Fresenius Fnvir. Bull.

6: 605-610 (1997)
© Editors, Freising- Weihenstephan/fRG
1018-4619/97/9-10/605-06 DM 2.50 + 0.30/0

DISTRIBUTION OF HEAVY METALS IN THE AQUATIC ENVIRONMENT

OF THE KERKINI LAKE (N. GREECE) : AN EXPLORATORY STUDY

K. Toli, P. Misaelides' and A. Godelitsas

Faculty of Chemistry, Aristotle University, GR-S4006 Thessaloniki, Greece

SUMMARY
The heavy metal distribution in water, sediment and suspended particle samples collected
from representative sites of the Kerkini artificial lake (Serres district, Macedonia, N. Greece)
has been determined by means of spectroscopic (RI-XRF, INAA, GF-AAS, PXRD) and
microscopic (SEM-EDS) analytical techniques. The results of this exploratory study indicated
a general absence of serious pollution in the lake due to heavy metals, whereas the
concentrations of the elements found could mainly be attributed to geological sources.
Key words: Greece, Kerkini; Environment, aquatic; Metals, heavy; Spectroscopy.

INTRODUCTION
The Kerkini artificial lake, situated in the Serres district, Macedonia, N. Greece, has
been created by the construction of a number of dams on the Strymon river and covers a total
area of ca. 73 km 2. The Strymon river forms one of the largest aquatic networks in Balean
Peninsula draining the S.W. part of Bulgaria and the Serres basin in Greece before discharging
into the Mediterranean sea. The water deposit of Kerkini lake is mainly used for irrigation
purposes. The whole area of Kerkini has been considered as one of the most important bio­
topes/wetlands in Europe protected by several international treaties (e.g. RAMSAR) [e.g. J, 2].
The main task of the present work was to elaborate an exploratory investigation of the
Kerkini aquatic environment in regard to hazardous heavy metals. For this purpose indicative
samples of water, sediments and suspended particles were studied using a combination of
spectroscopic and microscopic analytical techniques. It should be mentioned that, despite of

Corresponding author
606 K. Tali, P. Misaelides, A. Godelitsas

'* S;tlmr1il1f1 pol"!1l;

{- St'ymon
River

Fig. I: Map of the Kerkini artificial lake (adapted by permission from 14])

the environmental importance of the area, no relevant investigation has been reported so far
in the literature [3,4].

MATERIALS AND METHODS

The water samples were collected using standard procedures, filtered using a
Nuc1epore apparatus (membrane filters of 0.45 urn) and acidified by HNOJ The final samples
were analyzed using Radioisotope-Induced X-Ray Fluorescence I RI-XRF (preconcentration
with ammonium pyrrolidine dithiocarbamate. analysis using a 241Am-Sn secondary excitation
source and a CANBERRA planar Ge(i)-detector with 0.05 mm Be-window connected with a
CANBERRA S-100 computer-based multichannel analyzer system), lnstrumental Neutron
Activation Analysis I INAA (drying at 80 0C and irradiation of the solids with thermal
neutrons at the 5 MW research reactor of the N.R.C.P.S. "DEMOKR ITOS', analysis using a
CANBERRA REGe y-ray detector of 20% efficiency and 2.1 keV resolution for the 1.332 MeV
60Co-line, connected with a CANBERRA S-35 Plus multichannel analyzer) and Graphite
Furnace - Atomic Absorption Spectroscopy I GF-AAS (PERKIN ELMER 5200). The IAEA
certified reference materials Soli-7 and Soil-5 were used for the RI-XRF and INAA
investigations, whereas standard metal solutions (1.000± 0.002 gil) supplied by MERCK for the
AAS measurements. The sediment samples were picked-up from selected points.dried at 100°C
K. Tali, P. Misaelides, A. Gadelitsas 607

!l0000
80000

70000

60000

50000

~oooo

D 30000

Q. 20000

.3 10000

~--~---- - <,

Fig. 2: Schematic presentation of the experimental results (a: Water samples, b: Sediments,
c: Suspended particles). The minimum detectable concentrations of the elements
indicated are of the order of a few ppb.
608 K. Tali, P. Misaelides, A. Godelitsas

and sieved using ana\ytical sieves for the separation of the < 45 um particles-size fraction.
The final samples were investigated by means of powder X-Ray Diffraction / PXRD (PHILIPS
PW 1820, CuKa-radia-tion) and Scanning Electron Microscopy / SEM-EDS (JEOL JSM 840-/\
equipped with a LINK 10000 AN EDS). The sediment samples were further analyzed using RI­
XRF and INAA It should be noted, that both water and sediment samples were collected
during November 1994.

GENERAL GEot-OGle" L M" I'

or run STRYMON RIVER­
LAKE KERKINI ITYDROSYSTEM

toI

'------------------------------­

Fig. 3: General geological map of the Strymon River - Kerkini Lake hydrosystern in the
Greek and Bulgarian territory (adapted from l5,6J)
K. Toli, P. Misaelides, A. Godelitsas 609

Finally, the suspended particles were studied as they were obtained on the membrane filters,
after water filtration, using PXRD, SEM-EDS and RI-XRF.

RESULTS AND DISCUSSION

The results of the chemical analyses of the water samples obtained from three
representative sampling points (Fig. 1) are presented in Fig. 2a. The above mentioned data
reveal the absence of toxic concentrations of most heavy metals detected by the used
analytical techniques. Therefore the origin of these elements could be attributed to the
. geological environment [5,61 surrounding the river Stryrnon-Ker kini lake hydrosystern (Fig. 3).
Only the concentrations of Cd and Mo (max. 300 and 34 ppb respectively) can be considered
relatively elevated taking into account the recommended concentrations of trace elements in
irrigation waters (max. 10 ppb for both elements [7D. However, the determined amounts of Cd
and Mo are rather low to suggest a severe pollution connected with industrial activities and
could also be attributed to geological sources (such as the extended metal sulfide deposits
particularly occurring in the Bulgarian territory [e.g. 6,81). In this case the minerals sphalerite
(ZnS-normally containing Cd [e.g. 9]) and molybdenite (MoS2) may be responsible for the Cd
and Mo release in the environment. It should be mentioned, that Re-traces (an ordinary minor
element in molybdenite [e.g. 101) were detected by INNA in one of the water samples.
The study of the corresponding sediments also indicated the lack of remarkable
contamination due to hazardous heavy metals although a relative Fe- and Zn-enrichment was
observed (up to ca. 86 and 25 ppm respectively, s. Fig. 2b). Nevertheless, the chemistry of this
aquatic matter can sufficiently be explained on the basis of its mineralogical composition. The
PXRD analysis showed that the major mineral constituents of the Kerkini sediments are clay
minerals, quartz, micas, feldspars and calcite, whereas the SEM-EDS study indicated the
presence of several other phases (e.g. sphene crystals) including very small fragments or
metallic minerals (e.g. sphalerite).
The heavy metals detected In the suspended particles are shown in Fig. 2c. The
investigation of this material by means of SEM-EDS and PXRD provided the evidence for
high concentration of biogenic matter (mainly diatomes of different types), although clay
minerals and occasionaly Fe-bearing particles (most probably natural Pe-ox ides) were also
observed. The significant presence of diatornes in the Kerkini suspended particles has also
been reported in a previous study [4J. On the other hand, the EDS-spectra (individual
qualitative point analyses) obtained from the surface of the diatome cells showed, in some
cases, unusually raised concentrations of Fe and Mn but further investigations are required to
clarify these findings.
 610 K. Tali. P. Misaelides, A. Godelitsas

According to this exploratory study, it is concluded that at the present there is no

serious heavy metal pollution in the Kerkini lake and, in addition, the concentrations of the
elements detected could most probably be due to natural sources rather than to eventual
anthropogenic reasons. However, long-term investigations combined with a more systematic
sampling are aims of future work in order to achieve a better understanding of the
distribution of heavy metals in the Kerkini aquatic environment.

ACKNOWLEDGEMENTS
The financial support of the Ministry of Environment, Physical Planning and Public
Works of Greece is thankfully acknowledged. Many thanks are due to Mr. T. Anousis
(N.R.CP.S. "DEMOKRlTOS') for the irradiation of the samples as well as to Dr. K. Albanakis
and Prof. A. Psilovikos (Aristotle University) for their comments. The authors are also
grateful to the staff of Serres Prefecture for their help during the field work.

REFERENCES
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Received 19 March 1996
Accepted t 2 May t 997

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