The study of heavy metal pollution and accumulation in water

Environ Monit Assess (2010) 167:521–526
DOI 10.1007/s10661-009-1069-4
The study of heavy metal pollution and accumulation
in water, sediment, and fish tissue in Kızılırmak River
Basin in Turkey
Aydın Akbulut · Nuray Emir Akbulut
Received: 11 March 2009 / Accepted: 30 June 2009 / Published online: 16 July 2009
© Springer Science + Business Media B.V. 2009
Abstract The accumulation of heavy metals such
as Pb, Hg, Co, Cr, Cu, Zn, and Br were determined in water, sediment, muscle, and gill of
three fish species (Leuciscus cephalus, Capoeta
tinca, Capoeta capoeta) which were collected in
Kızılırmak River Basin (Delice River). The metal
concentration showed a general trend of Br>Zn>
Pb>Cr>Cu>Hg>Co in water and Cr>Zn>Pb>
Cu>Co>Hg>Br in sediment samples while Zn>
Cu>Pb>Br>Cr>Hg>Co were in muscle and
Zn>Pb>Cu>Cr>Br>Hg>Co were in the gill
tissue.
Keywords Heavy metals · Kızılırmak · Delice ·
Water · Sediment · Fish
Introduction
Human destructive influence on the aquatic environment is in the form of sublethal pollution
A. Akbulut
Faculty of Arts and Science, Department of Biology,
Gazi University, 06500 Teknikokullar,
Ankara, Turkey
e-mail: [email protected]
N. E. Akbulut (B)
Faculty of Science, Department of Biology,
Hacettepe University, 06800 Beytepe, Ankara, Turkey
e-mail: [email protected]
which results in chronic stress conditions that have
a negative effect on aquatic life (Javed 2005).
Heavy metals are stable and persistent environmental contaminants of aquatic environments
(Karadede Akın and Ünlü 2007) and enter the
aquatic environment, soil, and plants from natural
and anthropogenic sources (Gümgüm et al. 2001).
Some metals are essential whether Cd, Hg, Cr,
and Pb may exhibit extreme toxicity even at low
levels. The most important group of pollutants
like heavy metals in the environment created the
toxicity in proportion to the available amount
(Canpolat and Çalta 2001). The toxic effects of
metals can change according to the structure of
the metals. Generally, heavy metals create toxic
effects by forming complexes with organic compounds. The solubility of the metals primarily, depends on the pH, dissolved oxygen, and hardness
(Barlas 1999). Increase in pH generally decreases
the solubility of toxic heavy metals (Hellawel
1988).
Soylak et al. (1999) determined the heavy metal
bioaccumulation of Gelingüllüğü Dam Lake,
Karasu, Kaynak Suyu, and Delice River. The concentration ranges of nickel, lead, cadmium, copper, manganese, and iron were <1–5.0, 2.6–29.8,
2.2–9.4, 1.6–13.4, 13.8–47.2, and 33.4–284.4 μg/l,
respectively. Trace metal concentration in the
river water samples from Yozgat-Turkey were
found within the standard limits by the Water Pollution Control Regulation of Turkish Authorities.
522
Environ Monit Assess (2010) 167:521–526
Fig. 1 The map of the
study area and sampling
locations (modified from
Gul and Yilmaz 2002)
Gündoğan (2005) studied the heavy metal level
in Cladophora and the results showed that Zn,
Cu, Al, Ni, Cr, and Pb were of high level in
Cladophora sp. Gül and ve Yılmaz (2001) and Gül
and Yılmaz (2002) studied the growth properties
of Leuciscus cephalus and Capoeta tinca living in
Delice Stream, a tributary of Kızılırmak River.
Atıcı et al. (2003) were identified 68 taxa from
Delice River. Until now there are no comprehensive studies on the bioaccumulation of heavy
metals in sediment and fish samples.
Kızılırmak River water had been a source of
drinking water for a year of Ankara, the capital city, and to know the accumulation level of
the metals in sediment and fish is very important in order to evaluate future toxicity on living
organisms.
The present study was aimed at evaluating the
accumulation levels of Pb, Cr, Co, Hg, Zn, Cu, and
Br in the water, sediment, and fish samples in the
Kızılırmak River Basin (Fig. 1).
Materials and methods
The water, sediment, and fish samples were collected from four different stations in February,
May, and August 2008. Water samples were taken
0.5 L with polyethylene bottles and during the
summer sampling, 0.5% concentrated nitric acid
was added to the water samples. The samples were
brought to the laboratory on the same day. The
sediment samples were collected with an Ekman
sampler and fish samples were collected using
electroshock at the selected stations. In this sampling site, three fish species (C. tinca, Capoeta
capoeta, and L. cephalus) were collected. For the
heavy metal analyses, four specimens were selected. Gill and muscle samples were taken from
each fish species of the same length. Bernhard
(1976) and Yiğit and Altındağ (2002) methods
were used to analyse the samples. Heavy metals
were measured in Hacettepe University LA-ICPMS laboratory. The accuracy was also examined
by analyzing a blank. The field study of this work
was done together with the Project of H.U. BAB.
(07016010069) where the chemical data taken.
The determined heavy metal contents in the
water, sediment, fish muscle, and gill were evaluated statistically using analysis of variance
(ANOVA) technique (SPSS software version 15.0
program). The partition coefficient for the metal
concentration in water, sediment, and fish tissue
samples were normalized and determined as 0.01
and 0.05. The means with same letters (a and b)
show no statistically significant differences.
Results and discussion
The average content of seven metals examined
in water and sediment from Delice Stream were
Environ Monit Assess (2010) 167:521–526
523
Table 1 Mean, minimum, and maximum heavy metal concentration in the water and sediment samples
Water (μg/l)
Feb. 2008
Zn
Co
Cr
Cu
Pb
Hg
Br
84.31 ± 70.243
0–86.88
1.28 ± 0.324
0.73–1.789
10.43 ± 6.27
2.87–20,44
1.42 ± 3
0–7.48
33.7 ± 55.4
4.532–151.3
1.228 ± 0.44
0.728–2.243
398.85 ± 121.5
141.8–581.5
May 2008
August 2008
Sediment (μg/g)
Feb. 2008
May 2008
August 2008
6.36 ± 19.29
0–43.58
1.09 ± 0.356
0.543–1.5290
4.847 ± 1.65
1.724–7.378
nd
66.51 ± 103.82
28.48–377.9
0.006 ± 0.34
0–0.225
2.51 ± 4.96
0.042–17.31
31.46 ± 33.16
12.96–120.4
8.39 ± 16.19
2.28–56.91
5.92 ± 9.18
2.201–33.45
482.8 ± 315.7
211.8–1,409
170.6 ± 44.9
104.5–212.9
10.9 ± 1.49
9–13.1
74.4 ± 20.1
42.7–92.5
13.4 ± 2.28
9.48–14.9
39.7 ± 9.59
24.1–49.1
8.28 ± 1.71
6.25–10.9
17.17 ± 3.4
13.1–21.4
129.7 ± 72
57–243.9
6.57 ± 1.66
3.7–7.89
153.5 ± 189.4
30.4–481.2
7.111 ± 2.40
2.96–8.7
30.56 ± 20.7
11.6–64.6
14.81 ± 5.92
8.7–22.5
15.5 ± 7.38
6.9–27.3
86.2 ± 28.8
69.5–107.5
19.37 ± 12.74
9.92–41.2
237.4 ± 233.6
83.6–641.5
57.3 ± 30.44
35.5–109.6
27.99 ± 12.1
15.86–43.3
4.16 ± 4.25
0–10.0
nd
5.66 ± 1.936
2.97–8.247
0.137 ± 0.09
0–0.236
410.6 ± 102.5
245–508.1
nd not dedected
given in the Table 1 and the metal contents of fish
muscle and gill tissue were given in the Tables 2
and 3.
The accumulation order of heavy metals in
water samples was found to be Br>Zn>Pb>
Cr>Cu>Hg>Co in sediment and Cr>Zn>Pb>
Cu>Co>Hg>Br as seen on Table 1. Br is much
higher in the water and less in the sediment
samples, also nondetected in the August sampling. The accumulation order of the metal in
fish muscle tissue was found to be Zn>Cu>Pb>
Br>Cr>Hg>Co and in the gill it was Zn>Pb>
Cu>Cr>Br>Hg>Co.
Table 2 Mean, minimum,
and maximum heavy
metal concentration in
the muscle of three fish
species
Zn
Co
Cr
Cu
pb
Hg
Br
Statistical Result
Statistical results of ANOVA were given for water
and sediment samples in Tables 4 and 5. There
were no significant differences in fish tissue between the months and the data were not shown in
the tables. The means with the same letters show
no statistically significant differences (a, b).
There were no differences between the sampling periods and accumulation of muscle and
gill tissue (L. cephalus, C. tinca, and C. capoeta)
according to these heavy metals. Zn, Co, Pb, Cr,
and the results were not shown in the table.
February 2008
Capoeta tinca
May 2008
Capoeta capoeta
August 2008
Leuciscus cephalus
311.13
124.891–1,059
0.748
0.121–3.369
36.8
8.12–140.9
114.97
41.98–164
24.0
6.167–53.4
5.626
0.955–15.52
25.6
3.49–46.8
248.5
41.14–422.39
0.356
0.168–0.666
24.9
4.10–69.38
162.1
61.71–388
59
6.82–105
1.639
0–8.14
40
7.55–215.69
427.2
81.13–1,333.7
0.616
0.182–1.08
38.11
12.94–67.57
209.1
122.5–435.2
250
59.38–444.7
3.89
0–23.62
42.8
20–57
524
Environ Monit Assess (2010) 167:521–526
Table 3 Mean, minimum,
and maximum heavy
metal concentration in
the gill of three fish
species
Zn
Co
Cr
Cu
pb
Hg
Br
February 2008
Capoeta tinca
May 2008
Capoeta capoeta
August 2008
Leuciscus cephalus
952.1
238.9–1,014.4
1.321
0.88–1.57
159.3
23.74–391
159.6
15.08–438.7
121
21.08–308.6
12.42
0–23.78
85.24
0–227.7
1,259
176.74–2,383
2.85
1.38–6.10
113.4
20.26–224.28
179.9
91.78–357.2
261.6
19.63–531.4
11.97
nd–39.27
nd
986.3
610.8–1,284.4
1.91
1.41–2.41
160.41
25.61–306.7
139
2.148–335.8
250
59.38–444.7
nd
Measured physico-chemical data were: pH
ranged between 8.14–8.43; salinity was between
0.9–8.14 (ppm); and the temperature ranged between 13.9 and 17.6◦ C; the dissolved oxygen
changed according to the temperature and the
values ranged 5.32–8.84 ppm. EC measurement
ranged 280 μmhos and 15.8 mS.
The measured chemicals like sulfate ranged
between 153.2 and 746.5 ppm; chloride changed
between 261.7 and 537.3 ppm; bicarbonate was between 206.4 and 371.88 ppm and hardness ranged
between 44.64 and 79.88 (Fr) French hardness.
These parameters exceeded the limit values of
Ministry of Agriculture and Rural Affairs, Water
Control Administrative Regulations (TKB 2004).
The Illinois EPA had declared TDS general
use water quality standard of 1,000 mg/L, and replaced the sulfate general use water quality standard of 500 mg/L. Sulfate toxicity is dependent on
chloride and hardness concentration. The other
chemicals are insignificant when compared with
chloride and sulfate toxicity. When the chlorides
205.8
129.7–290
are high, the sulfate is more toxic to aquatic
organisms (Iowa’s water quality standard review
2008). In Delice stream and Kızılırmak river, these
parameters were measured as high and taken care
of, being drinking water sources.
Ministry of Agriculture and Rural Affairs, Water Control Administrative Regulations (2004)
was classified the natural waters from I to IV level
according to heavy metal contents. The results
showed that Delice stream water in the class of
I according to Zn, Co, Cr, and in the class of
II and III according to Hg, Cu, and Pb level.
These metals should not exceed the limit values
in natural water. The mean levels of these metals
were (μg/L): 6.36–84.31 Zn; 0.006–1.28 Co; 2.51–
10.43 Cr; 1.42–31.46 Cu; 5.66–33.7 Pb; 0.137–5.92
Hg; and 398.85–482.8 Br. In the Kızılırmak River
basin, bioaccumulation was high in the sediment.
The mean levels were (μg/g): 86–170.6; 6.57–19.37;
74.4–237.4; 7.111–57.3; 27.99–39.7; 4.16–14.81; and
15.5–17.4, respectively. But statistically Zn, Pb,
and Hg levels were found insignificant among the
Table 4 Statistical results of water samples
Parameter
February
May
August
F value ANOVA
Probability
Co
Cr
Cu
1.2805 ± 0.324a
10.43 ± 6.27a
7.109 ± 0.531a
1.091 ± 0.356a
4.847 ± 1.651a
0.538 ± 1.256a
0.006 ± 3.341b
2.510 ± 4.966b
31.466 ± 33.166b
43.305
13.326
43.061
P = 0.000 < 0.01
P = 0.000 < 0.01
P = 0.000 < 0.01
Among the months there were no differences in terms of values of Zn, Pb, and Hg and the results are not given in the table
Between February and May, there was no difference in terms of values of Co, Cr, and Cu in water but there was a difference
in the other month
Environ Monit Assess (2010) 167:521–526
525
Table 5 Statistical result of sediment samples
Parameter
February
May
August
F value ANOVA
Probability
Co
Cu
10.956 ± 1.499ab
13.431 ± 2.282a
6.571 ± 1.667a
7.111 ± 2.40a
19.373 ± 12.743b
57.361 ± 30.440b
4.788
22.005
P = 0.038 < 0.05
P = 0.000 < 0.05
Between months there are no differences in terms of values of Zn, Pb, Cr, and Hg. The results are not given in the table
Between May and August, there was difference in terms of values of Co in sediment, but there was no difference in the other
month
Between February and May, there was no difference in terms of values of Cu in sediment, but there was a difference in the
other month
months in the water while Co, Cr, and Cu accumulation level were observed significant among the
months. In the sediment there were no differences
in terms of Zn, Pb, Cr, and Hg while Co and
Cu accumulation level were observed significant
among the months (see Tables 4 and 5).
Dundar and Altundag (2007) had studied the
heavy metal accumulation in sediment of Sakarya
River and mean levels of copper, chromium,
lead, cadmium, and zinc for sediment samples are
4.630 μg g−1 , 8.780 μg g−1 , 2.550 μg g−1 , and
9.990 μg g−1 , respectively.
Akçay et al. (2003) had observed that the pollution levels were significant especially for Pb, Cr,
and Zn in the Gediz River and Co and Zn in
the Büyük Menderes River. In Sakarya River, the
mean levels of copper, chromium, lead, cadmium,
and zinc for water samples were 0.851 μg g−1 ,
0.027 μg g−1 , 1.786 μg g−1 , 0.236 μg g−1 , and
0.173 μg g−1 (Dundar and Altundag 2007).
Gümgüm et al. (2001) mentioned that the average
contents of Cu and Zn in the Tigris river water
were found as 0.03 and 0.14 mg/L. All Cu and
Zn values in the soils irrigated by the river water
were found higher than the non-irrigated soils
in the same area. In the Kızılırmak basin, these
metals were more accumulated in sediment when
compared with these Rivers.
In our study, Zn, Cr, Cu, Pb, and Br were accumulated in L. cephalus muscle tissue while Co and
Hg were highly accumulated in C. tinca muscle.
In gill samples, Cr and Br were accumulated in
L. cephalus while Zn, Co, Cu, Pb, and Hg were
higher in C. capoeta. But statistically there is no
difference in the accumulation of metals in muscle
and gill tissue among the months. The range of
international standards for Pb in fish is 0.5–10 μg/g
and 0.05 μg/g Zn (EU 2001; TFC 2002). These
two metal levels had exceeded the limit values in
Kızılırmak Basin. Pb values were found as 0.66–
0.68 μg/g in Atatürk Dam Lake and they also
observed that the metals Zn, Pb, Co, and Cr concentrations in gills were higher than in the muscles
of fish species (Alhas et al. 2009).
Erdoğrul (2007) determined the Hg levels in
various fish species in Sır Dam Lake and Hg levels ranged from 0.03 to 0.18 μg/g dry weight in
Cyprinus carpio and from 0.16 to 0.38 μg/g dry
weight in Silurus glanis samples. In our study,
the mean Hg level ranged 0–24.9 μg/g in gill and
1.639–10.25 μg/g in muscle.
Ünlü et al. (1996) had reported that the range
of heavy metals accumulation varied enormously
in cyprinid fish species in Tigris River: Cr, 6.28–
188.19 μg/g; Cu, 66.54–335.03 μg/g; and Zn,
32.29–317.36 μg/g
In conclusion, the heavy metal concentrations
in sediment and fish species were found to be
higher than the values recommended by inland
water source classification and food for fish (TKB
2004; TFC 2002). Biomonitoring is necessary for
this area to know the heavy metal contents if used
as potable and agricultural water source.
Acknowledgements The authors would like to thank the
Zoology Department for the use of their laboratory; Dr.
Serdar Bayarı and other laboratory personnel for their
kind help to measure the heavy metals and Hacettepe
University Research Fund.
References
Akçay, H., Oğuz, A., & Karapire, C. (2003). Study of heavy
metal pollution and speciation in Buyük Menderes
and Gediz river sediments. Water Research, 37(4),
813–822(10).
Alhas, E., Oymak Ahmet, S., & Karadede Akın, H. (2009).
Heavy metal concentrations in two barb Barbus
526
xanthopterus and Barbus rajonurum mystaceus from
Atatürk Dam Lake, Turkey. Environmental Monitoring Assessment, 148, 11–18.
Atıcı, T., Yılmaz, M., Gül, A., & ve Kuru, M. (2003). Delice
Irmağı Algleri. Gazi Üniversitesi Fen bilimleri Dergisi,
16(1), 9–17.
Barlas, N. (1999). A pilot study of heavy metal concentration in various environments and fishes in the
Upper Sakarya River Basin. Environmental Toxicology, 14(3), 367–373.
Bernhard, M. (1976). Manual of methods in aquatic environment research. FAO, Fisheries Technical Paper,
Rome, 58.
Canpolat, Ö., & Çalta, M. (2001). Keban Baraj Gölü’nden
(Elazığ) yakalanan Acanthobrama marmid (Heckel,
1843) de bazı ağır metal düzeylerinin belirlenmesi.
F.Ü. Fen ve Müh. Bilimleri Dergisi, 13(2), 263–
268.
Dundar, M. S., & Altundag, H. (2007). investigation of
heavy metal contaminants in the lower Sakarya river
water and its sediments. Environmental Monitoring
and Assessment, 128(1–3), 177–181.
Erdoğrul, Ö. (2007). Determination of mercury levels in
eddible tissues of various fish samples from Sır Dam
Lake. Turkish Journal of Biology, 31, 197–201.
EU (2001). Commission regulation as regards heavy metal
Directive 2001 EC No 466/2001.
Gül, A., & ve Yılmaz, M. (2001). Kızılırmak Nehri Delice
Irmağı’nda yaşayan Leuciscus cephalus’un büyüme
özellikleri. Gazi Üniversitesi Fen Bilimleri Enstitüsü
Dergisi, 15(2), 485–494.
Gül, A., & Yılmaz, M. (2002). Kızılırmak Nehri Delice
Irmağı’nda yaşayan Capoeta tinca (Heckel, 1843)nın
büyüme özellikleri. Gazi Üniversitesi Gazi Eğitim
Fakültesi Dergisi, 22(1), 13–24.
Gümgüm, B., Ünlü, E., Akba, O., Yıldız, A., & Namlı, O.
(2001). Copper and zinc contamination of the Tigris
Environ Monit Assess (2010) 167:521–526
River (Turkey) and its wetlands. Arch. für Nat-Lands,
40, 233–239.
Gündoğan, Y. (2005). Kızılırmak Nehri’ndeki Cladophora
da ağır metal birikimi üzerine bir çalışma. Gazi Üniversitesi, Çevre Bilimleri, Bilim Uzmanlığı tezi.
Hellawel, M. J. (1988). Toxic substances in rivers and
streams. Environmental Pollution, 50, 61–85.
Iowa’s water quality standart review (2008). www.iowadnr.
gov/water/standarts (16 p.).
Javed, M. (2005). Heavy metal contamination of freshwater fish and bed sediments in the river Ravi stretch
and related tributaries. Pakistan Journal of Biological
Sciences, 8(10), 1337–1341.
Karadede Akın, H., Ünlü, E. (2007) Heavy metal concentrations in water, sediment, fish and some benthic
organisms from Tigris River, Turkey. Environmental
Monitoring and Assessment 131, 323–337.
Soylak, M., Akkaya, Y., & Elci, L. (1999). Trace metal
levels of river water samples from Gelingüllüğü
Dam, Karasu, Kanak Suyu and Delice River, YozgatTurkey. Fresenius Environmental Bulletin, 8(7–8),
453–456.
TFC (2002). Turkish food codes, Official Gazete 23 September No.24885.
TKB (2004). Tarım ve Köyişleri Bakanlığı Su Kirliliği
Kontrol Yönetmeliği, Kıta içi su kaynaklarının
sınıflarına göre kalite kriterleri, su kirliliği kontrolü
yönetmeliği, 31 December official gazette, no.25687
51 s. (in Turkish).
Ünlü, E., Akba, O., Sevim, S., & Gümgüm, B. (1996).
Heavy metal levels in mullet Liza abu (Heckel, 1843)
Mugilidae from the Tigris River, Turkey. Fresenius
Environmental Bulletin, 5, 107–112.
Yiğit, S., & Altındağ, A. (2002). Accumulation of heavy
metals in the food web components of Burdur
lake, Turkey. Fresenius Environmental Bulletin,
11(No 12a), 1048–1052.