GEOLOGICA CARPATHICA
, OCTOBER 2019, 70, 5, 386–404
doi: 10.2478/geoca-2019-0022
www.geologicacarpathica.com
New
40
Ar/
39
Ar, fission track and sedimentological data
on a middle Miocene tuff occurring in the Vienna Basin:
Implications for the north-western Central Paratethys region
SAMUEL RYBÁR
1,
, KATARÍNA ŠARINOVÁ
2
, KARIN SANT
3
, KLAUDIA F. KUIPER
4
,
MARIANNA KOVÁČOVÁ
1
, RASTISLAV VOJTKO
1
, MARTIN K. REISER
5,7
, KLEMENT FORDINÁL
6
,
VASILIS TEODORIDIS
8
, PETRONELA NOVÁKOVÁ
1
and TOMÁŠ VLČEK
1
1
Department of Geology and Paleontology, Comenius University in Bratislava, Mlynská dolina, Ilkovičova 6, 842 15 Bratislava, Slovakia;
samuelrybar3@gmail.com
2
Department of Mineralogy and Petrology, Comenius University in Bratislava, Mlynská dolina, Ilkovičova 6, 842 15 Bratislava, Slovakia
3
Paleomagnetic Laboratory Fort Hoofddijk, Utrecht University, Budapestlaan 4, Utrecht,
Netherlands
4
Vrije Universiteit Amsterdam, Department of Earth Sciences, Faculty of Science, De Boelelaan 1085, 1081HV Amsterdam, Netherlands
5
Department of Geology, University of Innsbruck, Innrain 52f, 6020 Innsbruck, Austria
6
State Geological Institute of Dionýz Štúr, Mlynská dolina 1, 817 04 Bratislava, Slovakia
7
Geologische Bundesanstalt, Neulinggasse 38, 1030 Wien, Austria
8
Department of Biology and Environmental Studies, Charles University, M. Rettigové 4, 116 39 Prague, Czech Republic
(Manuscript received July 30, 2018; accepted in revised form September 18, 2019)
Abstract: The Kuchyňa tuff is found on the Eastern margin of the Vienna Basin and was formed by felsic volcanism.
The Ar/Ar single grain sanidine method was applied and resulted in an age of 15.23 ± 0.04 Ma, which can be interpreted
as the age of the eruption. The obtained numerical age is in accordance with the subtropical climate inferred by
the presence of fossil leaves that originated in an evergreen broadleaved forest. Furthermore, the described volcanism was
connected with the syn-rift stage of the back-arc Pannonian Basin system. The sedimentological data from the underlying
sandy mudstones indicate alluvial environment what confirms terrestrial conditions during deposition. Moreover, the tuff
deposition probably occurred shortly before the Badenian transgression of the Central Paratethys Sea.
Key words:
40
Ar/
39
Ar dating, fission track, Vienna Basin, middle Miocene.
Introduction
The analyzed Kuchyňa tuff (Šimon et al. 2009) was found
during geological mapping of Cenozoic sediments in the Vienna
Basin (Lat: 48.396428°, Lon: 17.164325°; Fig. 1). The out-
crop is localized in a wall of a deep scour and it is the only
known tuff section in this region. The total thickness of the tuff
was estimated as 30 cm (Fordinál et al. 2010). This tuff was
originally described as fine-grained and composed of plagio-
clase, biotite, quartz, orthopyroxene, apatite, ilmenite and tita-
nomagnetite together with vesiculated rhyolitic vitroclasts in
clay matrix (Šimon et al. 2009). The tuff also contains
fossil leaf imprints, determined as Daphnogene polymorpha,
Juglans sp., Dicotylophyllum sp., ?Salix varians, ?Ampelopsis
sp., ?Quercus sp. and Lauraceae indet. (Fordinál et al. 2010).
The recent excavations concentrated on this unique tuff,
with the ambition to extract additional information about
the extent of the middle Miocene volcanic activity in the
Carpathian–Pannonian Region. The main aim of this paper is
to provide radiometric age data using the
40
Ar/
39
Ar and fission
track (FT) methods supplemented by paleobotanical data.
Such age data in combination with information about chemi-
cal composition should enable a better understanding of
the tectono-sedimentary evolution of the Vienna Basin.
In addition, the age of the Kuchyňa tuff will allow stratigraphic
calibration of the determined paleoecological conditions.
Moreover, the tuff will serve as a chronostratigraphical marker
within the NW Pannonian Basin system.
Geological setting
The study area extends in the Kuchyňa highland at the
boundary between the Vienna Basin and the Malé Karpaty
Mountains (Western Carpathian mountain range). The geolo-
gical structure of the Malé Karpaty Mts. is divided into several
tectonic units of Paleozoic to Mezozoic age. In the study area
only Mesozoic sedimentary units are present (Fig. 1; Polák et
al. 2012; Fordinál et al. 2012a). The Vienna Basin started its
evolution in the early Miocene as a piggy back basin and later
(middle and late Miocene) evolved into a forearc basin (Kováč
2000; Vass 2002; Fordinál et al. 2012a). The Miocene infill of
the Vienna Basin in the study area is assigned to the Devínska
Nová Ves Fm. (Fordinál et al. 2012a; Fig. 1). This formation is
represented by breccias and conglomerates, rusty coloured to
spotty clays, coaly clays, lignite beds, non-calcareous sands
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NEW AGE DATA FROM THE MIDDLE MIOCENE TUFFS, VIENNA BASIN
GEOLOGICA CARPATHICA
, 2019, 70, 5, 386–404
and tuffs. The Devínska Nová Ves Fm. is either of middle
Badenian age (late Langhian; Fordinál et al. 2010, 2012a), or
of early Badenian age (Langhian) sense Kováč et al. (2007,
2018; Fig. 1). The paleoenvironment was described as terres-
trial, alluvial to deltaic (Fordinál et al. 2010, 2012a; Polák et
al. 2012). The formation is rarely overlain by conglomerates,
gravels and mudstones of late Badenian age (Studienka Fm.;
Fordinál et al. 2012a).
The middle Miocene volcanic fields in this region are con-
nected to the rifting of back-arc basins in the north part of the
Panonian Basin system (e.g. Kováč 2000; Konečný & Lexa
2002; Konečný et al. 2002b). The nearest volcanic centres are
buried in the neighbouring Danube Basin (e.g., Hrušecký 1999;
Kronome et al. 2014; Rybár et al. 2016). These centres were
not dated radiometrically, except for the Rusovce volcanic
centre, which was dated to 16.2 ± 0.5 Ma (Kantor 1987) by
using the whole rock K/Ar method. All of these centres are
overlain by Badenian sediments (Miháliková 1962; Gaža
1966; Bondarenková 1980; Rybár et al. 2016), except for the
Pásztori volcanic centre which is of middle to late Miocene
age (Harangi et al. 1995). Moreover in the north-western part
of the Danube Basin, several tuff horizons were dated biostra-
tigraphically to the early Badenian (NN5; Rybár et al. 2016;
Csibri et al. 2018). To the East, in the Central Slovak Volcanic
field (Lexa et al. 2010), the volcanic activity starts with
numerous volcanic centres located in shallow water conditions
Fig. 1. Location map of the study area: a — location within the Pannonian Basin System; VB — Vienna Basin, SB — Styrian Basin, the red
arrow indicates position of the study area; b — schematized geological map of the study area after Fordinál et al. (2012b); c — integrated
Miocene chronostratigraphy.
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RYBÁR et al.
GEOLOGICA CARPATHICA
, 2019, 70, 5, 386–404
(Neresnica, Vinica fms.). Their radiometric dating varies from
16.5–16 Ma (Konečný in Konečný et al. 1998) to 15 Ma
(Chernyshev et al. 2013). The activity continued with evolu-
tion of volcanoes and stratovolcanoes (Konečný et al. 1998).
The nearest exposed volcanic centre in the vicinity is the
Štiavnica stratovolcano, which was active from ~15 to 11 Ma
not counting the alkali basalt volcanism (Chernyshev et al.
2013). Within the exposed volcanic centres the Börzsöny and
Visegrád Mts. have to be mentioned, since they were active
from 16.5 to 13.5 Ma (Karátson et al. 2000, 2007). In the
Vienna Basin volcanic centres are missing, and only rare tuff
horizons were described at the base of the Jakubov Fm. (Sant
et al. in press).
Methods
Sedimentology and paleobotany
The outcrop was manually excavated to expose the full sec-
tion in the forest scour. To provide more insight, the section
was cleaned by palette knifes and brushes. The lithofacies
abbreviations were modified from Németh & Martin (2007)
and Miall (2006). Leaves were described using the current
terminology published by Ash et al. (1999) and Ellis et al.
(2009).
Petrology and chemistry
For grain-size analysis thin sections were used, and grain
dimensions were measured by metric scale. Measurements of
fine vitroclasts were not possible due to alteration. Therefore
only grains above 0.25 mm were labelled and their percen tage
was determined by image analysis using QuickPHOTO-
MICRO 3.1 (Comenius University in Bratislava). Image ana-
lysis of macro samples was used for determination of the
lapilly content. Mineral composition was analyzed under
polarizing microscope and under the Cameca SX 100 micro-
probe (State Geological Institute of Dionýz Štúr). Minerals
were measured using WDS analysis with accelerating voltage
15 keV, probe current 20 nA with a beam width of 10 µm.
The beam width of 2 µm was used on microlitic minerals in
lithoclasts. All vitroclasts were measured under 2 conditions:
probe current 3 nA (Na, K, Si) and 10 nA (other elements) for
elimination of mobile element loss. Raw analyses were recal-
culated to weight percent of oxide using the ZAF correction.
Other minerals were determined by EDAX analyses. Four
whole rocks samples were selected from different levels of
the section (Fig. 2). Samples were send to Bureau Veritas
mine ral laboratories (Canada, Vancouver). Samples were pul-
verized and prepared for analysis by Lithium Borate Fusion.
Major elements were analyzed by ICP-ES, and trace elements
by ICP-MS. X-ray analysis was performed by using the Bruker
D8 Advance (Earth Science Institute of SAS), with measure-
ment parameters: CuKα radiation generated by 40 kV and
40 mA, iris: 0.3°–6 mm–0.2062°, primary and secondary
Sollers iris: 2.5°; step: ≈ 0.02 °2θ; time/step: 1.25 and 0.8 s,
interval: 2–65 °2θ. Diffracted radiation was sensed by a posi-
tionally sensitive detector SSD 160 working in 1D regime.
Powdered whole rock samples and oriented slides from <2 and
<0.2 μm fractions were analyzed. Separation was done accor-
ding to Jackson (1975). Oriented slides were analyzed in two
states: natural state (Ca form) and following an ethylene
glycol saturation (8 hours at 60 °C).
40
Ar /
39
Ar dating
Approximately a 2 kg ash sample was processed at the
Mineral Separation facility of the Earth Sciences Department
at the VU University Amsterdam to separate sanidine and bio-
tite from the Kuchyňa tuff for
40
Ar/
39
Ar dating. First, the sam-
ple was crushed into ~1 cm
3
pieces, disintegrated in a diluted
calgon solution with a Robot Coupe blixer 4 v.v., treated in an
ultrasonic bath, and wet sieved into a fraction between 150
and 500 μm. K-feldspar (sanidine) grains were isolated from
the 2.54–2.59 g/cm
3
density fraction (using di-iodomethane)
and further purified by using magnetic separation over the
Frantz isodynamic separator and cleaned by a 10 minute ultra-
sonic HNO
3
bath (subsequently rinsed with distilled water).
The most transparent, inclusion free sanidine grains from
the 250–500 μm fraction were handpicked under an optical
microscope. Biotite was extracted from the density fraction
>3.00 g/cm
3
and cleaned in an ultrasonic bath. The thickest,
most angular hexagonal biotite crystals without visible inclu-
sions were handpicked under an optical microscope in the
200–400 μm fraction.
The selected mineral separates were packed in 6 mm ID AI
packages, loaded together with Fish Canyon Tuff sanidine
(FCs) standards in 25 mm ID Al cups and irradiated at the
Oregon State University TRIGA reactor in the cadmium
shielded CLICIT facility for 18 hours (irradiation code
VU107).
40
Ar/
39
Ar analyses were then carried out at the geo-
chronology laboratory of the VU University, Amsterdam, on
an ARGUS VI
+
noble gas mass spectrometer.
Single grain fusions were performed on 17 sanidine grains
and 5 biotite grains in June 2017. Ages are calculated with
Min et al. (2000) decay constants, atmospheric air value
298.56 (Lee et al. 2006) and 28.201± 0.022 Ma for FCs
(Kuiper et al. 2008). The correction factors for neutron inter-
ference reactions are (2.64 ± 0.02)×10
-4
for (
36
Ar/
37
Ar)
Ca
,
(6.73 ± 0.04)×10
-4
for (
39
Ar/
37
Ar)
Ca
, (1.21 ± 0.003)×10
-2
for
(
38
Ar/
39
Ar)
K
and (8.6 ± 0.7)×10
-4
for (
40
Ar/
39
Ar)
K
. Data analysis
and age calculations were performed in ArArCalc software
(Koppers 2002). All errors are quoted at the 2σ level and
include all analytical errors. All relevant analytical data for
age calculations can be found in the online supplementary
material.
FT dating
A 5 kg rock sample was crushed and sieved (<315 μm).
Apatite and zircon mineral concentrates were produced using
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NEW AGE DATA FROM THE MIDDLE MIOCENE TUFFS, VIENNA BASIN
GEOLOGICA CARPATHICA
, 2019, 70, 5, 386–404
the Wilfley table, a Frantz magnetic separator and conven-
tional heavy liquid methods. Handpicking under an optical
microscope was the final stage for apatite and zircon separa-
tion to provide pure concentrates. Final sample preparation
and analysis of fission track (FT) samples was carried out at
the University of Innsbruck. Mineral separates were mounted
in epoxy resin (apatite) and PFA®Teflon (zircon) was ground,
and polished with a series of polishing papers going from
1200, 1000, 9, 6 and 3 μm to provide a clear surface. Apatites
for age determination were etched for 40 seconds at 21 °C
with 6.5 % nitric acid; zircon mounts 3–6 h at 235 °C in
a NaOH–KOH eutectic melt to reveal spontaneous tracks
(Fleischer & Price 1964). Two U-free muscovite detectors
were sealed against the polished and etched surfaces (external
detector method; Gleadow & Duddy 1981).
For irradiation the samples were sent to the FRM II research
reactor in Garching, Germany. Two dosimeter glasses of
known uranium content, CN1 (for zircon) and CN5 (for
Fig. 2. a — Lithological column of the studied section; b — studied outcrop. The white line indicates the base of the tuff. The white T shaped
lines highlight the angular contact.
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, 2019, 70, 5, 386–404
apatite), were included to determine the neutron flux during
irradiation (Hurford & Green 1983). After irradiation, the
external mica detectors of samples and dosimeter glasses were
etched in 40 % hydrofluoric acid at 21 °C for 40 minutes.
Tracks in apatites, zircons, and mica detectors were counted
using a Zeiss Axio Imager A1m microscope equipped with
an AUTOSCAN stage (analyst: M. Reiser). FT ages were
determined using the Zeta calibration approach (Hurford &
Green 1983), with ζ = 318 ± 27 for apatite (dosimeter glass
CN-5) and ζ = 130 ± 10 for zircon (CN-1 dosimeter). They are
reported as central ages (Galbraith & Laslett 1993) with a 1σ
error.
FT etch-pit diameters (Dpar) were measured to estimate
the compositional influence on fission-track annealing (Carlson
et al. 1999). Ages were calculated using the TRACKKEY pro-
gram, version 4.2.g (Dunkl 2002). A central age is given for
samples that pass the Chi-square test (P > 5 %; Galbraith
1981). The partial annealing zone for apatite FT (APAZ)
ranges from 60 to 120 °C (e.g., Green et al. 1986; Green &
Duddy 1989; Gallagher et al. 1998) with a mean effective
closure temperature of 110 ±10°C (Gleadow & Duddy 1981).
For the interpretation of zircon FT data, this study used a zir-
con partial annealing zone (ZPAZ) between 200 and 300 °C
(cf. Tagami & O’Sullivan 2005).
Results
Sedimentology
The Kuchyňa section starts with thinly laminated or mas-
sive, muddy sandstones
of pale brown to yellow colour
(Figs. 2, 3). No signs of traction transport were observed.
The content of
rhizoids
and wood fragments
is high, but leaves
are not present in this level.
Moreover, no marine, brackish or
fresh water macrofauna was found. Foraminifers and calca-
reous nanofossils are also absent and the sediments show
no signs of bioturbation. A brick-red to brown coloured,
~ 8 cm thick clay layer is present on top of the sandy mud-
stones (Fig. 3f). above an angular contact between the muddy
sandstones and tuffs is observed. The muddy sandstones
show an average strike of 216° and dip of 78° and the over-
lying tuff layers display an average strike of 267° and dip
of 36.5°.
The total tuff thickness reaches ~ 97 cm which is more than
the formerly measured 30 cm (Šimon et al. 2009). The tuff is
overlain by recent soil and by deluvial muddy conglomerate,
so the total thickness of this tuff might probably be even larger.
Spherical weathering (exfoliation) has been observed. In a few
cases the tuff is cut by fissures filled with reddish mudstone.
These discontinuities seem to be almost perpendicular to
the bedding planes. A specific feature of the Kuchyňa tuff is
the high abundance of leaves and wood fragments, which are
more than 12.5 cm long.
The tuff consists of at least eight discontinuous parallel beds
with no interbeds of non-volcanic material. Due to the poor
preservation and high degree of fragmentation, description of
structures is difficult. The thickness of the individual tuff beds
ranges from 5 to 20 cm. The lowermost tuff bed contains two
visibly graded intervals (1–2 cm thick), which range from
coarse to medium grained ash based on visually observed
grain size characteristics. Rare accretionary lapilli have been
observed. The second bed shows gradation and abundant
leaves. The bed starts with coarse grained ash and passes to
fine grained ash. The following beds are composed of massive
medium to fine grained ash with abundant leaves at the lower
bed boundary. The leaves also occur within the bed and are
often plastically deformed. The n
ext bed yields matrix to
clast
supported accretionary lapilli (Fig. 2 n.5; Fig. 3). The accre-
tionary lapilli are often poorly recognizable macroscopically,
especially in dry samples. They are composed of internally
massive ash aggregates with a thin finer-grained outer rim
(Fig. 3a, b, d). Based on their structure they can be defined as
coated ash pellets or accretionary pellets (after Thordarson
2004; modified by Brown et al. 2010, 2012).
The lapilli are
often elliptical in shape and 3–6 mm long (rarely up to 16 mm
long; Fig. 3b, d).
They are deformed in the central part of
the layer, while the base and top of the bed yield undeformed
lapilli.
These deformed lapilli highlight a plastic deformation
of the bed (Fig. 3d).
The bed is cut by fissures filled with
sandy grains. A massive medium to fine grained ash bed fol-
lows. The section ends with layers that yield abundant admix-
ture of rounded non-volcanic granule to pebble size clasts and
plant fragments (Fig. 2 n.6–8; Fig. 3c).
The fossil leave association originally described by Fordinál
et al. (2010) is completed by newly discovered species like:
Quercus cf. drymeia and Trigonobalanopsis rhamnoides.
Petrography
The Kuchyňa tuff layers can be microscopically described
as crystallo–vitroclastic tuff with a little admixture of non-
volcanic lithoclasts. The basal tuff layers contain 8.7–13 %
particles above 0.25 mm in size (Table 1), which mostly con-
sist of pumice fragments. The following layers are composed
of fine tuffs (97–99 % of the clasts are smaller than 0.25 mm).
About 50 cm above the red clay layer a lapilly tuff with
29–38 % of accretionary lapilli occurs (Fig. 2). This layer is
covered by a fine tuff (97 % of the clasts are under 0.25 mm).
In the upper part
(85 cm and higher), the fine tuffs contain
admixture of ca. 5 % of nonvolcanic lithic clasts, which are
often larger than 2 mm in diameter.
Pumice fragments and glass shards are dominant in the tuff
composition (Fig. 4). The vitroclasts can be divided into two
types. One type is composed of volcanic glass with rough
boun daries. These volcanic glass shards of rhyolitic compo-
sition (Table 2, Fig. 5b) are often vesiculated or Y-shaped and
form the majority of the vitroclasts. However, the total sum
of oxides is low (92 wt. %; Table 2) and indicates alteration.
The very fine particles and highly vesiculated pumice frag-
ments were altered into clay minerals. The remaining vitro-
clasts are less frequent, microlithic and slightly altered
(Fig. 4a–b).
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NEW AGE DATA FROM THE MIDDLE MIOCENE TUFFS, VIENNA BASIN
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, 2019, 70, 5, 386–404
Fig. 3. Outcrop pictures: a — detail of the tuff layer with accretionary lapilli; b — tuff layer with deformed accretionary lapilli; c — tuff layer
with lithoclasts; d — synsedimentary folded accretionary lapilli, the black dashed line marks the presumed folding; e — contact layer between
sandy mudstones and the Kuchyňa tuff, also note the exfoliation in the tuff; f — detail onto individual layers of the section; g — underlying
sandy mudstone with rhizoliths. For other abbreviations see Fig. 2.
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The crystalloclasts are composed of plagioclase, sanidine,
biotite, amphibole, quartz and small amounts of pyroxene,
apatite, zircon, rutile and rare monazite. Some crystalloclasts
with remnants of adhering glass have been found (Fig. 4a).
Crystalloclasts do not show zonality and their shape is hypi-
diomorphic with marks of fragmentation in the solid state.
Among the feldspars, plagioclase crystalloclasts are dominant
and sanidine is less frequent. The chemical composition of
plagioclase varies in the range An
37–52
, but a crystalloclast of
An
79
was also found (Table 3, Fig. 6a). The chemical composi-
tion of sanidine crystalloclasts and composition of sanidine
crystals with adhering volcanic glass (Fig. 4a) varies from
Or
62–65
to Or
73–74
(Table 4, Fig. 6a). In addition, all sanidine
crystalloclasts contain 0.022–0.039 apfu of Ba. Amphibole
crystalloclasts are green to brown-green in colour and rela-
tively small. They are pargasite to magnesio-horblende in
composition (Table 5, Fig. 6b). Long, tabular biotites are
annite in composition (Table 5). Decay along cleavage planes
is documented by thin zones of different colours in the BSE
image (Fig. 4c). Some biotite crystalloclasts are bent and/or
frayed. Beside relatively fresh and large biotites, some altered
sagenitic biotite and sagenitic textures have also been
observed. However, based on the pre sence of non-volcanic
lithoclasts composed of quartz (Qz) and altered biotite (Bt)
with sagenite inclusions (Bt para gneiss), these sagenitized
biotites are interpreted as non-volcanic in origin. Both ortho-
pyroxene (enstatite) and clinopyroxene (augite) crystalloclasts
(Table 5) are also present. The rest of adhering microlithic
groundmass on the edge of an Opx crystalloclast (Fig. 4d) is
formed by plagioclase with An
63
,
Opx and ilmenite. However,
opx microliths did not reach the size required for the probe
measurement. The volcanic lithoclasts are extremely rare, due
to the fine grain size of the tuff.
The non-volcanic lithoclasts without any thermal effect are
composed of biotite paragneiss (Fig. 7a), cherts/felsites, low-
grade metapelites such as Qz–mica shale/phyllite (Fig. 7b),
carbonate shale and rare sandstones. The metasediment clasts
contain zircon, quartz, albite and mica (Fig. 4f). Polycrystal-
line quartz is also non-volcanic in origin. Given the purpose of
the paper, a lithoclast composed of quartz, biotite, monazite
and feldspar was also analyzed (Fig. 4e). The feldspar compo-
sition in the lithoclasts is between sanidine and anorthoclase
(Fig. 6a) and they do not contain Ba
(Table 4). However, these feldspars are
around 15 µm in size and, therefore,
could not affect the
40
Ar/
39
Ar dating
(Fig. 4e).
The Kuchyňa tuff also contains clay
minerals as products of alteration of
glass. X-ray analysis documented
a large portion of amorphous volcanic
glass, which is characterized by wide
diffusion reflex between 16 to 30 °2θ.
In both clay fractions smectite domina-
tes (Fig. 7c). Values d(060) =1.4969 Å
are characteristic for dioctahedral
forms of smectite. The chemical composition of the clays best
corresponds to montmorillonite, but the sum of oxide is very
low (Table 2). Moreover, halloysite was also identified. Pow-
dered, whole rock samples confirmed the presence of smec-
tite, plagioclase, biotite, quartz, crystobalite and ilmentite.
Due to alteration, the whole rock chemical composition is
influenced by alkali loss. So it must be interpreted carefully
mainly in regard to the major oxides. Based on whole rock
analyses, the Kuchyňa tuff belongs to the calc–alkaline series
of the peraluminous type. The Zr/Y ratio (7.5–10.3; Table 2)
also indicates affinity to the calc–alkaline series (Barret &
MacLean 1994). Based on the TAS diagram (Le Bas et al.
1986) the tuff is rhyolite to dacite in composition (Fig. 5b,
Table 2). However, a high content of volatile components
(LOI 13.9–9.3 %) and alteration to clay mineral excludes
the use of the TAS diagram. Samples are displayed in a clas-
sification diagram based on trace elements (Pearce 1996;
Fig. 5a) in the trachyte to rhyolite/dacite field. The CIPW
calculation (Table 6) also indicates rhyolitic composition.
Discrimination based on Co–Th (Fig. 5c; Hastie et al. 2007),
and K
2
O–SiO
2
(Fig. 5d; Peccerillo & Taylor 1976) indicates
rhyodacite rocks of high-K calc–alkaline series. The Kuchyňa
tuff shows an Eu anomaly of 0.59, high LREE content
(Table 2), depletion in P, Nb, Ta, Ti and enrichment in Pb
(Fig. 5e, f). The
Eu anomaly of 0.59 indicates plagioclase frac-
tionation during magma evolution. The LREE/HREE ratio
indicates a possible garnet fractionation.
40
Ar/
39
Ar dating results
The majority of single grain fusion feldspar measurements
yield high radiogenic
40
Ar values (> 90 %
40
Ar*), and, thus,
relatively low amounts of atmospheric
36
Ar, indicating a mini-
mal impact of potential alteration of the dated mineral (ESM. 1).
The
37
Ar values are for most samples between 0.3 and 2.2 fA.
High
37
Ar values reflect high Ca-content pointing to plagio-
clase instead of sanidine (K-feldspar). Plagioclase can result in
lower quality age determinations than sanidine because of its
low K content. Incorporation of excess argon will have large
effects on the measurements and may result in overestimated
ages (McDougall & Harrison 1999). Moreover, neutron inter-
ference corrections are more substantial for plagioclase (due
Depth (cm over tuff base)
10
20
25
40
70
85
95
45–60
Layer
n.1
n.2b
n.2a
n.3–4
n.6
n.7
n.8
n.5*
Fraction (mm)
%
%
%
%
%
%
%
%
> 2
4.34
1.64
29–38
1–2
2.02
0.19
1.98
0.5–1
3.68
2.76
0.19
0.70
0.52
0.43
2.34
0.25–0.5
2.98
10.40
0.60
2.24
2.24
2.84
1.75
˂ 0.25
91.32
86.85
99.20
97.06
97.25
92.19
92.30
61–71
Grains above 0.25 mm (%)
8.68
13.16
0.79
2.94
2.76
7.80
7.71
acc.
Vitroclasts & pumice
6.43
10.42
0.66
1.94
1.77
2.32
1.66
lapilli
Crystalloclasts
2.00
2.41
0.13
0.83
0.56
0.80
0.53
Lithoclasts
0.25
0.33
0.00
0.17
0.43
4.68
5.52
Table 1: Grain size composition of the Kuchyňa tuff and modal analysis of clasts larger than
0.25 mm in diameter.
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NEW AGE DATA FROM THE MIDDLE MIOCENE TUFFS, VIENNA BASIN
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to the
40
Ca (n, nα)
36
Ar and
42
Ca(n,α),
39
Ar reactions during irra-
diation) yielding larger analytical uncertainties (McDougall &
Harrison 1999). Therefore, only the most reliable grains with
40
Ar >90 % and
37
Ar <1.5 fA are considered for the age deter-
mination. These generally yield the highest measured values
of
40
Ar. The weighted mean age (assumed to be the age of
the volcanic eruption) is based on the youngest grains that
define a plateau and the data are included as long as the mean
weighted standard deviation (MWSD) is < statistical T-test
at a confidence level of p5 %. The mean weighted age is
15.23 ± 0.04 Ma (n = 3; Fig. 8). The full range of the reliable
sanidine grains is 15.22 ± 0.02 Ma to 15.40 ± 0.01 Ma.
The small set (n = 5) of single grain biotite measurements is
characterized by low
40
Ar* values, pointing to alteration for
Fig. 4. Kuchyňa tuffs in BSE images: a — crystalloclast of sanidine with adhering glass (analysis 4 core, analysis 5 rim); b — sanidine crys-
talloclast (analysis 1 core, analysis 2 rim); c — biotite crystalloclast (analysis 22); d — orthopyroxene crystalloclast (analysis 31) with adhering
microlithic glass; e — granitoid/gneiss lithoclast composed of Kfs (analysis 6+7), Qz, Bt and Mnz; f — metapelite lithoclast composed of Ab,
Qz, Ser and Zr.
394
RYBÁR et al.
GEOLOGICA CARPATHICA
, 2019, 70, 5, 386–404
most of the samples. Moreover, they generally yielded lower
beam intensities (< 90 fA) of
40
Ar than the Kuchyna tuff, so
the results are less precise. The most reliable biotite analysis
(067_VU107) with
40
Ar* of 74 % yields an age of 15.05 ±
0.12 Ma, and might be close to the eruption age (Fig. 8).
FT results
The measured apatite grains are predominantly tabular and
prismatic crystals or crystal fragments. D
par
(average etch pit
diameter) measurements indicate a fluorine dominated apatite
composition (D
par
< 2.0 µm). Presence of fluorapatite was also
confirmed by the microprobe (Table 5). However, no correla-
tion between age and composition has been observed. Based
on mesurement of 24 grains an age of 14.5 ± 2.8 Ma was
obtained (Table 7). It should be noted that several grains
exhibit very low track densities (average Ns < 2 per grain).
After including these grains in the calculation the resulting
ages will be younger (12.1 ± 2.3 Ma; Table 7). Zircon FT ana-
lyses based on 15 grains yields a central age of 13.7 ± 1.2 Ma
(Table 7). Controversially to their respective closure tempera-
tures, the zircon age is younger than the apatite age, but they
still overlap within their respective error bars.
Discussion
Age of the Kuchyňa tuff
The juvenile origin of sanidine is documented by the pre-
sence of adhering glass on the rim of the crystalloclasts
(Fig. 4a). The 15.23 ± 0.04 Ma plateau age of sanidine is in
accordance with the assignment of the Devínska Nová Ves
Fm. to the middle Badenian (Langhian; Fordinál et al. 2010,
Analyse
Whole rock
Glass shards
Clay
Sample
n-1
n-3
n-4
n-5
anal.
38
39
1/19
2/19
3/19
4/19
5/19
anal.
40
41
SiO
2
%
56.68
59.21
65.12
64.08
SiO
2
71.38
71.78
72.94
73.23
72.14
72.72
69.31
SiO
2
27.56
28.09
TiO
2
0.25
0.15
0.12
0.23
TiO
2
0.05
0.06
0.09
0.08
0.02
0.06
0.06
TiO
2
0.05
0.04
Al
2
O
3
18.12
17.00
14.55
15.52
Al
2
O
3
11.64
11.49
11.59
11.55
11.76
11.44
12.05
Al
2
O
3
12.85
13.92
Fe
2
O
3
3.22
2.93
2.77
2.44
FeO
0.65
0.86
1.03
0.99
0.72
0.96
0.81
*Fe
2
O
3
*1.38
*1.44
Cr
2
O
3
n.d.
n.d.
n.d.
0.002
Cr
2
O
3
0.00
0.00
0.00
0.01
0.01
0.00
0.00
Cr
2
O
3
0.02
0.02
MgO
2.04
1.57
1.42
1.36
MgO
0.01
0.03
0.06
0.07
0.06
0.08
0.04
MgO
0.48
0.78
MnO
0.05
0.05
0.04
0.04
MnO
0.06
0.05
0.12
0.04
0.00
0.00
0.10
MnO
0.00
0.00
CaO
2.34
1.56
1.52
1.80
CaO
0.64
0.80
1.01
1.05
0.77
0.98
0.80
NiO
0.02
0.00
Na
2
O
1.35
1.25
1.34
1.59
NiO
0.00
0.01
0.00
0.01
0.03
0.01
0.00
CaO
0.61
0.62
K
2
O
1.78
2.49
3.40
3.43
Na
2
O
2.94
3.32
3.07
3.03
2.99
3.13
3.33
K
2
O
0.11
0.14
P
2
O
5
0.06
0.03
0.03
0.06
K
2
O
4.70
4.30
3.89
4.19
4.76
4.04
4.50
Na
2
O
0.02
0.05
LOI
13.9
13.6
9.5
9.3
P
2
O
5
0.00
0.01
0.00
0.03
0.02
0.02
0.04
Cl
0.56
0.51
sum
99.89
99.92
99.81
99.85
SO
3
0.00
0.00
0.01
0.00
0.00
0.02
0.00
F
0.00
0.00
C
tot
0.22
0.18
0.02
0.17
Cl
0.07
0.05
0.10
0.10
0.10
0.09
0.09
Tot
43.66
45.61
S
tot
n.d.
n.d.
n.d.
n.d.
Tot
92.14
92.75
93.93
94.39
93.37
93.56
91.13 Si
7.536
7.365
Sc
ppm
5
3
3
4
Tot-Cl
92.13
92.74
93.90
94.36
93.35
93.54
91.11
T
Al
0.464
0.635
Ba
759
908
788
693
Sum
8.000
8.000
Co
2.8
2.6
3.6
2.3
Al
3.677
3.664
Cs
3.7
3.6
4
5
Ti
0.011
0.008
Ga
18.0
16.2
15.4
14.8
Fe
3+
0.189
0.190
Hf
5.1
4.3
3.7
4.3
Mg
0.195
0.304
Nb
17.9
16.2
14.5
14.4
Mn
0.000
0.000
Rb
70.3
76.2
104.3
106.8
Cr
0.004
0.004
Sr
125.7
81.5
89.2
105.7
Ni
0.004
0.000
Ta
1.6
2.0
1.6
1.4
sum
4.082
4.171
Th
23.2
23.6
18.9
18.2
Ca
0.178
0.175
U
2.4
3.5
4.1
4.1
K
0.040
0.047
V
21
15
9
21
Na
0.012
0.023
Zr
175.1
125.4
114.0
132.4
sum
0.230
0.245
Y
16.9
14.4
13.9
17.7
La
37.7
27.2
26.8
34.3
Ce
68.0
51.2
43.7
56.5
Pr
6.81
5.01
5.30
6.43
Nd
22.4
16.2
18.0
20.9
Sm
3.79
2.89
3.06
3.76
Eu
0.72
0.51
0.54
0.70
Gd
3.07
2.47
2.56
3.45
Tb
0.49
0.39
0.43
0.54
Dy
2.94
2.22
2.68
3.15
Ho
0.53
0.47
0.49
0.64
Er
1.63
1.35
1.67
1.97
Tm
0.25
0.21
0.23
0.31
Yb
1.65
1.48
1.57
2.18
Lu
0.27
0.23
0.29
0.33
Eu/Eu*
0.645
0.584
0.588
0.592
La/Yb
16.39
13.18
11.60
10.69
Zr/Y
10.36
8.71
8.20
7.48
Table 2: Whole rock chemical composition of tuffs together with probe analysis of glass shards and indicative probe analyses of clay matrix
*
Fe
2
O
3
, was recalculated from FeO. Clay minerals were normalized to 44 total cation charges, to balance O
20
(OH)
4
and all Fe was considered
as Fe
3+
. Analyses of clay minerals must be taken as informative, because the thin sections were not prepared and measured with respect to clay
minerals.
395
NEW AGE DATA FROM THE MIDDLE MIOCENE TUFFS, VIENNA BASIN
GEOLOGICA CARPATHICA
, 2019, 70, 5, 386–404
Fig. 5. Chemical composition of the Kuchyňa tuff. Note that the major element diagrams are only illustrative, because of the low oxide sum in
the Kuchyňa tuff (see Table 2). Analyses were recalculated to 100 % free of volatiles before plotting in b and d diagrams. Comparative samples
taken from: Börzsöny–Visegrád region — Harangi et al. 1995; Karátson et al. 2000, 2007; Demjén Unit — Lukács et al. 2018; CSVF (Central
Slovak volcanic field) — Harangi et al. 1995; Konečný et al. 1995, 1998; Chernyshev et al. 2013; Danube Basin — Šarinová (personal data
from tuffs occurring within the NN5 zone). a — Pearce (1996) diagram; b — TAS diagram (Le Bas et al. 1986); c — discrimination based on
Co–Th (Hastie et al. 2007), IAT — island arc tholeiite; CA — calc–alkaline; H-K — high-K calc–alkaline; SHO — shoshonite; d — discri-
mination based on major oxides (Peccerillo & Taylor 1976), I: tholeiite series, II: calc-alkaline series, III: high-K calc–alkaline series,
IV: shoshonite series; e — Chondrite-normalized REE distribution (after McDonough & Sun 1995); f — primitive mantle-normalized multi-
element diagram (normalizing values after Sun & McDonough 1989).
396
RYBÁR et al.
GEOLOGICA CARPATHICA
, 2019, 70, 5, 386–404
2012a; Polák et al. 2012) or to the early Badenian sense Kováč
et al. (2007, 2018; Fig. 1c).
The results of AFT data are put in question due to the pre-
sence of apatites with no tracks (Table 7). If the age value
gained from apatites without tracks is excluded, the AFT indi-
cates an age of 14.5 ± 2.8 Ma. This is roughly consistent with
the sanidine age data, taking into account the error bars.
However, zircon FT analyses yielded an age of 13.7 ± 1.2 Ma
which is younger than the
40
Ar/
39
Ar sanidine age. The younger
zircon age cannot be interpreted as a later thermal overprint
because the closing temperature for zircon FT is higher than
the closing temperature for apatite FT and sanidine. The small
number of the measured zircon grains may account for the
larger errors in the results.
These results are not fully compatible. But, if the sanidine is
really juvenile, the Ar/Ar single grain age data are prioritized.
Additionally, a tuffite horizon overlaid by the Jakubov Fm.
(younger than 14.6 Ma based on Orbulina suturalis) was found
in the Bernhardsthal-4 well, in the NE Vienna Basin (Sant et
al. in press). Based on Ar/Ar dating of biotite, the tuf fite from
Bernhardsthal-4 well yields an age range of ~15–16 Ma, what
is in accordance with the age of the Kuchyňa tuff. Other
supporting argument for the middle Miocene age is the occur-
rence of Trigonobalanopsis rhamnoides. Since Trigono
balanopsis rhamnoides is absent in the late Miocene of the
northern parts of the Paratethys region (Kovar-Eder & Hably
2006), the presence of the taxon indicates a close relation to
the early and middle Miocene plant record in the Paratethys
realm. The tuff age points to the fact that the Badenian trans-
gression did not reach the area sooner than around 15 Ma,
what is in accordance with the general setting for this region
(e.g., Sant et al. 2017).
Depositional setting
Based on the floral assemblages determined by Fordinál et
al. (2010) together with the new findings of this work, it is
possible to interpret climatic conditions during the time of tuff
deposition. Fossil leaves of Quercus cf. drymeia, Lauraceae
gen. et sp. indet., Trigonobalanopsis rhamnoides document
subtropical, humid continental conditions with hinterland
and lowland evergreen broadleaved forests. The presence of
Fig. 6. a — Feldspar classification diagram; b — Amphibole classification diagrams (Hawthorne et al. 2012).
Analyse
3
17
18
19
20
21
36
Comment
clast
clast
clast
clast
clast
clast
microlith
SiO
2
56.73
57.12
59.15
47.38
55.06
55.20
54.47
Al
2
O
3
27.31
26.50
25.22
33.32
28.03
27.47
27.72
SrO
0.09
0.05
0.03
0.08
0.09
0.09
0.04
FeO
0.18
0.24
0.27
0.23
0.38
0.24
0.90
MgO
0.00
0.00
0.00
0.00
0.02
0.00
0.37
CaO
9.61
9.04
7.75
16.61
10.81
9.88
11.96
Na
2
O
6.13
6.21
6.85
2.26
5.21
5.69
3.63
K
2
O
0.32
0.36
0.51
0.08
0.31
0.33
0.35
Total
100.36 99.52
99.78
99.94
99.90
98.90
99.45
Si
2.544
2.578
2.652
2.179
2.490
2.516
2.478
Al
1.443
1.410
1.333
1.806
1.494
1.476
1.486
Sr
0.002
0.001
0.001
0.002
0.002
0.002
0.001
Fe
0.007
0.009
0.010
0.009
0.014
0.009
0.034
Mg
0.000
0.000
0.000
0.000
0.001
0.000
0.025
Ca
0.462
0.437
0.372
0.818
0.524
0.482
0.583
Na
0.533
0.543
0.596
0.202
0.457
0.503
0.320
K
0.019
0.021
0.029
0.005
0.018
0.019
0.020
Cat sum
5.010
4.999
4.994
5.021
5.000
5.007
4.949
Or %
1.83
2.05
2.95
0.44
1.77
1.89
2.22
Ab %
52.61
54.28
59.74
19.69
45.76
50.09
34.66
An %
45.56
43.67
37.32
79.87
52.47
48.01
63.12
Table 3: Composition of plagioclase. Chemical composition was
calculated based on 8 oxygens.
397
NEW AGE DATA FROM THE MIDDLE MIOCENE TUFFS, VIENNA BASIN
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, 2019, 70, 5, 386–404
ripa rian forests and coastal swamps is indicated by azonal
vegetation (e.g. Salix). The preserved root trace fossils in
the under lying sandy mudstones, as well as the high content of
leaves within the tuff, confirms that the area was overgrown
by land plants before the tuff deposition.
The presence of elliptical ash accretionary pellets indicated
syn-depositional deformation from a wet landing or gliding.
Consequently, post-depositional deformation under the load of
the overlying sediments is out of question. Wet landing is typi-
cal for fall deposits in terrestrial environment (e.g., Brown et
al. 2010, 2012; Eaton & Wilson 2013). This is consistent with
the original interpretation of the Kuchyňa tuff as an ash-fall
deposit (Šimon et al. 2009) and with the assumed terrestrial
environment of the Devínska Nová Ves Fm. (Fordinál et al.
2010, 2012a; Polák et al. 2012). However, deformation of ash
pellets (Fig. 3d) can be also linked with gliding of the tuff in
a plastic state. Sliding of wet, freshly deposited tuff is sup-
ported by various deformations of fossil leaves inside the ash
layers. Some movement can also be interpreted based on
the angular discontinuity between the underlying muddy sand-
stones and the tuffs (Fig. 2). The overall tilt of the layers may
be caused by a nearby normal fault that was active before
deposition of the tuff.
The admixture of nonvolcanic, rounded granule to pebble
size clasts in the upper part of the tuff indicate rainwash
conditions, which caused some reworking at the end of the
process. Since the ~ 30 cm thick upper part is reworked
(epiclastic) the total thickness needs to be reduced to ~ 70 cm.
The non-volcanic admixture is only partially compatible with
Devínska Nová Ves Fm. conglomerates (Vass et al. 1988;
Fordinál et al. 2010) and documents surface exposure of
the biotite paragneisses in the vicinity.
Origin of the tuff
Due to the poor outcropping conditions and high level of
fracturing of the section it is very difficult to interpret the ori-
ginal bedding features. The presence of an original bedding
plane is supported by leaf accumulation at the base of some
beds. The fact that the tuff does not contain any interlayer of
non-volcanic material points to a deposit which originated
from a single eruption event. Detected grain size variation
indicates decrease in intensity of volcanic activity during this
time. The clast supported accretionary lapilli bed (n.5, Fig. 2)
and graded intervals indicate ash-fall. Large, complexly laye-
red accretionary lapilli or fractured aggregates typical for
pyro clastic density flows (e.g., Brown et al. 2010, 2012;
Eaton & Wilson 2013) have not been observed. Additionally,
the presence of ash pellets (accretionary lapilli) points to wet
conditions within the eruption cloud. This can be caused by
phreatomagmatic eruptions or by presence of rain moisture.
However, phreatomagmatic eruptions, caused by contact of
magma and water saturated sediments, typically generate acci-
dental clasts (clast of surrounding sediments; White 1996;
Németh & Martin 2007) and in the Kuchyňa tuff, the portion
of accidental clasts is very low, and nonvolcanic clasts are
metamorphic in origin (gneisses). Therefore, based on the
thickness together with the ash-fall origin, and composition
(dominance glass shards and one layer of clast supported
lapilli tuff), the Kuchyňa tuff was most likely derived from
a Plinian type (phreato-Plinian) eruption. In this case, forma-
tion of ash pellets was probably caused by presence of rain
clouds typical for the determined subtropical humid climate.
A relative proximity to the volcanic centre can also be
deduced from grain size of accretionary pellets that are more
Table 4: Composition of K-feldspar. Chemical composition was calculated based on 8 oxygens.
Analyse
1
2
4
5
8
9
10
11
12
13
14
15
16
6
7
N. crystal
1core
1rim
2core
2rim
3core
3rim
4
5
6
7
8
9
10
11
12
Position
clast
clast
clast
clast
clast
clast
clast
clast
clast
clast
clast
clast
clast
lithoclast lithoclast
SiO
2
64.05
64.21
64.73
64.56
64.09
64.30
64.51
65.19
64.12
64.14
65.17
64.69
64.17
66.55
66.33
Al
2
O
3
20.47
20.11
20.43
20.64
20.23
20.12
20.34
20.33
20.47
20.45
20.41
20.47
20.28
20.82
21.77
FeO
0.10
0.13
0.13
0.10
0.11
0.13
0.27
0.08
0.05
0.12
0.14
0.11
0.11
0.17
0.19
MgO
0.01
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.01
0.03
0.00
BaO
2.13
2.10
1.37
1.30
1.88
2.02
1.53
1.22
2.16
2.14
1.76
1.27
1.87
0.15
0.15
CaO
0.14
0.15
0.19
0.22
0.15
0.16
0.14
0.23
0.17
0.19
0.20
0.15
0.18
1.05
1.98
Na
2
O
2.78
2.77
3.93
4.03
2.68
2.77
2.81
3.64
2.81
2.74
3.72
2.75
2.73
5.66
7.44
K
2
O
11.89
11.92
10.78
10.38
12.06
12.05
12.20
10.85
11.96
11.94
10.85
12.30
12.21
7.25
4.05
Total
101.57
101.40
101.56
101.23
101.19
101.54
101.79
101.55
101.73
101.73
102.25
101.73
101.56
101.69
101.91
Si
2.917
2.929
2.924
2.918
2.926
2.929
2.925
2.937
2.917
2.918
2.930
2.927
2.922
2.935
2.895
Al
1.099
1.081
1.088
1.100
1.088
1.080
1.087
1.079
1.097
1.097
1.081
1.091
1.089
1.082
1.120
Fe
0.004
0.005
0.005
0.004
0.004
0.005
0.010
0.003
0.002
0.005
0.005
0.004
0.004
0.006
0.007
Mg
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.001
0.002
0.000
Ba
0.038
0.038
0.024
0.023
0.034
0.036
0.027
0.022
0.039
0.038
0.031
0.023
0.033
0.003
0.003
Ca
0.007
0.007
0.009
0.011
0.007
0.008
0.007
0.011
0.008
0.009
0.010
0.007
0.009
0.049
0.092
Na
0.245
0.245
0.345
0.353
0.237
0.244
0.247
0.318
0.248
0.241
0.324
0.241
0.241
0.484
0.630
K
0.691
0.694
0.621
0.599
0.702
0.701
0.706
0.623
0.694
0.693
0.622
0.710
0.709
0.408
0.226
Cat sum
5.002
5.000
5.015
5.008
4.999
5.003
5.008
4.994
5.005
5.001
5.003
5.003
5.009
4.970
4.973
Or %
73.28
73.32
63.70
62.21
74.14
73.55
73.57
65.41
73.08
73.45
65.09
74.12
73.93
43.30
23.79
Ab %
26.01
25.92
35.34
36.69
25.07
25.64
25.71
33.40
26.07
25.58
33.91
25.14
25.14
51.44
66.46
An %
0.72
0.76
0.96
1.10
0.78
0.80
0.72
1.18
0.85
0.97
0.99
0.74
0.94
5.26
9.75
398
RYBÁR et al.
GEOLOGICA CARPATHICA
, 2019, 70, 5, 386–404
than 5 mm in diameter. This usually indicates deposition in
a radius of 10s of km from the source (Brown et al. 2012).
Only in the case of extremely large eruptions can the pellets be
deposited at a distance larger than 100 km.
The characterization of the parental magma is difficult,
because the Kuchyňa tuff contains high proportions of slightly
altered volcanic glass and its actual composition is also
influenced by segregation during transportation and depo-
sition. The monocrystalline quartz, plagioclase, sanidine,
non-altered biotite, amphibole and vitroclasts of the first type
(microlithe free) can be considered juvenile. The crystallo-
clasts of Px and basic plagioclase (An
79
) together with micro-
lithic glass can be sourced from the magma chamber or may
have been incorporated during explosions, from older volca-
nic rocks. Based on the results of chemical analyses, presence
of sanidine crystalloclasts and based on plagioclase composi-
tion (An
37–52
), the Kuchyňa tuff can be diagnosed as high-K
calk–alkaline rhyodacite (Fig. 5). Higher LREE content,
depletion in P, Nb, Ta, Ti and enrichment in Pb (Fig. 5e, f)
is typical for subduction related magmas (Bailey 1981).
The K
2
O–Rb ratio as well as the values of Rb, Ba, Pb, La, Zr,
Hf, K/La, La/Y, Zr/Y, Hf/Yb, Ni/Co, Sc/Ni (Table 2) show
affinity to the Andean arc type volcanism (thick continental
margins; Bailey 1981). These signatures are typical for the
Western Segment of the Carpathian–Pannonian region (e.g.,
Konečný et al. 1995, 1998, 2002; Karátson et al. 2000, 2007;
Seghedi et al. 2004), where volcanic activity in the Badenian
is linked with subduction related back-arc extension, for
example, with the syn-rift stage of the Pannonian Basin sys-
tem (e.g., Seghedi et al. 2004; Kováč et al. 2007). In this case,
subduction-induced, mantle-derived magmas were affected by
long-term fluid and sediment contamination as well as by
mixing of crustal melts with mantle-derived magmas (Seghedi
et al. 2004; Harangi & Lenkey 2007). Based on these facts,
the origin of the Kuchyňa tuff must be somewhere within
the Western segment of the Pannonian Basin System.
If the source area really is in the Western segment of the
Pannonian Basins, the Kuchyňa tuff must have been transport
from the East towards the West. This is in accordance with
findings of Lukács et al. (2018) from the Bükkalja Volcanic
Field. Moreover, similar interpretations about the Pannonian
source (based on the
143
Nd/
144
Nd ratio) which indicates East to
West transport of silicic tuffs (16.1–14.5 Ma), comes from
the Upper Freshwater Molasse in Germany (Rocholl et al.
2008; Aziz et al. 2010).
Table 5: Composition of mafic minerals and apatite. Chemical composition of amphiboles was calculated after Hawthorne et al. (2012) using
the Excel spreadsheet by Locock (2014). Composition of pyroxene was calculated based on 6 oxygens. Content of Fe
3+
was calculated from
stechiometry after Droop (1987). Biotite was normalized to a 22 cation charges after Rieder et al. (1998). Apatite was calculated based on 26 anions.
amphibole
apatite
biotite
pyroxene
Analyse
25
26
27
33
6/19
7/19
23
24
30
31
34
32
29
Formula
Prg
Prg
Prg
Mg-
Hbl
fluorapatite
Ann
Ann
Ann
En
En
Aug
Aug
SiO
2
43.62
42.84
44.18
44.42 P
2
O
5
41.77
40.73 SiO
2
35.86
35.54
36.12 SiO
2
51.19
53.88
52.44
52.11
TiO
2
2.39
2.32
2.68
2.19
SiO
2
0.28
0.27
TiO
2
3.81
4.42
4.35
TiO
2
0.11
0.31
0.51
0.48
Al
2
O
3
10.67
10.11
10.57
9.51
UO
2
0.03
0.02
Al
2
O
3
13.47
13.75
13.98 Al
2
O
3
0.89
1.27
1.70
1.86
Cr
2
O
3
0.02
0.02
0.00
0.00
ThO
2
0.04
0.00
Cr
2
O
3
0.01
0.00
0.00
Cr
2
O
3
0.00
0.01
0.02
0.00
MnO
0.23
0.58
0.19
0.24
Al
2
O
3
0.03
0.03
MnO
0.31
0.23
0.18
MnO
0.85
0.50
0.33
0.27
FeO
14.07
18.57
13.39
16.42 La
2
O
3
0.07
0.05
FeO
23.30
22.87
22.85 FeO
27.64
18.61
9.98
9.30
MgO
12.68
9.52
13.19
11.29 Ce
2
O
3
0.39
0.34
MgO
7.71
8.38
8.25
MgO
17.32
23.84
14.32
14.50
CaO
11.10
10.90
11.45
10.72 Y
2
O
3
0.17
0.06
CaO
0.24
0.06
0.07
CaO
1.27
1.51
20.37
20.88
Na
2
O
2.01
2.01
1.98
1.84
MnO
0.14
0.22
Na
2
O
0.34
0.41
0.41
Na
2
O
0.01
0.02
0.27
0.29
K
2
O
0.57
0.59
0.59
0.60
FeO
0.55
0.24
K
2
O
8.14
8.44
8.36
Total
99.28
99.98
99.93
99.71
F
0.00
0.00
0.00
0.00
MgO
0.00
0.00
F
0.00
0.00
0.00
Si
1.980
1.975
1.958
1.944
Cl
0.03
0.02
0.02
0.05
CaO
54.19
54.85 Cl
0.24
0.18
0.21
T
Al
0.020
0.025
0.042
0.056
Init. Tot.
97.37
97.49
98.29
97.27 SrO
0.03
0.04
Total
93.42
94.28
94.78 Al
0.020
0.030
0.032
0.026
*FeO
12.14
16.86
11.78
14.53 Na
2
O
0.04
0.01
Si
2.853
2.799
2.821 Fe
3+
0.001
0.026
*Fe
2
O
3
2.14
1.90
1.79
2.10
K
2
O
0.00
0.00
T
Al
1.147
1.201
1.179 Ti
0.003
0.009
0.014
0.014
*H2O
+
2.03
1.98
2.04
2.01
F
2.36
2.08
Al
0.116
0.074
0.108 Cr
0.000
0.000
0.001
0.000
Total
99.62
99.66
100.51
99.49 Cl
0.48
0.47
Ti
0.228
0.262
0.255 Mg
0.999
1.303
0.797
0.807
Si
6.448
6.482
6.456
6.627 Total
100.5
99.41 Fe
1.550
1.506
1.492 Fe
2+
0.894
0.571
0.311
0.264
T
Al
1.552
1.518
1.544
1.373 P
5.993
5.806 Mg
0.914
0.984
0.961 Mn
0.028
0.016
0.010
0.008
Ti
0.265
0.264
0.295
0.246 Si
0.047
0.045 Mn
0.021
0.016
0.012 Ca
0.053
0.059
0.815
0.835
C
Al
0.307
0.285
0.277
0.300 Th
0.002
0.000 Cr
0.001
0.000
0.000 Na
0.001
0.001
0.019
0.021
Cr
0.002
0.003
0.000
0.000 U
0.001
0.001 Ca
0.020
0.005
0.006 Cat sum 3.997
3.989
4.000
4.001
Fe
3+
0.239
0.216
0.196
0.236 La
0.004
0.003 K
0.826
0.848
0.833
C
Fe
2+
1.392
2.085
1.352
1.707 Ce
0.024
0.021 Na
0.052
0.063
0.063
Mg
2.795
2.147
2.873
2.511 Y
0.015
0.006 Cat sum
7.727
7.757
7.728
B
Mn
2+
0.028
0.075
0.024
0.030 Al
0.006
0.005
B
Fe
2+
0.109
0.049
0.088
0.105 Fe
0.078
0.034
B
Ca
1.758
1.768
1.792
1.713 Mn
0.021
0.032
B
Na
0.105
0.108
0.095
0.152 Mg
0.000
0.000
A
Na
0.471
0.480
0.465
0.382 Ca
9.839
9.896
K
0.108
0.114
0.110
0.115 Sr
0.003
0.004
O
22.000 22.000 22.000 22.000 Na
0.013
0.004
OH
1.992
1.995
1.995
1.988 K
0.000
0.000
F
0.000
0.000
0.000
0.000 OH
0.593
0.759
Cl
0.008
0.005
0.005
0.012 F
1.267
1.107
Cat sum
15.579 15.594 15.573 15.497 Cl
0.139
0.134
399
NEW AGE DATA FROM THE MIDDLE MIOCENE TUFFS, VIENNA BASIN
GEOLOGICA CARPATHICA
, 2019, 70, 5, 386–404
Source of the Kuchyňa Tuff
In general, the Badenian or younger silicic volcanism was
focused further south in the Pannonian Basin (e.g., Pécskay et
al. 2006; Lexa et al. 2010). The comparison of the different
ages of the volcanic activity is often complicated due to the
variation in quality of the dating methods. However, some
radiometric ages have been refined in the recent years by U/Pb
and Ar/Ar dating (e.g., Lukács et al. 2018).
The deposition of the Kuchyňa tuff is relatively synchro-
nous with a large caldera-forming eruption in the Bükkalja
Volcanic Field (Lukács et al. 2018). This volcanic event pro-
duced high amounts of ignimbrites and tuffs, which were
marked as the Demjén Unit. The Demjén Unit forms a key
stratigraphic horizon in the Pannonian Basin with an age of
14.88 ± 0.014 Ma (Lukács et al. 2018). This unit is formed by
a high-K dacite–rhyodacite ignimbrite, ash flow and fall
deposits composed of plagioclase, biotite, amphibole, ± quartz.
This is relatively consistent with the composition of the
Kuchyňa tuff. However, the Demjén Unit has a well characte-
rized trace element pattern with depleted heavy rare earth
elements and no pronounced negative Eu-anomaly (Eu/Eu*=
0.8–0.9; Lukács et al. 2018; Fig. 5). The Kuchyňa tuff, on
the other hand, displays an Eu-anomaly of 0.59 (Table 2,
which questions their connection.
Another significant horizon
is the Dej tuff (Transylvanian Basin), which was dated to
Table 6: CIPW normative calculation of the Kuchyňa tuffs. All Fe
was calculated as FeO.
wt. % normative minerals
Layer
n-1
n-3
n-4
n-5
quartz
32.27
35.06
37.11
35.82
corundum
10.37
9.90
6.14
7.51
orthoclase
10.52
14.71
20.09
20.27
albite
11.42
10.58
11.34
13.45
anorthite
9.83
6.41
6.88
4.60
diopside
0.00
0.00
0.00
0.00
hypersthene
10.49
8.84
8.19
7.49
magnetite
0.00
0.00
0.00
0.00
hematite
0.00
0.00
0.00
0.00
ilmenite
0.00
0.00
0.00
0.00
apatite
0.14
0.07
0.07
0.14
rutile
0.25
0.15
0.12
0.23
calcite
0.50
0.07
0.17
1.42
Fig. 7. a — Bt-paragneiss lithoclast in tuff, crossed polars; b — Qz-mica shale lithoclast in tuff, crossed polars; c — clay fraction X-ray record
from an oriented slide. Sm — smectite, Hal — halloysite, Bt — biotite, Qz — quartz.
400
RYBÁR et al.
GEOLOGICA CARPATHICA
, 2019, 70, 5, 386–404
14.8–15.1 Ma (K/Ar, Ar/A
multigrain
, FT; Szakács et al. 2012).
The tuff is subduction related and similar in composition:
quartz, plagioclase, biotite, K-feldspar, amphibole ± pyroxene.
But, de Leeuw et al. (2013) updated this age to 14.38 Ma
based on single grain Ar/Ar dating, and this age is not compa-
tible with the Kuchyňa tuff.
On the other hand, the source area of the Kuchyňa tuff may
be found in the nearby Börzsöny–Pilis–Visegrád volcanic
field or in the Central Slovakian volcanic field (after Lexa
et al. 2010). In the time of Kuchyňa tuff deposition, the Bör-
zsöny–Pilis–Visegrád sub-region was much closer to the juve-
nile Danube and Vienna basins and also to the Carpathian
Foredeep (e.g., Kováč 2000; Kováč et al. 2017; Fig. 9). In this
region dacitic and andesitic volcanism with a similar age range
is present and three small-scale caldera forming events were
described (Karátson et al. 2000, 2007; Fig. 5). But around 15
Ma, andesitic activity dominated, which again questions the
connection with Kuchyňa tuff. However, this area remains one
of the best candidates for the source of the Kuchyňa tuff.
Activity of the Central Slovak volcanic field starts in shal-
low water condition (Vinica, Nerestnica fms.). These deposits
of a freatomagmatic eruption were previously dated to
~16.4–15.9 Ma (Konečný in Konečný et al. 1988) but were
recently redated to 15 Ma (Chernyshev et al. 2013). However,
these volcanic and volcanoclastic rocks (tuffs) are mainly
amphibole andesite in composition (amphibole, plagioclase,
± pyroxene, garnet, quartz, biotite), which excludes connec-
tion with the Kuchyňa tuff (Fig. 5). Some rhyodacite tuffs
occur below the Vinica formation, but these ranked to the early
Miocene (Konečný et al. 1998). In this region, volcanic acti-
vity continues with formation of andesitic volcanos and strato-
volcanoes (Konečný et al. 1995; Lexa et al. 2010). Rhyolitic
volcanism in the Central Slovak volcanic field (Jastrabá and
Strelníky fms.), as well as rhyolitic volcanism in the southern
part of East Slovakia can be excluded due to their mostly
Sarmatian (late Serravallian) age 13–11 Ma (e.g., Pécskay et
al. 2002, 2006; Demko 2010; Chernyshev et al. 2013). So,
these volcanic fields cannot be connected to the Kuchyňa tuff.
Another potential source is in the neighbouring Danube
basin, where buried Badenian volcanic centres are present
(Šurany, Kráľová, Rusovce, Trakovice centers; e.g., Hrušecký
1999; Vass 2002; Kronome et al. 2014; Rybár et al. 2016).
But they are also formed by products of biotite-amphibole to
pyroxene andesite volcanism (Kantor 1987; Miháliková 1962;
Gaža 1966; Rybár et al. 2016). However, information about
composition of these volcanoes comes only from disconti-
nuous well cores, still sourcing from these centres is unlikely,
but cannot be fully excluded. Additionally, in the Slovak part
Age data
Length data
Mineral
N
grains
N
rej
ρ
s
N
s
ρ
i
N
i
P(χ
2
)
Age
±1σ
D
U
D
par
SD
Dpar
MTL
±1σ
SD
L
N
L
× 10
6
cm
-2
× 10
6
cm
-2
%
Ma
Ma
ppm
µm
µm
AP
24
0
0.008
35
0.121
547
100.00
14.5
2.8
0.00
116
1.6
0.6
−
−
−
−
AP
31
0
0.007
35
0.126
656
99.96
12.1
2.3
0.00
119
1.6
0.6
−
−
−
−
ZR
15
0
0.45
498
0.735
814
93.87
13.7
1.2
0.00
7121
-
-
-
-
-
-
Table 7: Fission track analyses with their calculated ages (MAKUCH01-sample). First row (AP) does not contain grains with low density
tracks. Abbreviations are as follows: AP = apatite; ZR = zircon; N
grains
is the total number of grains counted; N
rej
represent the number of grains
rejected from final age calculation respectively; ρs and ρi (tracks/cm
2
) are spontaneous and induced track densities respectively; Ns and Ni are
the number of spontaneous and induced tracks counted respectively; P(χ2) is the probability obtaining Chi-square (χ
2
) for n degrees of freedom
(where n is the number of crystals minus 1); age represents a central age for samples that pass P(χ
2
) at 5%, otherwise the mean age is reported
(in bold italics); the age is reported with the 1σ standard error (± 1σ); D is dispersion in single grain age (Galbraith and Laslett 1993); U is
U-content in parts per million; Dpar is average etch pit diameter given with 1σ standard deviation (SD Dpar).
Fig. 8. a — Summary of the single grain
40
Ar/
39
Ar data with error bars for different groups of grains and the mean weighted age of KU
(Kuchyňa tuff) sample (see legend). b — Inverse isochron; the grey line is defined by the grains included for the mean weighted age calcula-
tion. The star represents the atmospheric
40
Ar/
36
Ar composition. All errors are given at 2σ.
401
NEW AGE DATA FROM THE MIDDLE MIOCENE TUFFS, VIENNA BASIN
GEOLOGICA CARPATHICA
, 2019, 70, 5, 386–404
of the Danube Basin, tuff layers occur within the calcareous
nannofossil NN5 Zone (14.9–13.5 Ma; Martini 1971), for
example, in the Trakovice-4, Cífer-2, Špančince-4, Modrany-2
wells (Rybár et al. 2016; Csibri et al. 2018; Hudáčková et al.
2018). Furthermore, all these Danube Basin tuffs show dif-
ferent trace element associations (Fig. 5), thus they cannot be
associated with the Kuchyňa tuff.
Finally, the tuffs in the Western Carpathian Foredeep need
to be also considered. Two main phases of felsic tuffs were
dated by zircon FT; lower Miocene 20.3 ± 2.4 Ma and middle
Miocene 16.2 ± 2.1 Ma (Nehyba 1997; Nehyba et al. 1999;
Nehyba & Roetzel 1999). However, the results of the pre-
sented study show that the FT data may be incoherent.
Additionally, the lower Miocene tuffs from the south-eastern
margin of the Bohemia Massif were refined by
40
Ar/
39
Ar to
17.23 Ma (Roetzel et al. 2014) and the middle Miocene
tuffs located on the Czech–Polish boundary (North-Western
Car pathian Foredeep Basin) were dated by
40
Ar/
39
Ar to
14.27 ± 0.03 Ma (Bukowski et al. 2018). So again connection
to the Kuchyňa tuff cannot be confirmed.
In summary, the Kuchyňa tuff cannot be clearly connected
to a particular volcanic centre. However, the Börzsöny–Pilis–
Visegrád sub-region and the Demjén unit are the best potential
candidates for the source of the Kuchyňa tuff. With regard to
other tuff occurrences, the Kuchyňa tuff can only be clearly
correlated with the above mentioned tuffite from the Bern-
hardsthal-4 well, Vienna Basin (Sant et al. in press).
Conclusions
The deposition of the Kuchyňa tuff took place in terrestrial
conditions, short before the onset of the Badenian (Langhian)
transgression of the Central Paratethys Sea. Fossil leaves indi-
cate subtropical climate with evergreen broadleaved forests.
The studied rhyodacitic, fine grained and lapilly tuffs were
Fig. 9. Paleogeographic reconstruction of the North-Western part of the Carpathian–Pannonian Region showing the possible transport direction
of the ash cloud, which deposited the Kuchyňa tuff. BM — Bohemian massif; NCA — Northern Calcareous Alps; L — Leitha Mts.;
MK — Malé Karpaty Mts.; PI — Považský Inovec Mts.; T — Tribeč Mts.; CWC — Central Western Carpathians; TR — Transdanubian Range;
CF — Carpathian Foredeep; SB — Styrian Basin; VB — Vienna Basin; BD — Blatné Depression (Danube Basin); ŽD — Želiezovce
Depression (Danube Basin); NNB — Novohrad Nógrád Basin; JB — Jászág Basin; RL — Rába Line, HDL — Hurbanovo–Diósjenő Line.
Volcanic centers: 1 — Styrian Basin, 2 — Rusovce, 3 — Kráľová, 4 — Trakovice, 5 — Štiavnica stratovolcano, 6 — Vtáčnik, 7 — Javorie,
8 — Čelovce, 9 — Visegrád-Börzsöny-Burda, 10 — Mátra. The image was modified after Kováč (2000); Pécskay et al. (2006) and Kováč
et al. (2017, 2018).
402
RYBÁR et al.
GEOLOGICA CARPATHICA
, 2019, 70, 5, 386–404
produced by an explosive, possibly Plinian eruption. The Ar/Ar
single grain sanidine age of 15.23 ± 0.04 Ma is interpreted as
the age of this eruption. The origin of the Kuchyňa tuff can be
connected with the syn-rift stage of the Pannonian Basin
system and the tuff most likely originated in the northern parts
of the basin (Börzsöny–Pilis–Visegrád sub-region) and was
transported towards the West.
Acknowledgements: This research was supported by the
Slovak Research and Development Agency under contracts
No. APVV-16-0121, APVV-15-0575, APVV-0315-12; by
the Netherlands Geosciences Foundation (ALW) with funding
from the Netherlands Organization for Scientific Research
(NWO) by VICI grant 865.10.011 of WK; by Grants
UK/70/2019 and UK/211/2019. The authors wish to express
their gratitude to T. Csibri, M. Jamrich, T. Klučiar, A. Lačný,
M. Šujan from Comenius University in Bratislava for help
during field work and sampling. A special thanks goes to
Roel van Elsas for his support in the mineral separation lab at
the VU University and to A. Biroň from the Earth Science
Institute of the SAS for X-ray diffraction analysis. We also
express gratitude the Editors and Reviewers for guidance and
insightful comments.
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i
NEW AGE DATA FROM THE MIDDLE MIOCENE TUFFS, VIENNA BASIN
GEOLOGICA CARPATHICA
, 2019, 70, 5, 386–404
K4 — sample KU-s (sanidine) — 250–500 μm fraction
Negative values in red
Age result PT4 (sanidine)
40(a)/36(a) ± 2σ
40(r)/39(k) ± 2σ
Age (Ma) ± 2σ
MSWD N
K/Ca ± 2σ
Weighted mean age
1.82417
± 0.00250
15.23
± 0.04
2.58 22.71
25.0 ± 20.4
± 0.14 %
± 0.24 %
8 % 3
External error ± 0.32
3.00 2σ Confidence Limit
Analytical Error ± 0.02
1.6074 Error Magnification
Normal Isochron
284.81
± 9.94
1.82718
± 0.00247
15.26
± 0.04
0.58 22.71
± 3.49 %
± 0.14 %
± 0.24 %
45 % 3
External error ± 0.32
3.83 2σ Confidence Limit
Analytical Error ± 0.02
1.0000 Error Magnification
1 Number of Iterations
0.0000000691 Convergence
Inverse Isochron
287.02
± 10.08
1.82650
± 0.00253
15.25
± 0.04
0.25 22.71
± 3.51 %
± 0.14 %
± 0.24 %
62 % 3
External error ± 0.32
3.83 2σ Confidence Limit
Analytical Error ± 0.02
1.0000 Error Magnification
2 Number of Iterations
0.0001677194 Convergence
5 % Spreading Factor
K4 — sample KU-b (biotite) — 200–400 μm
Cannot be calculated — no reliable data
Supplement
The results from single grain
40
Ar/
39
Ar dating of sanidine and biotite; x- grain selected for mean age
calculation.
ii
RYBÁR et al.
GEOLOGICA CARPATHICA
, 2019, 70, 5, 386–404
K4 — sample KU
s (sanidine) — 250–500
μm fraction
Negative values in red
Relative abundances
Selected for
mean
age calc.
36Ar
%1σ
37Ar
%1σ
38Ar
%1σ
39Ar
%1σ
40Ar
%1σ
40(r)/39
(k)
± 2σ
Age
± 2σ
40Ar(r)
39Ar(k)
K/Ca
± 2σ
[fA]
[fA]
[fA]
[fA]
[fA]
075_VU107-K4
0.0132193
4.140
7.174052
3.932
0.049756
21.501
4.0750
0.181
8.0108
0.156
1.13656
± 0.08140
9.51
± 0.68
57.75
0.25
0.2
± 0.0
21
1_VU107-K4
0.0291440
2.582
1.212332
22.274
0.005477
215.355
0.8359
0.895
9.9421
0.091
1.59951
± 0.54206
13.36
± 4.51
13.43
0.05
0.3
± 0.1
242_VU107-K4
0.0003642
113.798
7.243833
12.508
0.083863
11.446
4.0421
0.217
5.7919
0.174
1.60373
± 0.07132
13.40
± 0.59
11
1.79
0.25
0.2
± 0.1
230_VU107-K4
0.0192783
3.589
1.458021
41.410
0.170930
4.131
12.3140
0.082
25.7768
0.043
1.63475
± 0.03459
13.66
± 0.29
78.09
0.75
3.6
± 3.0
234_VU107-K4
0.0152665
3.295
6.170400
10.050
0.015649
68.741
1.9039
0.413
7.4708
0.127
1.78840
± 0.16731
14.94
± 1.39
45.48
0.12
0.1
± 0.0
238_VU107-K4
0.0076510
6.213
2.201901
19.572
0.450208
1.782
34.9232
0.042
65.8318
0.022
1.81386
± 0.00854
15.15
± 0.07
96.23
2.13
6.8
± 2.7
226_VU107-K4
x
0.0501951
0.807
0.378289
167.106
1.720144
0.590
139.8449
0.032
269.9246
0.009
1.82239
± 0.00225
15.22
± 0.02
94.42
8.51
159.0
± 531.3
233_VU107-K4
x
0.0096753
5.678
0.129908
460.776
1.823573
0.586
148.3744
0.033
273.8608
0.006
1.82537
± 0.00262
15.24
± 0.02
98.90
9.03
491.1
±
4526.0
239_VU107-K4
x
0.0034848
13.822
1.448549
40.360
1.052024
0.979
85.0259
0.034
156.5442
0.013
1.82672
± 0.00379
15.25
± 0.03
99.22
5.17
25.2
± 20.4
072_VU107-K4
0.0167818
3.087
0.3071
18
70.271
2.776837
0.293
227.7500
0.031
421.7969
0.005
1.82928
± 0.00180
15.28
± 0.01
98.77
13.86
318.9
± 448.2
266_VU107-K4
0.0247442
2.474
0.134052
201.821
2.678822
0.423
216.7077
0.032
404.2145
0.009
1.83029
± 0.00209
15.28
± 0.02
98.13
13.19
695.1
±
2805.9
237_VU107-K4
0.0634326
0.968
1.076633
48.939
1.343396
0.748
106.7418
0.032
214.3803
0.008
1.83099
± 0.00374
15.29
± 0.03
91.17
6.50
42.6
± 41.7
076_VU107-K4
0.0010689
51.639
0.328175
82.682
1.190355
0.841
96.5392
0.033
176.8512
0.017
1.83467
± 0.00371
15.32
± 0.03
100.15
5.87
126.5
± 209.2
073_VU107-K4
0.0191579
2.438
0.439096
50.843
3.235765
0.268
264.2576
0.032
493.2103
0.007
1.84405
± 0.00162
15.40
± 0.01
98.80
16.08
258.8
± 263.1
241_VU107-K4
0.0378894
1.516
2.190971
42.256
1.006295
0.855
79.1695
0.036
158.0834
0.014
1.85533
± 0.00494
15.49
± 0.04
92.91
4.82
15.5
± 13.1
232_VU107-K4
0.0634702
0.966
0.999862
48.595
2.21
1824
0.522
177.9574
0.032
351.6283
0.008
1.86816
± 0.00246
15.60
± 0.02
94.55
10.83
76.5
± 74.4
229_VU107-K4
0.0043769
12.090
1.122332
59.607
0.547795
1.405
42.8203
0.043
79.4559
0.019
1.88745
± 0.00798
15.76
± 0.07
101.72
2.61
16.4
± 19.6
K4 — sample KU-b (biotite) — 200–400 μm
Relative abundances
36Ar
[fA]
%1σ
37Ar
[fA]
%1σ
38Ar
[fA]
%1σ
39Ar
[fA]
%1σ
40Ar
[fA]
%1σ
40(r)/39
(k)
± 2σ
Age
± 2σ
40Ar(r)
39Ar(k)
K/Ca
± 2σ
070_VU107-K5
1.4371723
0.221
0.2366880
90.996
1.2446337
0.731
67.39425
0.039
516.90946
0.007
1.30299
± 0.031
13
10.89
± 0.26
16.99
49.51
122
± 223
064_VU107-K5
0.1323083
0.533
0.221
1982
109.773
0.2120470
3.795
12.85359
0.074
60.47030
0.019
1.63224
± 0.03363
13.64
± 0.28
34.69
9.44
25
± 55
066_VU107-K5
0.0975658
0.751
0.1241427
226.806
0.3252785
3.043
22.48018
0.055
67.73521
0.031
1.71629
± 0.01993
14.34
± 0.17
56.96
16.52
78
± 353
067_VU107-K5
0.0706030
1.133
0.0569915
452.144
0.4854014
1.965
33.30935
0.043
81.1
1578
0.021
1.80201
± 0.01457
15.05
± 0.12
74.00
24.47
251
± 2273
069_VU107-K5
0.0000030
15120.1
18
0.0218049
985.218
0.0057293
148.214
0.08031
12.135
0.30658
4.225
3.82740
± 3.53960
31.82
± 29.17
100.25
0.06
2
± 31
iii
NEW AGE DATA FROM THE MIDDLE MIOCENE TUFFS, VIENNA BASIN
GEOLOGICA CARPATHICA
, 2019, 70, 5, 386–404
K4 — sample KU-s (sanidine) — 250–500 μm fraction
Negative values in red
Procedure
Blanks
36Ar
[fA]
1s
37Ar
[fA]
1s
38Ar
[fA]
1s
39Ar
[fA]
1s
40Ar
[fA]
1s
075_VU107-K4
0.0576419
0.0002875
0.0112875
0.0002127
0.0907446
0.0069851
0.0843214
0.0044608
12.8121465
0.0079092
211_VU107-K4
0.0462685
0.0005383
0.0114935
0.0002019
0.0982028
0.0073493
0.1112209
0.0033841
9.3666217
0.0062690
242_VU107-K4
0.0340295
0.0003026
0.0209043
0.0004184
0.0541622
0.0071173
0.0280898
0.0056539
6.6272261
0.0079850
230_VU107-K4
0.0370447
0.0004599
0.0207755
0.0002200
0.0313227
0.0035205
0.0329262
0.0058807
7.8470666
0.0081272
234_VU107-K4
0.0300846
0.0003327
0.0223419
0.0002316
0.0254738
0.0083092
0.0410613
0.0060767
5.5256340
0.0066072
238_VU107-K4
0.0300262
0.0003731
0.0222138
0.0001942
0.0331927
0.0057509
0.0297939
0.0033783
5.5774083
0.0048996
226_VU107-K4
0.0309244
0.0002346
0.0217698
0.0002382
0.0134130
0.0063271
0.0309833
0.0043349
5.7567186
0.0041848
233_VU107-K4
0.0300846
0.0003327
0.0223419
0.0002316
0.0254738
0.0083092
0.0410613
0.0060767
5.5256340
0.0066072
239_VU107-K4
0.0300262
0.0003731
0.0222138
0.0001942
0.0331927
0.0057509
0.0297939
0.0033783
5.5774083
0.0048996
072_VU107-K4
0.0472019
0.0003194
0.0114294
0.0001770
0.0807464
0.0050695
0.0762645
0.0036624
9.3936982
0.0078200
266_VU107-K4
0.0448238
0.0003445
0.0112556
0.0001523
0.0916567
0.0057580
0.0889090
0.0055367
8.9034586
0.0072972
237_VU107-K4
0.0300262
0.0003731
0.0222138
0.0001942
0.0331927
0.0057509
0.0297939
0.0033783
5.5774083
0.0048996
076_VU107-K4
0.0576419
0.0002875
0.0112875
0.0002127
0.0907446
0.0069851
0.0843214
0.0044608
12.8121465
0.0079092
073_VU107-K4
0.0472019
0.0003194
0.0114294
0.0001770
0.0807464
0.0050695
0.0762645
0.0036624
9.3936982
0.0078200
241_VU107-K4
0.0340295
0.0003026
0.0209043
0.0004184
0.0541622
0.0071173
0.0280898
0.0056539
6.6272261
0.0079850
232_VU107-K4
0.0300846
0.0003327
0.0223419
0.0002316
0.0254738
0.0083092
0.0410613
0.0060767
5.5256340
0.0066072
229_VU107-K4
0.0370447
0.0004599
0.0207755
0.0002200
0.0313227
0.0035205
0.0329262
0.0058807
7.8470666
0.0081272
K4 — sample KU-b (biotite) — 200–400 μm
Procedure
Blanks
36Ar
[fA]
1s
37Ar
[fA]
1s
38Ar
[fA]
1s
39Ar
[fA]
1s
40Ar
[fA]
1s
070_VU107-K5
0.0505644
0.0003093
0.0117142
0.0001730
0.0781906
0.0049747
0.0670506
0.0077162
10.436953
0.009939
064_VU107-K5
0.0451061
0.0003777
0.0114143
0.0001677
0.0909624
0.0044538
0.0798352
0.0052203
8.777078
0.005512
066_VU107-K5
0.0466496
0.0003859
0.0117590
0.0002199
0.0801151
0.0062311
0.0664830
0.0042479
9.244781
0.006819
067_VU107-K5
0.0466496
0.0003859
0.0117590
0.0002199
0.0801151
0.0062311
0.0664830
0.0042479
9.244781
0.006819
069_VU107-K5
0.0505644
0.0003093
0.0117142
0.0001730
0.0781906
0.0049747
0.0670506
0.0077162
10.436953
0.009939
Sample
Parameters
Material
Standard
(Ma)
%1s
J
%1s
MDF
%1s
Day
Time
075_VU107-K4
sanidine
28.201
0.08
0.004579
0.1
0.9944
0.03
8.2.17
18:27
211_VU107-K4
sanidine
28.201
0.08
0.004579
0.1
0.9944
0.03
14.3.17
19:54
242_VU107-K4
sanidine
28.201
0.08
0.004579
0.1
0.99286
0.03
14.3.17
13:18
230_VU107-K4
sanidine
28.201
0.08
0.004579
0.1
0.99286
0.03
14.3.17
8:53
234_VU107-K4
sanidine
28.201
0.08
0.004579
0.1
0.99286
0.03
14.3.17
10:08
238_VU107-K4
sanidine
28.201
0.08
0.004579
0.1
0.99286
0.03
14.3.17
11:14
226_VU107-K4
sanidine
28.201
0.08
0.004579
0.1
0.99286
0.03
13.3.17
16:58
233_VU107-K4
sanidine
28.201
0.08
0.004579
0.1
0.99286
0.03
14.3.17
9:49
239_VU107-K4
sanidine
28.201
0.08
0.004579
0.1
0.99286
0.03
14.3.17
11:32
072_VU107-K4
sanidine
28.201
0.08
0.004579
0.1
0.9944
0.03
8.2.17
17:34
266_VU107-K4
sanidine
28.201
0.08
0.004579
0.1
0.9944
0.03
16.2.17
12:03
237_VU107-K4
sanidine
28.201
0.08
0.004579
0.1
0.99286
0.03
14.3.17
10:53
076_VU107-K4
sanidine
28.201
0.08
0.004579
0.1
0.9944
0.03
8.2.17
18:45
073_VU107-K4
sanidine
28.201
0.08
0.004579
0.1
0.9944
0.03
8.2.17
17:52
241_VU107-K4
sanidine
28.201
0.08
0.004579
0.1
0.99286
0.03
14.3.17
12:59
232_VU107-K4
sanidine
28.201
0.08
0.004579
0.1
0.99286
0.03
14.3.17
9:30
229_VU107-K4
sanidine
28.201
0.08
0.004579
0.1
0.99286
0.03
14.3.17
8:34
Sample
Parameters
Material
Standard
(Ma)
%1s
J
%1s
MDF
%1s
Day
Time
070_VU107-K5
biotite
28.201
0.08
0.004579
0.1
0.9944
0.03
8.2.17
16:58
064_VU107-K5
biotite
28.201
0.08
0.004579
0.1
0.9944
0.03
8.2.17
15:12
066_VU107-K5
biotite
28.201
0.08
0.004579
0.1
0.9944
0.03
8.2.17
15:47
067_VU107-K5
biotite
28.201
0.08
0.004579
0.1
0.9944
0.03
8.2.17
16:05
069_VU107-K5
biotite
28.201
0.08
0.004579
0.1
0.9944
0.03
8.2.17
16:41
iv
RYBÁR et al.
GEOLOGICA CARPATHICA
, 2019, 70, 5, 386–404
Information on Analysis and used Constants for samples of KU
(K4: sanidine, K5: biotite)
Analysis
Material
sanidine, biotite
Location
Kuchyna, Slovakia
Analyst
K. Kuiper
Project
VU107
Mass Discr. Law
LIN
Irradiation
VU109
J (K4)
0.00457860 ± 0.00000458
FCs
28.201 ± 0.023 Ma
Heating
45 sec
Isolation
3.00 min
Instrument
ARGUS
Constants
Age Equations
Min et al. (2000)
Negative Intensities
Allowed
Decay Constant 40K
5.460 ± 0.053 E-10 1/a
Decay Constant 39Ar
2.940 ± 0.016 E-07 1/h
Decay Constant 37Ar
8.230 ± 0.012 E-04 1/h
Decay Constant 36Cl
2.257 ± 0.015 E-06 1/a
Decay Activity 40K(EC,β
+
)
3.310 ± 0.030 1/gs
Decay Activity 40K(β
−
)
27.890 ± 0.150 1/gs
Atmospheric Ratio 40/36(a)
298.56 ± 0.31
Atmospheric Ratio 38/36(a)
0.1885 ± 0.0003
Production Ratio 39/37(ca)
0.000673 ± 0.000004
Production Ratio 36/37(ca)
0.000264 ± 0.000002
Production Ratio 40/39(k)
0.000860 ± 0.000070
Production Ratio 38/39(k)
0.012110 ± 0.000030
Production Ratio 36/38(cl)
262.80 ± 1.71
Scaling Ratio K/Ca
0.43
Abundance Ratio 40K/K
1.1700 ± 0.0100 E-04
Atomic Weight K
39.0983 ± 0.0001 g