THE ORIGIN OF CALCAREOUS SINTER FROM POKRZYWIANKA
GÓRNA (HOLY CROSS MTS, POLAND) BASED ON THE CHEMISTRY
OF ROCK AND PRESENT WATERS.
Sabina Dołęgowska, Joanna Masternak, Artur Michalik
Institute of Chemistry, Faculty of Mathematical and Natural Sciences Pedagogical
University, 5 Chęcińska Str., 25-020 Kielce.
Artur.Michalik@pu.kielce.pl
ABSTRACT
The calcareous sinter, spring and stream waters from Pokrzywianka Górna (Holy
Cross Mts) were analyzed to explain the origin of calcareous sinter (travertine). The
concentrations of selected metals, i.e. Cu, Cd, Fe, Ni, Mn, Pb and Zn, were
determined in the rock and waters using flame atomic absorption spectrometry (PU
9100 X UNICAM). In addition, pH, conductivity, alkalinity and concentrations of
selected ions (SO42-, Cl-, NO2-, NO3-, NH4+, PO43-, Fetotal, Mn2+) in water
samples were measured using a portable spectrophotometer SLANDI LF205 and
field ELMETRON pH- and conductivity-meters. The results revealed a substantial
enrichment of rock in Mn and other metals, which can support the hypothesis on the
hydrothermal origin of calcareous sinter from Pokrzywianka Górna. The chemistry of
present waters is not affected by the sinter outcrop. The high alkalinity of waters
seems to be associated with a widespread thick cover of loesses that contain about
12% of calcium carbonate.
INTRODUCTION
At the western boundary of the Pokrzywianka Górna village located northeast of
Nowa Słupia (northeastern part of the Holy Cross Mountains), a unique calcareous
sinter outcrop of about 9 x 2 m occurs. About 50 m west of it there is a cased spring
(well) and a flowing northward small stream charged by some nearby seeps and the
spring (fig. 1). The sinter (travertine) is a chemical sedimentary rock that consists
primarily of calcite (CaCO3) or silica (SiO2). It forms by precipitating chemical
compounds from spring water as a result of the rapid changes in physicochemical
conditions (temperature, pressure etc.), e.g. appearance of geochemical barriers
[1,2]. Silica and calcareous sinters are being formed now around hot springs, the best
examples of which are contemporary hydrotherms of Yellowstone National Park [3].
The calcareous sinter from Pokrzywianka Górna originated in the Holocene, about
several thousand years ago [4]. The field observations indicated that the sinter small
dome occurs within a tectonic fault zone separating the Pokrzywianka elevation from
Chełmowa Mount. The principal objective of this study was to find any chemical
relationships between the sinter outcrop and nearby waters.
EXPERIMENTAL
The rock and water samples were collected from the sinter outcrop on May 5th of
2005. The pH and conductivity of waters were measured directly in the field with a
portable ELMETRON pH- and conductivity-meters. The collected samples were
transported to the Geochemistry and Environment Division Laboratory of
Pedagogical University in Kielce on the same day. The waters were analyzed without
sample preservation. This paper also encompasses the results derived from the
previous analyses of spring waters (January and April of 2005). The sampling design
and localization of the study area are shown in figure 1.
Fig. 1. Localization of investigation sites within the study area.
The determinations of alkalinity and concentrations of selected ions (i.e. sulfate,
phosphate, chloride, iron, manganese, zinc, nitrite, nitrate, ammonium) were
performed with a portable SLANDI LF205 spectrophotometer. The sets of reagents
that were used for these analyses have been supplied by SLANDI. The detection
limits for this method are presented in tables 2 and 3 contained in the next section.
The concentrations of Cu, Cd, Zn, Ni, Mn, Fe and Pb were determined in the rock
and spring water samples with an Atomic Absorption Spectrometer PU 9100 X
UNICAM. The rock sample (2.932 g) was digested with aqua regia. The water
samples were evaporated to obtain a tenfold concentrate. The detection limits for the
described method are presented in tables 1 and 2 of the next section.
RESULTS AND DISCUSSION
The results of rock and water analyses from Pokrzywianka Górna are shown in tables
1 through 3. The chemical analyses of calcareous sinter reveal a considerable
enrichment of this rock in Mn (16323.8 mg kg-1d.w.). It should be stressed that the
remaining metals (Cd, Cu, Pb, Zn, Ni and Fe) also show raised levels. The pH values
of the water analyzed were in the range of 6.26 - 7.44, which is typical for surface
waters (6.5-8.5) [5]. The conductivity was relatively high and reached 694 mS cm -1 in
the spring water. The concentrations of Cd, Ni, Mn and Fe did not exceed 10 mg dm -
3,
whereas Pb - 30 mg dm-3. Only the spring water was highlighted by a higher
concentration of Cu (39 mg dm-3) and Zn (45 mg dm-3). The waters examined also
revealed high alkalinity (260 - 334 mg CaCO3 dm-3), which is unique for surface
waters yielding a typical range of 60 - 90 mg CaCO3 dm-3 [5]. In author's opinion, the
high alkalinity of these waters can be explained by a presence of thick loess cover in
this part of the Holy Cross Mts. The loesses contain a substantial amount of
scattered calcium carbonate (averaging 12%), which can be easily washed out by
rain, thus enriching surface and underground waters in Ca(HCO3)2.
Table 1. Concentrations of selected elements in calcareous sinter
Element Detection limit Concentrations mg kg-1 (d.w.)
Cd
3.4
13.1
Cu
3.4
9.4
Fe
3.4
141.6
Mn
3.4
16323.8
Ni
3.4
11.8
Pb
30.0
28.2
Zn
3.4
42.4
Table 2. The chemical analyses of spring water
Element
Unit
Analytical method
Detection limits Results
Cd
10
<10
Cu
10
39
Fe
30
<10
Atomic absorption spectrometry 10
<10
Ni
10
<10
Pb
10
<30
Zn
10
45
-
1.) 6.57a
2.) 6.26b
3.) 7.44c
-
1.) 683a
2.) 694b
3.) 558c
0-500
1.) 334a
2.) 282c
10-1000
1.) 32a
2.) 37b
3.) 33c
μg dm-3
Mn
pH
-
Conductivity μS cm
Electrochemical
-1
Alkalinity
mgMgCO3 dm-3
2-
-3
Electrochemical
Spectrophotometric
SO4
mg dm
Cl-
2-100
14.6
0.1-2.0
<0.1
0.5-50.0
6.8
0.02-1.00
0.07
NH4+
0.1-3.0
0.2
Fetotal
0.05-6.0
<0.05
2+
0.05-2.0
0.22
PO4
3-
NO3NO2
-
Mn
NOTE: dates of analyses: a - January 12th of 2005; b - April 1st of 2005; c - May 5th
of 2005
The physicochemical and chemical parameters of the examined spring water differ
depending on the season of sampling. The seasonal variability is probably connected
with different climatic factors (snowmelt, precipitation, temperature), and should be
further studied.
Table 3. The results of spring and stream analyses
Parameter
Unit
pH
-
Conductivity μS cm
Alkalinity
SO4
Detection limits Results
-1
2-
3-
NO3-
7.85
-
626
mgMgCO3 dm-3 0-500
ClPO4
-
mg dm-3
260
10-1000
57
2-100
26
0.1-2.0
<0.1
0.5-50.0
11.3
NO2
-
0.02-1.00
0.07
NH4
+
0.1-3.0
0.1
CONCLUSIONS
The analyses of the sinter, spring and stream waters from Pokrzywianka Górna allow
us to conclude that: 1.The calcareous sinter shows raised concentrations of metals,
especially Mn. 2.The analyzed spring and stream waters are depleted in metals and
show high alkalinity that can be linked to the presence of thick loess cover within the
study area. The results indicate that there is no genetic relationship between the
examined waters and the sinter formation. 3.The calcareous sinter from
Pokrzywianka Górna is a remnant deposit of a hot spring linked to the fault zone
which was reactivated in Holocene time.
ACKNOWLEDGMENTS
The authors would like to thank Prof. Zdzisław M. Migaszewski and Dr. Agnieszka
Gałuszka of the Pedagogical University in Kielce for reviewing this article and
valuable remarks.
REFERENCES
[1] W. Ryka, A. Maliszewska, Słownik petrograficzny. Wyd. Geol. Warszawa. 1991.
[2] Z. Migaszewski, A. Gałuszka, Zarys Geochemii Środowiska. Wyd. Akademii
Świętokrzyskiej. Kielce. 2003.
[3] A.G. Harris, E. Tuttle, Geology of National Parks. Kendall/Huet Publishing Co.
Iowa. U.S.A. 1990.
[4] E. Stupnicka, M. Stempień-Sałek, Poznajemy Góry Świętokrzyskie. Wycieczki
geologiczne. Wyd. Nauk. PWN. Warszawa. 2001.
[5] J. Dojlido, Fizyczno-chemiczne badanie wody i ścieków. "Arkady". Warszawa.
1999.