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Geochemical distribution of Ti, Mn, V, Fe, Zn and Pb in stream sediments in

relation to geology, lithology and anthropogenic activities: Oltet river basin,
Romania

Article  in  Environmental Earth Sciences · July 2019

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 Ecology and Environmental Protection

GEOCHEMICAL DISTRIBUTION OF Ti, Mn, V, Fe, Zn AND Pb IN STREAM

SEDIMENTS IN RELATION TO GEOLOGY, LITHOLOGY AND
ANTHROPOGENIC ACTIVITIES: OLTET RIVER BASIN, ROMANIA

Dr. Adriana Ion1, 2, Ing. Ana Cosac1 and PhD student D.Bargaoanu1

1
Geological Institute of Romania, Bucharest, 012270, Romania
2
ICUB - University of Bucharest, Bucharest, 050107, Romania

ABSTRACT
This study examined the spatial relations of the selected metals in stream sediments
tributary of the Oltet River in longitudinal profile, along the entire length (185 km) in
relation to geology, lithology and anthropogenic activities.
Differences in regional geology from the northern to the southern of the Oltet River
Basin are reflected in stream sediment geochemistry. The Olteț River crossing
crystalline formations belonging to the Danubian Domain represented by metamorphic
rocks (schist, gneisses, mica-schiste) and the Pre-Alpine granite and granitoide massifs
(Suşiţa, Tismana, Novaci, Cărpiniş type) associated (granitoide rocks are crossed by
veins of microgranite, aplite, pegmatite and lamprophyre) of Upper Carboniferous,
Permian and Mesozoic ages, followed by the Cenozoic formations belonging to the
Dacian Basin. From the sequence of Cenozoic deposits, are remarkable the Pontian –
Romanin deposits composed of clays, marnes, sands, that are characterized by the
presence of lignite seams. Over Cenozoic deposits, in the midline and to the
confluence with the Olt River zone, occurs the Quaternary formation (Lower, Middle
and Upper Pleistocene). The Lower Pleistocene, rich in vertebrate fossils is composed
by marnes, sands, gravels, with lenticular sandy-clay sequences and layers of coal. The
Middle Pleistocene deposits are separated as sand-dusty deposits with high content of
clays, whereas Upper Pleistocene is represented by the alluvial deposits (sands,
gravels, clays) belonging to the Olt terrace.
The type of methodology used in this study consists of geochemical sampling of
stream sediments, mineralogical analysis, and quantitative determination of metals,
GIS database and comparison of the stream sediments content with standards and
levels recorded in the literature. Most metal concentrations can by spatially correlate
to the regional geology, structural trends and the local effects of individual rocks units.
Higher concentrations of vanadium, lead in stream sediments may have resulted from
some anthropogenic activities. Activities that appear to have affected stream sediment
include exploitation of the lignite in open pit and urban centers.

Keywords: stream sediments, geochemical distribution, geology, anthropogenic

activities

INTRODUCTION
The sediments are constituted as an archive of explorable geochemical datasets for
natural elements generated by petrographic variability of riverbed material composition
18th International Multidisciplinary Scientific GeoConference SGEM 2018

explained in relation to the petrography of the source area. Stream sediments

geochemistry represents the average composition of rocks within each drainage from
which those sediments are derived. Stream sediments geochemistry can be used to
quantify natural geochemical baselines and anthropogenic effects. Natural elements
enrichments caused by mineralization, host rock sources and landscape type can be
distinguished from anthropogenic effects in stream sediments. [2] The heavy metal
concentration in sediments depends by the geological setting and anthropogenic
activities. [9] The occurrence of heavy metals in excess of natural background
concentration level in aquatic ecosystems can affect the water quality has drawn
attention do to their toxicity. The increasing of heavy metals concentration in water has
been associated to anthropogenic activities, including mining and industrial activities,
domestic wastes, urban run-off, leaching of metals from garbage and solid wastes dump.
Also, agricultural, medical and technological applications have led to their wide
distribution in the environment; raising concerns over their potential effects on human
health and the environment. [8]
The hydrographic basin of Oltet has a great importance mainly in the middle zone,
where the coal deposits are extracted in open pit and the Olteț River crossing these
deposits, and washing upstream metamorphic magmatic and sedimentary rocks. The
upper area of the basin is affected by the presence of many waste dumps resulted by
exploitation of graphit deposits, limestone and granite exploitation in open pit.
The present study proposes to evaluate the geochemical distribution of manganese
(Mn), titanium (Ti), iron (Fe), vanadium (V), lead (Pb) and zinc (Zn) in stream
sediments from Oltet River in relation to geology, lithology and anthropogenic
activities. The heavy metals investigated are Pb and Zn. Fe, Mn, Ti and V are selected
because on their role played in availability of heavy metals to stream water or their
potential use in interpreting the distribution of heavy metals in relation with litological
and geological features of the area investigated.

THE STUDY AREA DESCRIPTION AND GEOLOGICAL SETTING

The drainage basin of the Olteţ River is located in the southern central part of the
country, having an area of 2663 km2 and a length of principal stream by 185 Km. Most
of the important tributaries of Olteţ River are Cerna, Saşa and Tîrlea and, the range of
elevation on flowing varies between 1963 m in the springs area (Parîng Mountains –
Negovanu Peak) and 200 m at the confluence with the Olt River. The relief of Olteţ
Basin has fragmented character, manifested by the presence of numerous forms of relief
from, starting with major mountainous heights and ending with low-lying plains
regions. The relief in the upper zone, the southern slopes of the Parîng Mountains, is the
result of glacial action of quaternary glaciers, being represented by valleys, ridges and
alpine glacial cirques. Below, the Olteţ River crosses the hillside of the Getic Sub-
Carpathians and piedmont area represented by Olteţ Hills. In the South, toward the
confluence with the Olt River, the Olteţ River crosses a hills area and makes the
transition between the Getic Piedmont and Romanian Plain. As result of almost abrupt
passage between mountain and hilly terrains, at contact between the highlands and the
lowlands the torrents were deposited large quantities of clastic material [1]. The climate
is temperate continental with a wide variety of shades, due to its geograph. ical position,
atmospheric circulation and relief components present.
 Ecology and Environmental Protection

From the geological point of view, in cross section from North to South, the Olteț River
cuts across basement formations belonging to the Danubian domain represented by
metamorphic rocks (schist, gneisses, quartzite, marble, mica-schist’s) and associated
Pre-Alpine granite and granitoid massifs (granitoide rocks are intruded by veins of
microgranite, aplite, pegmatite and lamprophyre), and Paleozoic to Mesozoic
sedimentary (carbonate rocks), followed by post-tectonic Cenozoic formations
belonging to the Dacian Basin. From the sequence of Cenozoic deposits, remarkable are
the Pontian – Romanian deposits composed of clays, marls, sands, that are characterized
by the presence of lignite seams. On top of the Cenozoic deposits, a Quaternary
formation occurs in the midline and to the confluence with the Olt River zone. [3] The
Quaternary deposits, enriched in fossil vertebrates are composed by marls, sands,
gravels, with lenticular sandy-clayey sequences and layers of coal (figure 1). [1]

MATERIAL AND METHODS

A number of 44 stream sediment samples were collected at location from Oltet River
shown in the map (figure 1). The sediments were collected in the dry season (summer of
2016) from sampling points distributed along the river with an equidistance of about 4-5
km. The samples, with a weight of about 10 Kg, were placed into plastic bags. In
laboratory, the stream sediment samples were dried at room temperature and then sieved
by a Teflon sieves with a 2mm, respectively 0.63 mm mesh. [7] The fraction of 0.63
mm was quartered and homogenized in a mill to a grain size below 0.15 mm.
The fraction of the 0.15 mm was used for chemical analysis of Mn, Ti, Fe, Vn, Pb and
Zn. The selected elements were quantitatively determined by XRF spectrometry, using
an Innov X Delta spectrometer (DPO – 6000) Olympus, with following characteristics:
Si- X ray detector, 4 W X-ray tube and 200µA current (max). The exposure time was 60
s and the lower limit of detection for investigated elements is 2 ppm.
Exploratory statistical parameters of geochemical data set were calculated using SPSS
17 software. Each variable (concentration of element) was estimated in terms of
minimum, maximum, mean, standard deviation (SDEV), skewness, variance and
kurtosis. The correlation analysis was based on the Pearson’s coefficients. The
assumptions of normality for the geochemical data set were evaluated by Kolmogorov –
Smirnov test (ap).The spatial distribution of the investigated elements (Mn, Ti, Fe, Vn,
Pb and Zn) in stream sediments was assessed through the elemental geochemical
distribution maps. The spatial point grid was built using the geographic coordinates for
each sampling point, by attributing in each point individual values of Mn, Ti, Fe, Vn, Pb
and Zn contents. Inverse Distance Weighting (IDW) is the interpolation method that
was chosen to obtain the spatial distribution of selected elements in longitudinal profile
of the Oltet River. The software used for graphical representation and interpolation of
the data is Arc GIS 9.3 from ESRI.

RESULTS AND DISSCUTION

Table 1 shows the values of the main statistics parameters for selected elements.
Statistical analysis showed large variation of the Ti, Mn, Fe, V, Zn and Pb contents in
18th International Multidisciplinary Scientific GeoConference SGEM 2018

Fig. 1. Geological map of Oltet River Basin (redraw after geological map – Tirgu Jiu
sheet L- 34 - XXX, 1: 200.000 scale).
 Ecology and Environmental Protection

stream sediments of Oltet River. The Kolmogorov – Smirnov test was employed for the
distribution test of stream sediments metals. It was found that Mn concentration was in
normal distribution and Ti, Fe, V, Pb and Zn indicated a log-normal distribution. The
standard deviation shows a very high degree of dispersion.
The spatial distribution of Ti, Mn, Fe, V, Zn and Pb in Oltet River sediments are
presented in figure 2 (2.a – 2.f). The correlations between elements are shows in table 2.
Table 1. Statistical summary for selected elements in stream sediments of Oltet River
Statistical parameter Ti Mn Fe V Zn Pb
Minimum 981.00 218.80 4623.00 184.50 10.21 8.85
Maximum 7794.00 1433.14 56829.00 559.00 73.11 36.21
Mean 2389.57 527.052 16291.7021 340.8936 26.6491 14.8430
Std. Deviation 1346.15 233.47 11355.11 83.83 15.62 4.66
Variance 1812131.8 54510.967 1.289 7028.688 244.284 21.727
Skewness 1.932 1.575 1.546 0.585 1.217 2.506
Kurtosis 4.848 3.905 2.918 0.535 0.899 9.256
a
p 0.004 0.076 0.001 0.028 0.001 0.011
a
p- value from Kolmogorov - Smirnov normality test
In a normal distribution, significant values must be great that 0.05 (sig.>0.05)
Titanium (Ti) is a lithophile metallic element and has a concentration in the sediment
samples that varies between 981 ppm and 7794 ppm, with an average value of 2389.57
ppm. The mean of Ti in Oltet River sediments is comparable with value of crustal
abundance – 6320 ppm. [7] Ti has very low mobility under almost all environmental
condition and reflected the geological features. The Ti distribution map show high
values over northern areas with outcropping Paleozoic and crystalline basement rocks.
Table 2. Pearson correlation among selected elements in stream sediments (N=44)
Ti Mn Fe V Zn Pb
** * **
Pearson Correlation 1 .201 .510 .352 .504 .322*
Ti
Sig. (2-tailed) .176 .000 .015 .000 .027
Pearson Correlation .201 1 .060 .151 .062 .084
Mn
Sig. (2-tailed) .176 .690 .310 .677 .575
** * **
Pearson Correlation .510 .060 1 .293 .736 .327*
Fe
Sig. (2-tailed) .000 .690 .046 .000 .025
Pearson Correlation .352* .151 .293* 1 .240 .000
V
Sig. (2-tailed) .015 .310 .046 .104 .999
** **
Pearson Correlation .504 .062 .736 .240 1 .038
Zn
Sig. (2-tailed) .000 .677 .000 .104 .800
Pearson Correlation .322* .084 .327* .000 .038 1
Pb
Sig. (2-tailed) .027 .575 .025 .999 .800
**. Correlation is significant at the 0.01 level (2-tailed).
*. Correlation is significant at the 0.05 level (2-tailed).
18th International Multidisciplinary Scientific GeoConference SGEM 2018

Fig.2. Spatial distribution of titanium (2.a), manganeses (2.b), iron (2.c), vanadium (2.d), zinc
(2.e) and lead (2.f)
Manganese (Mn) in stream sediments is relatively abundant with an average of 527.05
ppm, comparable with values reported by Mc Lennen and Taylor (1999) for upper
crustal abundance. The content of Mn varies between (218.8 – 1433 ppm). [5] The
geochemical map of Mn (fig. 2.b) indicates high values in middle part of the basin in
area with coal deposits that reflecting bedrock signatures. From this maximum point, the
manganese concentration decreases concentrically to the south, where are present the
sandy deposits and to the north where metamorphic and sedimentary rocks occurs.
Iron (Fe) is a major element in analyzed stream sediment samples, with an average of
16291 ppm. The abundance of Fe is determined by provenance, pH –Eh conditions,
alteration and grain size. [4] Iron is relatively immobile under most environmental
 Ecology and Environmental Protection

conditions; its solubility is strongly influence by redox conditions. The spatial

distribution of iron show high concentration in the midline of Oltet River, and
downstream of coal seams at confluence with the Olt River (fig. 2.c). This trend in
distribution suggests coprecipitation of metal on surface coatings in stream sediment,
reflecting surficial processes rather than underlying bedrock signatures.
Vanadium (V) in stream sediment samples has higher values (184.05 – 559.00 ppm),
with an average of 340.89 ppm, that is much higher that values reported by Rudnick &
Gao (2004) for upper continental crust (97 ppm). The V distribution map (fig. 2.d) has
many similarities to the Fe distribution. Low V area is located in the north of perimeter
being associated with the presence of metamorphic and sedimentary rocks and reflects
the abundance of minerals, such as Fe – Ti – Cr oxides. High V area is placed in the
median zone, where the water of Oltet River washing the seams coal, and reflecting
both affinity of the element for organic sorption sits and its relative immobility under
reduction conditions.
Zinc (Zn) is a calcophile metallic element with content values in Oltet River stream
sediments vary between 10.21ppm and 73.11 ppm, has an average value of 14.84 ppm.
These concentrations of Zn found in the study area as well as of the normal values being
under threshold values of Romanian Sedimentary Quality Guidelines (100 ppm). The
distribution map of Zn (fig. 2.e) draw area of the plain (in southwest) where the
concentration of Zn is highest, and probably reflects the low influence of coal mining,
road traffic and phosphate fertilizer used in agriculture. The spatial distribution of Zn is
correlates with the Fe, and suggesting distribution of the ferromagnesian silicates in the
parent rocks.
Lead (Pb) is a calcophile element with an average in upper continental crust by 14 ppm.
[6] In the analyzed stream sediment samples Pb content has an average of 14.84 ppm,
with limits of values between 8.85ppm and 36.21 ppm. All concentration results are
under threshold values of Romanian Sedimentary Quality Guidelines (100 ppm). The Pb
distribution map (fig. 2.f) shows low values in stream sediment (< 14 ppm) in most of
the study area and reflects petrographically features of the parent rocks being controlled
by the presence of primary minerals, such as feldspar, mica, sulphides and clay
minerals. The maximal Pb concentration point is located in the vicinity of inhabited
area, near national road DN 67 characterized by intense road traffic. Lead show a weak
correlation (< 0.3) with zinc, but also with the other elements analyzed.

CONCLUSION
The concentration of the selected elements in the studied stream sediments of the Oltet
River marks their geogenic origin. The variations in concentration of Mn, Ti, Fe, V, Pb
and Zn are correlate to the regional geology, structural trends and local effects of
individual rocks units. The spatial distributions of the elements reflect the role played by
alteration and transport processes in mobilization and deposition of the material
throughout the hydrographic basin. Along to the river course migration of the elements
is influenced by climate vertical zonality and the mechanical degradation of the rocks
exceeds their chemical decomposition. The mechanical migration of Mn, Ti, Fe, V, Pb
and Zn bearing mineral resistant determines the movement of rock particles under the
impetus of various external factors, especially of moving water, and redistributing
 18th International Multidisciplinary Scientific GeoConference SGEM 2018

among alluvial sediments with keeping the native features. In all geochemical maps the
abrupt passage between mountain and hilly terrains, at contact between the highlands
and the lowlands where the torrents are deposited large quantities of clastic material, is
evidenced by element enrichment.
The concentrations of vanadium, lead and zinc in stream sediments may have resulted
from some anthropogenic activities: vanadium concentration can be associated with
coal mining, lead with road traffic and zinc with phosphate fertilizer used in
agriculture.

ACKNOWLEDGEMENTS

This work was supported by a grant allowed by University of Bucharest, under the
projects ICUB-22453/2017 and the project PN 18470202/2018 funded by Ministry of
Research and Innovation.

REFERENCES
[4] Bercia I., Marinescu Fl., Mutihac V., Pavelescu Maria, Stancu Iosefina. Harta
geologică, scara 1:200.000, L-34-XXX (Targu Jiu), IGR, 1968.
[2] Cocker, M.D., Distribution of selected elements in stream sediments, stream
hydrogeochemistry, and geology of the Oconee River Basin: Georgia Geologic
SurveyBulletin 121, 79 pp, 1996.
[3] Ion Adriana, Natural radioactivity in stream sediments of Oltet River, Romania,
EGU General Assembly 2017, Geophysical Research Abstracts, Vol. 19, EGU 2017-
9965, 2017.
[4]. Kabata Pendias A., Pendias H., Trace elements in Soils and Plants, CRC Press,
Boca Raton, London, New York, Washinton D.C., pp 315, 2001.
[5]. McLennan, S.M., Murray, R.W., Geochemistry of Sediments. In: Marshall, C.P. &
Fairbridge, R.W. (eds.) Encyclopedia of geochemistry, Dordrecht: Kluwer Academic,
1999.
[6]. Rudnick R.L., Gao S., Composition of the continental cruste. In R.J. Roberta (Ed.),
The Crust, Volume 3: Treatise on Geochemistry (H.D. Holland & K.K. Turekian, Series
Editors), Elsevier – Pergamon, Amsterdam pp 1-64, 2004.
[7] Salminen R., Batista M.J., Bidovec M., Demetriades A., De Vivo B., De Vos W.,
Duris M., Gilucis A., Gregorauskiene V., Halamić J., Heitzmann P., Jordang, Klaver G.,
Klein P., Lis J., Locutura J., Marsina K., Mazreku A., O’connor P.J., Olsson, S.A.,
Ottesen,R.T., Petersell V., Plant J.A., ReederS., Salpeteur I., Sa., Siewers U., Steenfelt
A. & Tarvainen T. Geochemical Atlas of Europe, Part 1, Background Information,
Methodology and Maps.– Geological Survey of Finland, Espoo, 526 pp. 2005.
[8] Tchounwou P.B., Yedjou C.G., Patlolla A.K., Sutton D.J., Heavy Metals Toxicity
and the Environment, NIH Public Access, vol. 101, pp. 133 – 144, 2014.
[9] Wijaya A.R., Ouchi A.K. Tanaka K, Cohen, M.D. Name1 N.A., Name2 S. T.,
Evaluation of heavy metal contents and Pb isotopic compositions in the Chao Phraya
River sediments: Implication for anthropogenic inputs from urbanized areas, Bangkok
Journal of Geochemical ExplorationVol.126–127, pp 45 - 54, 2013.

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