher

especially with increasing shale contamination into the lime-

stones. However, some indices may still work in impure lime-

stones with Mn*, Ce/Ce* and Eu/Eu* especially useful in the

case of separating oxic from low-oxic/anoxic palaeoenviron-

ments. All of these indices generally indicate deposition of the

Leitha limestones under oxic conditions; only exceptional

cases indicate low-oxic/anoxic conditions (e.g., negative Mn*

values), also proven by faunal evidence such as the preserva-

tion of fish remains (Schmid et al. 2001). Other proxies show

normal marine conditions as indicated by “normal” seawater

values without further specifications.

Conclusions

The five studied Middle Miocene Leitha limestone occur-

rences exhibit various mineralogical, geochemical and environ-

mental features. These features can be summarized as follows:

• The limestones were classified into pure limestones with

content below 0.42 wt. % and the absence of clay

minerals while impure limestones have higher Al

and

a detectable amount of clay minerals induced by the detrital

input. Both limestone types exist in the studied localities

with variable abundances.

• Limestones from Mannersdorf and Wöllersdorf (southern

Vienna Basin) are influenced by detrital input during depo-

sition which varies between intermediate to silicic sources

in origin. This input appears in the mineralogy of the lime-

stones which contain quartz and clay minerals in most of the

samples. The input decreased with respect to age, probably

due to the palaeoclimatic change to a slightly cooler climate

during the Middle Miocene. Geochemically, the marine

signal deduced by REEs patterns, Ce anomaly and Y/Ho

ratio is masked by the detrital input in most of the samples.

No clear relationship between facies types and geochemical

characteristics can be deduced due to both significant

detrital input and diagenetic influence.

• The Leitha limestones from Kummer and Fertőrákos

(Eisenstadt–Sopron Basin) are purer with regard to the

detrital input in which no clay minerals were detected. This

criterion makes limestones from these localities excellent

tracers for the primary depositional environments; at the

same time it inhibits clear determination of provenance.

REEs patterns, Ce anomaly and Y/Ho ratio indicate the

deposition of limestones under oxic shallow marine condi-

tions. The origin of the siliciclastics in the marly facies and

in clay layers in Kummer quarry is from silicic igneous

rocks. The palaeoenvironments of these siliciclastics were

oxygen-deficient.

• The limestones from the Rosenberg quarry (Styrian Basin)

were influenced by volcano-siliciclastic events during the

Badenian, displayed by quartz, clay minerals, feldspars and

dolomite especially in samples near the contact with the

siliciclastics. The low degree of chemical weathering evi-

denced by low CIA values also assures the nearby and less

altered volcano-siliciclastic source of the detrital input.

The marine signal of these facies is not obvious due to this

influence, while in the facies away from the contact with

siliciclastics oxic shallow marine conditions represent the

depositional environment. The source of the siliciclastics at

Rosenberg is silicic igneous rocks for both underlying and

overlaying ones.

In general, provenance signals are detectable going from

(siliciclastic) sediments to impure limestones which contain

down to 2.5 wt. %. The source rock signal is thus the

main influence on limestone geochemistry in impure lime-

stones, and classical provenance indicators like immobile

elemental ratios, CIA and CIW` are applicable and interpretable

even in slightly impure limestones. Proxies for reconstructing

environmental conditions during deposition are mainly indices

that may separate oxic from low-oxic/anoxic palaeoenviron-

ments like Mn*, Ce/Ce* and Eu/Eu* which worked reliably

going from impure to pure limestones.

Acknowledgements: We thank the quarry companies,

especially Lafarge Zementwerke GmbH (former Lafarge-

Perlmoser) for making available sampling in the active quarry

sites, and for hospitality and support for the work. Thanks go

to the Egyptian Cultural Affairs & Missions Sector for provi-

ding a PhD scholarship for the first author. Field work was

partly financed by UNESCO-IUGS IGCP 609 and the Austrian

Academy of Sciences. We also thank Shahid Iqbal and

Wolfgang Knierzinger for assistance during field work, Sabine

Hruby-Nichtenberger and Maria Meszar for sample prepara-

tion and lab work.

266

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, 2017, 68, 3, 248 – 268

References

Ali Sh. & Ntaflos Th. 2013: Petrogenesis and mantle source charac-

teristics of Quaternary alkaline mafic lavas in the western

Carpathian–Pannonian Region, Styria, Austria. Chem. Geol.

337–338, 99–113.

Anderson P.E., Benton M.J., Trueman C.N., Paterson B.A. & Cuny G.

2007: Palaeoenvironments of vertebrates on the southern shore

of Tethys: the nonmarine early cretaceous of Tunisia. Palaeo-

geogr. Palaeoclimatol. Palaeoecol. 243, 118–131.

Ando A., Kawahata H. & Kakegawa T. 2006: Sr/Ca ratios as indicators

of varying modes of pelagic carbonate diagenesis in the ooze,

chalk and limestone realms. Sediment. Geol. 191, 37–53.

Arndt S., Jørgensen B.B., LaRowe D.E., Middelburg J.J., Pancost R.D.

& Regnier P. 2013: Quantifying the degradation of organic

matter in marine sediments: A review and synthesis. Earth Sci.

Rev. 123, 53–86.

Azmy K., Brand U., Sylvester P., Gleeson S.A., Logan A. & Bitner

M.A. 2011: Biogenic and abiogenic low-Mg calcite (bLMC and

aLMC): evaluation of seawater-REE composition, water masses

and carbonate diagenesis. Chem. Geol. 280, 180–190.  

Baker P.A. & Bloomer S.H. 1988: The origin of celestite in deep-sea

carbonate sediments. Geochim. Cosmochim. Acta 52, 335–340.

Balogh K., Ebner F., Ravasz C., Herrmann P., Lobitzer H. & Solti G.

1994: K/Ar-Alter tertiärer Vulkanite der südöstlichen Steiermark

und des südlichen Burgenlandes. In: Lobitzer H., Császár G. &

Daurer A. (Eds.): Jubiläumsschrift 20 Jahre Geologische Zusam-

menarbeit Österreich–Ungarn. Geol. Bundesanst. Vienna, 55–72.

Bau M. 1991: Rare-earth element mobility during hydrothermal and

metamorphic fluid- rock interaction and the significance of the

oxidation state of europium. Chem. Geol. 93, 3, 219–230.

Bau M. & Dulski P. 1999: Comparing yttrium and rare earths in

hydrothermal fluids from the Mid-Atlantic Ridge: implications

for Y and REE behaviour during near-vent mixing and for the

Y/Ho ratio of Proterozoic seawater. Chem. Geol. 155, 1, 77–90.

Bau M. & Möller P. 1992. Rare earth element fractionation in meta-

morphogenic hydrothermal calcite, magnesite and siderite.

Mineral. Petrol. 45, 3–4, 231–246.

Bau M., Dulski P. & Möller P. 1995: Yttrium and holmium in South

Pacific seawater: vertical distribution and possible fractionation

mechanisms. Chem. Erde 55, l–15.

Bau M., Möller P. & Dulski P. 1997: Yttrium and lanthanides in

eastern Mediterranean seawater and their fractionation during

redox-cycling. Mar. Chem. 56, 123–131.

Bau M., Balan S., Schmidt K. & Koschinsky A. 2010: Rare earth

elements in mussel shells of the Mytilidae family as tracers for

hidden and fossil high-temperature hydrothermal systems. Earth

Planet. Sci. Lett. 299, 310–316.

Bojar A-V., Hiden H., Fenninger A. & Neubauer F. 2004: Middle

Miocene seasonal temperature changes in the Styrian basin,

Austria, as recorded by the isotopic composition of pectinid and

brachiopod shells. Palaeogeogr. Palaeoclimatol. Palaeoecol.

203, 95–105.

Boswell S.M. & Elderfield H. 1988: The determination of zirconium

and hafnium in natural waters by isotope dilution mass spectro-

metry. Mar. Chem. 25, 197–210.

Brand U. & Veizer J. 1980: Chemical diagenesis of a multicomponent

carbonate system-1: trace elements. J. Sediment. Petrol. 50,

1219–1236.

Calvert S.E., Burtin R.M. & Ingall E.D. 1996: Influence of water

column anoxia and sediment supply on the burial and preserva-

tion of organic carbon in marine shales. Geochim. Cosmochim.

Acta 60, 1577–1593.

Campbell A.C., Palmer M.R., Klinkhammer G.P., Bowers T.S.,

Edmond J.M., Lawrence J.R., Casey J.F., Thompson G.,

Humphris S., Rona R. & Karson J.A. 1988: Chemistry of hot

springs on the Mid- Atlantic Ridge. Nature (London) 335, 514-519.

Chittleborough D.J. 1991: Indices of weathering for soils and palaeo-

sols formed on silicate rocks. Austr. J. Earth Sci. 38, 115–120.

Craddock P.R., Bach W., Seewald J.S., Rouxel O.J., Reeves E. &

Tivey M.K. 2010: Rare earth element abundances in hydrother-

mal fluids from the Manus Basin, Papua New Guinea: indicators

of sub-seafloor hydrothermal processes in back-arc basins.

Geochim. Cosmochim. Acta 74, 5494–5513.

Cullers R.L. 1988: Mineralogical and chemical changes of soil and

stream sediment formed by intense weathering of the Danberg

granite, Georgia, USA. Lithos 21, 301–314.

Cullers R.L. 1994: The controls on the major and trace element

variation of shales, siltstones and sandstones of Pennsylvanian-

Permian age from uplifted continental blocks in Colorado to

platform sediment in Kansas, USA. Geochim. Cosmochim. Acta

58, 4955–4972.

Cullers R.L. 2000: The geochemistry of shales, siltstones and sand-

stones of Penn- sylvanianePermian age, Colorado, U.S.A.:

implications for provenance and metamorphic studies. Lithos 51,

305–327.

Cullers R.L. 2002: Implications of elemental concentrations for

prove nance, redox conditions, and metamorphic studies of

shales and limestones near Pueblo, CO, USA. Chem. Geol. 191,

305–327.

Cullers R.L. & Podkovyrov V.N. 2000: Geochemistry of the Meso-

proterozoic Lakhanda shales in southeastern Yakutia, Russia:

implications for mineralogical and provenance control, and

recycling. Precambrian Res. 104, 77–93.

Cullers R.L., Basu A. & Suttner L. 1988: Geochemical signature of

provenance in sand-size material in soils and stream sediments

near the Tobacco Root batholith, Montana, USA. Chem. Geol.

70, 335–348.

de Baar H.J.W., Bacon M.P. & Brewer P.G. 1983: Rare-earth distribu-

tions with a positive Ce anomaly in the western North Atlantic

Ocean. Nature 301, 324–327.

de Baar H.J.W., Bacon M.P., Brewer P.G. & Bruland K.W. 1985: Rare

earth elements in the Pacific and Atlantic Oceans. Geochim.

Cosmochim. Acta 49, 1943–1959.

Dubinin A.V. 2004: Geochemistry of rare earth elements in the ocean.

Lithol. Min. Resour. 39, 289–307.

Dullo W.C. 1983: Fossildiagenese im miozänen Leitha-Kalk der

Paratethys von Österreich: Ein Beispiel für Faunenverschiebung

durch Diageneseunterschiede. Facies 8, 1–112.

Ebner F. & Sachsenhofer R.F. 1995: Palaeogeography, subsidence

and thermal history of the Neogene Styrian basin (Pannonian

basin system, Austria). Tectonophysics 242, 133–150.

Elderfield H. 1988: The oceanic chemistry of the rare-earth elements.

Philos. Trans. R. Soc. London,325, 105–126.

Elderfield H. & Greaves M.J. 1982: The rare earth elements in sea-

water. Nature 296, 214–219.

Fenninger A. & Hubmann B. 1997: Palichnologie an der Karpatium/

Badenium-Grenze des Steirischen Tertiärbeckens (Österreich).

Geol.-Paläontol. Mitt. Innsbruck, 22, 71–83.

Haley B.A., Klinkhammer G.P. & McManus J. 2004: Rare earth

elements in pore waters of marine sediments. Geochim. Cosmo-

chim. Acta 68, 1265–1279.

Garbelli C., Angiolini L., Brand U., Shen S.Z., Jadoul F., Posenato R.,

Azmy K. & Cao C.Q. 2016: Neotethys seawater chemistry and

temperature at the dawn of the end Permian mass extinction.

Gondwana Res. 35, 272–285.

Handler R., Ebner F., Neubauer F., Hermann S., Bojar A.-V.,

Hermann S. 2006. 40Ar/39Ar dating of Miocene tuffs from

Styrian part of the Pannonian Basin: an attempt to refine the

basin stratigraphy. Geol. Carpath. 57, 483–494.

Haq B.U., Hardenbol J. & Vail P.R. 1987: Chronology of fluctuating

sea levels since the Triassic. Science 235, 1156–1166.

267

GEOCHEMISTRY AND PROVENANCE STUDY OF THE LEITHA LIMESTONES, CENTRAL PARATETHYS

GEOLOGICA CARPATHICA

, 2017, 68, 3, 248 – 268

Harangi S., Downes H. & Seghedi I. 2006: Tertiary-Quaternary sub-

duction processes and related magmatism in the Alpine-Medi-

terranean region. In: Gee D.G. & Stephenson R.A. (Eds.): Euro-

pean Lithosphere Dynamics. Geol. Soc. London Memoir 32,

167–190.

Harnois L. 1988: The CIW index: a new chemical index of weathe-

ring. Sediment. Geol. 55, 319–322.

Harzhauser M. & Piller W.E. 2010: Molluscs as a major part of

subtropical shallow-water carbonate production-an example

from a Middle Miocene oolite shoal (Upper Serravallian,

Austria). Spec. Publ. Int. Ass. Sed. 42, 185–200.

Hedberg H.D. 1976: International Stratigraphic Guide. John Wiley,

New York, 1–200.

Hinkley T.K. & Tatsumoto M. 1987: Metals and isotopes in Juan de

Fuca Ridge hydrothermal fluids and their associated solid mate-

rials. J. Geophys. Res. 92, 1943–1959.  

Hohenegger J. & Wagreich M. 2012: Time calibration of sedimentary

sections based on isolation cycles using combined cross-correla-

tion: dating the gone Badenian stratotype (Middle Miocene,

Paratethys, Vienna Basin, Austria) as an example. Int. J. Earth

Sci. (Geol. Rundsch.) 101, 339–349.

Hohenegger J., Ćorić S., Khatun M., Pervesler P., Rögl F., Rupp C.,

Selge A., Uchman A. & Wagreich M. 2009: Cyclostratigraphic

dating in the Lower Badenian (Middle Miocene) of the Vienna

Basin (Austria): the Baden-Sooss core: Int. J. Earth Sci. (Geol.

Rundsch.) 98, 915–930.

Hohenegger J., Ćorić S. & Wagreich M. 2014: Timing of the Middle

Miocene Badenian Stage of the Central Paratethys. Geol.

Carpath. 65, 1, 55–66.

Hongo Y. & Nozaki Y. 2001: Rare earth element geochemistry of

hydrothermal deposits and Calyptogena shell from the Iheya

Ridge vent field, Okinawa Trough. Geochem. J. 35,5, 347–354.

Ivanov D., Ashraf A.R., Mosbrugger V. & Palamarev E. 2002: Palyno-

logical evidence for Miocene climate change in the Forecarpathian

Basin (Central Paratethys NW Bulgaria). Palaeogeogr. Palaeo-

climatol. Palaeoecol. 178, 19–37.

Johannesson K.H., Telfeyan K., Chevis D.A., Rosenheim B.E. &

Leybourne M.I. 2014: Rare earth elements in stromatolites-1.

Evidence that modern terrestrial stromatolites fractionate rare

earth elements during incorporation from ambient waters. In:

Evolution of Archean Crust and Early Life. Springer Nether-

lands, 385–411.

Kim J.H., Torres M.E., Haley B.A., Kastner M., Pohlman J.W., Riedel

M. & Lee Y.J. 2012: The effect of diagenesis and fluid migration

on rare earth element distribution in pore fluids of the northern

Cascadia accretionary margin. Chem. Geol. 291, 152–165.

Kocsis L., Trueman C.N. & Palmer M.R. 2010: Protracted diagenetic

alteration of REE contents in fossil bioapatites: direct evidence

from Lu–Hf isotope systematics. Geochim. Cosmochim. Acta

74, 21, 6077–6092.

Kováč M., Andreyeva-Grigorovich A., Bajraktarević Z., Brzobohatý

R., Filipescu S., Fodor L., Harzhauser M., Nagymarosy A.,

Oszczypko N., Pavelić D., Rögl F., Saftić, B., Sliva L. &

Studencka B. 2007: Badenian evolution of the Central Para-

tethys Sea: paleogeography, climate and eustatic sea level

changes. Geol. Carpath. 58, 579–606.

Kováčová P., Emmanuel L., Hudáčkova N. & Renard N. 2009:

Central Paratethys paleoenvironment during the Badenian (Mid-

dle Miocene): evidence from foraminifera and stable isotope

(∂

C and ∂

O) study in the Vienna Basin (Slovakia). Int. J.

Earth Sci. (Geol. Rundsch.) 98, 1109–1127.

Kröll A. 1988: Reliefkarte des prätertiären/Untergrundes. In: Kröll

A., Flügel H.W., Seiberl W., Weber F., Walach G. & Zych D.

(Eds.): Erläuterungen zu den Karten über den prätertiären

Untergrund des Steirischen Beckens und der Südburgen län-

dischen Schwelle. Geologische Bundesanstalt, Vienna, 16–20.

Kulp J.L., Turckian K. & Boyd D.W. 1952: Sr content of limestones

and fossils. Geol. Soc. Am. Bull. 63, 701–716.

Land L.S. & Hoops G.K. 1973: Sodium in carbonate sediments and

rocks: a possible index to the salinity of diagenetic solutions.

J. Sediment. Petrol. 43, 614–617.

Lankreijer A., Kováč M., Cloetingh S., Pitoňák P., Hlôška M. &

Biermann C. 1995: Quantitative subsidence analysis and forward

modelling of the Vienna and Danube basins: thin-skinned versus

thick skinned extension. Tectonophysics 252, 433–451.

Laskarev V.N. 1924: Sur les equivalentes du Sarmatien supérieur en

Serbie. Recueil de traveaux ofert a M. Jovan Cvijic par ses amis

et collaborateurs, 73–85.

Lee E.Y. & Wagreich M. 2017: Polyphase tectonic subsidence evolution

of the Vienna Basin inferred from quantitative subsidence analysis

of the northern and central parts. Int. J. Earth Sci. 106, 687–705.

Madhavaraju J., González-León C.M., Lee Yong Il., Armstrong-

Altrin J.S. & Reyes-Campero L.M. 2010: Geochemistry of the

Mural Formation (Aptian–Albian) of the Bisbee Group, Northern

Sonora, Mexico. Cretaceous Res. 31, 400–414.

McLennan S.M., Taylor S.R. & Eriksson K.A. 1983: Geochemistry of

Archean shales from the Pilbara Supergroup, Western Australia.

Geochim. Cosmochim. Acta 47, 1211–1222.

McLennan S.M., Taylor S.R., McCulloch M.T. & Maynard J.B. 1990:

Geochemistry and Nd-Sr isotopic composition of deep-sea

turbidites: Crustal evolution and plate tectonic associations.

Geochim. Cosmochim. Acta 54, 2014–2050.

McLennan S.M., Hemming S., McDaniel D.K. & Hanson G.M. 1993:

Geochemical approaches to sedimentation, provenance, and tec-

tonics. In: Johnsson M.J. & Basu A. (Eds.): Processes Con-

trolling the Composition of Clastic Sediments. Geol. Soc. Am.,

Spec. Pap. 284, 21–40.

Michard A., Albarède F., Michard G., Minster J.F. & Charlou J.L.

1983: Rare earth elements and uranium in high-temperature

solutions from East Pacific Rise hydrolhermal vent field (13º N).

Nature (London), 303, 795–797.

Mielke J.E. 1979: Composition of the Earth’s crust and distribution of

the elements. In: Siegel F.R. (Ed.), Review of Research on Modern

Problems in Geochemistry. UNESCO Report, Paris, 13–37.

Morrison J.O. & Brand U. 1986: Geochemistry of recent marine

invertebrates. Geoscience Canada, 13, 237–254.

Morse J.W. & Mackenzie F.T. 1990: Geochemistry of Sedimentary

Carbonates. Elsevier, Amsterdam, 1–707.

Nesbitt H.W. & Young G.M. 1982: Early Proterozoic climates and

plate motions inferred from major element chemistry of lutites.

Nature 299, 715–717.

Neuhuber S., Gier S., Hohenegger J., Wolfgring E., Spötl C., Strauss

P. & Wagreich M. 2016: Palaeoenvironmental changes in the

northwestern Tethys during the Late Campanian Radotruncana

calcarata Zone: Implications from stable isotopes and geoche-

mistry. Chem. Geol. 420, 280–296.

Nothdurft L.D., Webb G.E. & Kamber B.S. 2004: Rare earth element

geochemistry of Late Devonian reefal carbonates, Canning

Basin, Western Australia: confirmation of seawater REE proxy

in ancient limestones. Geochim. Cosmochim. Acta 68, 263–283.

Nozaki Y. 2001: Rare earth elements and their isotopes. Encycl.

Ocean Sci. 4, 2354–2366.

Nozaki Y., Zhang J. & Amakawa H 1997: The fractionation between

Y and Ho in the marine environment. Earth Planet. Sci. Lett.

148, 329–340.

Olivarez A.M. & Owen R.M. 1991: The europium anomaly of sweater:

implications for fluvial versus hydrothermal REE inputs to the

oceans. Chem. Geol. 92, 317–328.

Papp A., Cicha I., Senes J. & Steininger F. 1978: M4-Badenien

(Moravien, Wielicien, Kosovien). Chronostratigraphie und

Neostratotypen. Miozän der Zentralen Paratethys. Slowakische

Akademie der Wissenschaften, Bratislava, 1–594.

268

ALI and WAGREICH

GEOLOGICA CARPATHICA

, 2017, 68, 3, 248 – 268

Piepgras D.J. & Jacobsen S.B. 1992: The behavior of rare earth

elements in seawater: Precise determination of variations in the

North Pacific water column. Geochim. Cosmochim. Acta 56,

1851–1862.

Piller W.E. & Kleemann K. 1991: Middle Miocene Reefs and related

facies in eastern Austria. 1) Vienna Basin: VI International

Symposium on Fossil Cnidaria including Archaeocyatha and

Porifera. Excursion Guidebook, Excursion B4, 1–28.

Piller W.E., Decker K. & Haas M 1996: Sedimentologie und Becken-

dynamik des Wiener Beckens: Sediment 96, 11. Sedimentologen-

treffen, Exkursion guide, Geol. Bundesanst., Wien, 1–41.

Piller W.E., Summesberger H., Draxler I., Harzhauser M. & Mandic

O. 1997: Meso- to Cenozoic tropical/subtropical climates —

Selected examples from the Northern Calcareous Alps and the

Vienna Basin. In: Kollmann H.A. & Hubmann B. (Eds.) Excur-

sion Guides, Second European Paleontological Congress,

Climates: Past, Present and Future, Wien, 70–111.

Piller W.E., Harzhauser M. & Mandic O. 2007: Miocene Central

Paratethys stratigraphy-current status and future directions.

Stratigraphy 4, 151–168.

Piper D.Z. 1974: Rare earth elements in the sedimentary cycle: a sum-

mary. Chem. Geol. 14, 285–304.

Reuter M., Piller W.E. & Erhart C. 2012: A Middle Miocene carbo-

nate platform under silici-volcaniclastic sedimentation stress

(Leitha Limestone, Styrian Basin, Austria)- Depositional envi-

ronments, sedimentary evolution and palaeoecology: Paleo-

geogr. Paleoclimatol. Paleoecol. 350–352, 198–211.

Riegl B. & Piller W.E. 2000: Biostromal coral facies - a Miocene

example from the Leitha Limestone (Austria) and its actualistic

interpretation. Palaios 15, 399–413.

Rohatsch A. 2005: Neogene Bau- und Dekorgesteine Niederöster-

reichs und des Burgenlandes. Mitteilungen IAG BOKU, 9–56.

Rostá E. 1993: Gilbert-type delta in the Sarmatian-Pannonian sedi-

ments, Sopron, NW Hungary. Földtani Közlöny 123, 2, 167–193.

Royden L.H. 1985: The Vienna Basin: a thin-skinned pull-apart basin.

In: Biddle K.T. & Christie-Blick N. (Eds) Strike-Slip deforma-

tion, basin formation, and sedimentation. SEPM Spec. Publ. 37,

319–338

Salvador A. 1994: International stratigraphic guide. International

Union of Geological Sciences and The Geological Society of

America, 1–214.

Schieber J. 2011: Marcasite in black shales- a mineral proxy for oxy-

genated bottom waters and intermittent oxidation of carbona-

ceous muds. J. Sediment. Res. 81, 447–458.

Schmid H.P., Harzhauser M. & Kroh A. 2001: Hypoxic events on

a Middle Miocene carbonate platform of the Central Paratethys

(Austria, Badenian, 14 Ma). Ann. Naturhist. Mus. Wien 102, 1–50.

Schmidt K., Garbe-Schönberg D., Bau M. & Koschinsky A. 2010:

Rare earth element distribution in >400 ºC hot hydrothermal

fluids from 5º S, MAR: the role of anhydrite in controlling

highly variable distribution patterns. Geochim. Cosmochim.

Acta 74, 4058–4077.

Scholle P.A. & Ulmer-Scholle D.S. 2003: A Color Guide to the

Petrography of Carbonate Rocks. AAPG Memoir 77, 1–474.

Schreilechner M.G. & Sachsenhofer R.F. 2007: High resolution

sequence stratigraphy in the eastern Styrian Basin (Miocene,

Austria). Austrian J. Earth Sci. 100, 164–184.

Schuster R. & Nowotny A. 2015: Die Einheiten des Ostalpinen

Kristallins auf den Kartenblättern GK50 Blatt 103 Kindberg und

135 Birkfeld. Arbeitstagung der Geologischen Bundesanstalt

Mitterdorf im Mürztal, 10–37.

Seghedi I. & Downes H. 2011: Geochemistry and tectonic develop-

ment of Cenozoic magmatism in the Carpathian-Pannonian

region. Gondwana Res. 20, 655–672

Slapansky P., Belocky R., Fröschl H., Hradecký P. & Spindler P.

1999: Petrography, Geochemie und geotektonische Einstufung

des miozänen Vulkanismus im Steirischen Becken (Österreich).

Abhandlungen der Geologischen Bundesanstalt 56, 419–434.

Steininger F.F. & Piller W.E. 1999: Empfehlungen (Richtlinien) zur

Handhabung der stratigraphischen Nomenklatur. Courier For-

schungsinstitut Senckenberg 209, 1–19.

Strauss P., Harzhauser M., Hinsch R. & Wagreich M. 2006: Sequence

stratigraphy in a classic pull-apart basin (Neogene, Vienna

Basin). A 3D seismic based integrated approach. Geol. Carpath.

57, 185–197.

Suess E. 1860: Erhaltung von Fossilresten im Leithakalk. Verhand-

lungen der Geologischen Reichsanstalt, 1860, 1–9.

Taylor S.R. & McLennan S.M. 1985: The continental crust, its com-

position and evolution. Blackwell, 1–328.

Tollmann A. 1985: Geologie von Österreich. Band II. Außerzentral-

alpiner Anteil: Deuticke, Wien, 1–710.

Ullmann C.V., Campbell H.J., Frei R. & Korte C. 2016: Oxygen and

carbon isotope and Sr/Ca signatures of high-latitude Permian to

Jurassic calcite fossils from New Zealand and New Caledonia.

Gondwana Res. 38, 60–73.

Veizer J. 1983: Trace elements and isotopes in sedimentary carbo-

nates. In: Reeder RJ (ed.): Carbonates: Mineralogy and

Chemistry. Mineral. Soc. Am. 11, 265–299.

Wagreich M. & Schmid H.P. 2002: Backstripping dip-slip fault histo-

ries: apparent slip rates for the Miocene of the Vienna Basin.

Terra Nova 14, 163–168.

Webb G.E., Nothdurft L.D., Kamber B.S., Kloprogge J.T. & Zhao J.

2009: Rare earth element geochemistry of scleractinian coral

skeleton during meteoric diagenesis: a sequence through neo-

morphism of aragonite to calcite. Sedimentology 56, 1433–1463.

Wedepohl K.H. 1978: Manganese: abundance in common sediments

and sedimentary rocks. Handbook of Geochemistry. Springer,

Berlin, 1-17.

Wessely G. 1983: Zur Geologie und Hydrodynamik im südlichen-

Wiener Becken und seiner Randzone. Mitt. Geol. Ges. Wien 76,

27–68.

Wessely G. 2006: Geologie der Österreichischen Bundesländer —

Niederösterreich. Geologische Bundesanstalt, Wien, 1–416.

Wiedl T., Harzhauser M. & Piller W.E. 2012: Facies and synsedi-

mentary tectonics on a Badenian carbonate platform in the

southern Vienna Basin (Austria, Central Paratethys). Facies 58,

523–548

Wiedl T., Harzhauser M., Kroh A., Ćorić S. & Piller W.E. 2013:

Ecospace variability along a carbonate platform at the northern

boundary of the Miocene reef belt (Upper Langhian, Austria).

Palaeogeogr. Palaeoclimatol. Palaeoecol. 370, 232–246.

Wiedl T., Harzhauser M., Kroh A., Ćorić S. & Piller W.E. 2014: From

biologically to hydrodynamically controlled carbonate produc-

tion by tectonically induced paleogeographic rearrangement

(Middle Miocene, Pannonian Basin). Facies 60, 865–881.

Zhang J., Amakawa H. & Nozaki Y. 1994: The comparative behaviors

of yttrium and lanthanides in the seawater of the North Pacific.

Geophys. Res. Lett. 21, 2677–2680.

Zhao M.Y. & Zheng Y.F. 2014: Marine carbonate records of terri-

genous input into Paleotethyan seawater: Geochemical con-

straints from Carboniferous limestones. Geochim. Cosmochim.

Acta 141, 508–531.