Environ Geol (2008) 54:1155–1163 DOI 10.1007/s00254-007-0884-6
ORIGINAL ARTICLE
Multivariate analysis of heavy metal contents of sediments from Gumusler creek, Nigde, Turkey M. Gurhan Yalcin Æ Ibrahim Narin Æ Mustafa Soylak
Received: 30 January 2007 / Accepted: 18 June 2007 / Published online: 18 July 2007 Springer-Verlag 2007
Abstract In this study, heavy metal contents of samples from Gumusler creek in Turkey were studied and the metal contamination characteristics were investigated. In this respect, considering the pollutant sites in the area, systematic sediment samples were collected in a zone starting from the manifestation part of the water to the entrance of the Karasu creek in Gumusler town. Samples were taken from lower section of the river bed at 30 stations along Gumusler creek, 13 km in length and their heavy metal contents were analyzed with XRF Spectrometer. Correlation coefficients, element coefitic coefficient correlation, dendogram hierarchical cluster, model summary and Annova analysis statistical methods were applied to data. Strong positive correlations were determined for some elements which are believed to have possibly the same origin. In addition, mineralizations in the area are thought to cause variation in metal contents. Results of chemical analysis show that soil limit values and clark values were exceeded. The heavy metal accumulation in the creek is believed to be derived from non-operated Sb-Hg-W and Fe quarries.
M. G. Yalcin Department of Geological Engineering, Faculty of Engineering and Architecture, Nigde University, 51200 Nigde, Turkey I. Narin (&) Faculty of Pharmacy, Erciyes University, 38039 Kayseri, Turkey e-mail:
[email protected] M. Soylak Department of Chemistry, Faculty of Science and Art, Erciyes University, 38039 Kayseri, Turkey
Keywords Gumusler creek Heavy metal Nigde Massive Geostatistics Geochemistry Pollution
Introduction In parallel to increase in types of use, the need of drinking and usage waters, river waters are significantly contaminated especially with metals due to improper irrigation in agriculture, increasing use of fertilizers and increasing number of industrial facilities. Metals are very important for humans, plants and environment. Some of these elements are indispensable for humans and plants while some are toxic. In addition, concentrations of beneficial elements above a certain level may also create toxic effect. Metals can move with food chain. Therefore, in order to define concentrations of most metals in waters and soil; some regulations are applied (Yalcin et al. 2007; Ensafi et al. 2003). The determination of trace metal contents in river sediments is one of the important indicators for the assessment of environmental pollution (Soylak et al. 1999). Routine works on determination of trace metal contents in soils are rapidly continued (Forstner 2004; Mwamburi 2003; Gue´guen et al. 2000; Dalman et al. 2006; Capilla et al. 2006). The city of Nigde in central Anatolia is an old settlement region. Gumusler town with a population of 2,600 is located 8 km north of Nigde and most people are reside along the Gumusler creek (Fig. 1). Sb-Hg-W and Fe quarries in Gumusler town are settled along the Gumusler creek. House wastes of residents are dumped to Gumusler creek without any refinement. Agriculture is well developed in the settlement part of Gumusler town through which the Gumusler creek runs and these lands are irrigated with water from Gumusler creek. Water from the
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Environ Geol (2008) 54:1155–1163
Fig. 1 Geology, sampling and location map of the study area
creek flows to the Karasu creek and is delivered to the Aktas irrigation dam by a water canal (Narin and Soylak 1999). Although there are several works on heavy metal contents of the Karasu creek, the metal pollution in Gumusler creek has not been studied (Yalcin et al. 2007; Yalcin 1995; Yalcin and Yaman 1996). The aim of this study is to determine heavy metal contents of sediments and possible contaminated areas along Gumusler creek. Continuous and hygienic use of Gumusler creek water is only possible if river basin is kept clean and contamination along the creek has is mitigated as much as possible. Therefore, determination of possible
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contaminant sites along the creek will provide more healthy use of this water body.
Materials and methods Coordinates of sample sites were determined with Garmin brand GPS-12CX device. Analyses of elements investigated was performed with Spectro-Xepos Benchtop X-Ray Fluorescence Spectrometer. Analyses of metals were done on samples with double-sided film tablets, 32 mm in diameter. Detection System is drift detector with Peltier
Environ Geol (2008) 54:1155–1163
1157
Table 1 Element concentrations of sediment samples from Gumusler creek, mg/kg (n = 30, P = 26) Sb
W
Ag
Mo
Co
V
Cu
As
Sn
Hg
Ni
Zn
Cd
Min
6.4
5.0
2.6
20
22.0
11.5
17.3
71.3
5.8
1.1
16
36.9
3.7
Max
840.5
84.2
8.2
25
38.5
199.0
44.2
659.1
17.3
21.7
50.7
202.3
5.3
Mean
154.6
19.1
4.4
22
26.4
98.6
26.2
268.6
8.3
5.5
28.3
64.8
4.4
Pb
Si
Al
Fe
Ca
Mg
S
Na
K
Cl
Ti
Cr
Mn
Min
17.5
122,600
38,590
23,790
33,080
5,680
15.6
24.2
6,772
3.4
2,616
87.1
517
Max
133.8
214,100
79,820
56,550
168,600
15,770
496.8
5,530.0
22,460
106.8
5,742
1,223.0
1,082
Mean
49.1
168,797
52,779
35,399
73,345
9,497
222.1
2,627.6
15,584
39.8
3,850
496.4
734
cooling, energy resolution FWHM < 170 eV, measured for the Mn Ka line with an input count vote of 10,000 pulses, microprocessor controlled detector and electronics. Results are given as mg/kg. Sediment sampling was made in November 2005. A total of 30 samples were collected of which 26 were from Gumusler creek with 500-m interval and four were from tributaries of the creek. Coordinates of samples were Table 2 Abundance of heavy elements in soil and earth crust and their acceptable limits
Elements Earth crust (mg/kg) (Krauskopf 1979 )
measured with GPS and marked on 1/25,000 scaled topographic map. Samples were collected with hard plastic sample shovel and stored in 1-kg plastic bags for analyses. Before use, bags were washed with 6 mol l–1 HNO3 to avoid contamination and rinsed with distilled water and then heated at 70C. Sediment samples were heated at 105C for 24 h. Dried samples were sieved through a 2-mm plastic sieve to be separated from conglomerates. In
Acceptable limit for Turkey (mg/ kg) (Anonymous 2005)
Soil (Wedepoh 1969–1978; Maynard 1983; Connor and Shacklett 1975; Brooks 1972; Boyle 1975; Brady 1974)
Variation of average concentration in soil (fold)
Variation of maximum concentration in soil (fold)
Fe
5.4 · 104
–
2.1 · 104
2
2.7
Cu
50
50
15
1.7
3
Pb
12.5
50
17
3
8
Zn Cd
70 0.15
150 1
36 0.1–0.5
1.8 8.8
5.6 10.6
Ni
75
30
17
1.7
3
Cr
100
100
43
11.5
28.4
Co
20
20
10
2.6
3.9
Mn
1,000
–
320
2.3
3.4
Ti
5,000
–
–
–
–
Sn
2.5
20
10
0.8
1.7
As
1.8
20
7.5
35.8
87.9
Al
8.1 · 104
–
14.7
3,590.4
5,429.9
Sb
0.2
–
2
77.3
420.2
W
1.2
–
1
19.1
84.2
Ag
0.07
–
0–0.56
8
14.6
Mo
1.5
–
2–5
4.3
12.5
V
110
–
57
1.7
3.5
Hg Si
0.02 28.2 · 104
– –
0–0.56 –
9.8 –
38.8 –
Ca
4.1 · 104
–
–
–
–
4
–
Mg
2.3 · 10
–
–
–
S
300
–
100–200
2.2
5
Na
2.4 · 104
–
–
–
–
K
2.1 · 104
–
11,000
1.4
2
Cl
130
–
–
–
–
123
1158
1.0
Sb Pb W As Cd Hg V Cu Mg Mn Co Ni Fe Ti Al Si K Ag Na Cr Mo Ca Sn S Cl Zn
0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 -0.1
Fig. 2 Coefitic correlation dendorgam for elements
the next stage, samples were homogenized with an agate mortar to a grain size of less than 2 mm. The mortar was washed with 6 mol l–1 HNO3 and rinsed with distilled water and dried before each sample process. Gumusler creek under investigation is in the Kozan M33b1 quadrangle of 1/25,000 scale (Fig. 1). The Karasu creek in which Gumusler creek starts in the northeast part of Nigde (Kayseri L33d3) continues through the city and flows into the Aktas dam (Kozan M33a2). Metamorphic rocks of the Paleozoic-Mesozoic Nigde Massive comprise the basement area around the Gumusler creek. The metamorphic rocks of the Nigde Massive from bottom to top are composed of Gumusler, Kaleboynu and
Fig. 3 Hierarchical cluster analysis dendogram for sediment samples from Gumusler creek
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Environ Geol (2008) 54:1155–1163
Asigedigi Formations. These units are cut by the Sineksizyayla Metagabbro and Uckapili Granotoid. The Cretaceous Gumusler Formation within the Nigde Massive is made of various genies and amphibolite, schist and thin marble bands. The overlying Kaleboynu Formation is comprised by quartzite and gneiss alternation. The Asigedigi Formation that conformably overlies the Kaleboynu Formation is composed of marble, lesser quartzite, gneiss and micaschist. Gumusler Formation is exposed at the base of the Kaleboynu and Asigedigi Formations. Sb-Hg-W and Fe quarries with Gumusler Formation were excessively exploited in the past years (Yalcin 1995; Yalcin and Yaman 1996; Goncuoglu 1986). Statistical calculations were performed using a software package, of SPSS version 10.0.
Results and discussion Waters of Gumusler creek are commonly used for agriculture. Creek flowing in its natural channel is in close association with the soil. Metal contents of sediment samples collected along the creek are given in Table 1. Sb, W, Ag, Mo, Co, V, Cu, As, Sn, Hg, Ni, Zn, Cd, Pb, Si, Al, Fe, Ca, Mg, S, Na, K, Cl, Ti, Cr and Mn concentrations are between 6.4–840.5, 5–84.2, 2.6–8.2, 20–25, 22–38.5, 11.5–199, 17.3–44.2, 71.3–659.1, 5.8–17.3, 1.1–21.7, 16–50.7–36.9– 202.3, 3.7–5.3, 17.5–133.8, 122,600–214,100, 38,590– 79,820, 23,790–56,550, 33,080–168,600, 5,680–15,770, 15.6–496.8, 24.2–5,530, 6,772–22,460, 3.4–106.8, 2,616– 5,742, 87.1–1,223 and 517–1,082 mg/kg, respectively. Average concentrations of Sb, W, Ag, Mo, Co, V, Cu, As, Sn, Hg, Ni, Zn, Cd, Pb, Si, Al, Fe, Ca, Mg, S, Na, K, Cl, Ti, Cr and Mn are found as 154.6, 19.1, 4.4, 21.8, 26.4, 98.6, 26.2, 268.6, 8.3, 5.5, 28.3, 64.8, 4.4, 49.1, 168,796.9, 52,779.1, 35,398.8, 73,344.7, 9,497.2, 222.1, 2,627.6, 15,583.9, 39.8, 3,849.6, 496.4 and 733.7 mg/kg, respectively. According to the results of chemical analyses, maximum values of Sb, W, Ag, Mo, Co, V, Cu, As, Sn, Hg, Ni, Zn, Cd, Pb, Al, Fe, S, K, Ti, Cr and Mn were found to be above their acceptable limits in soil, earth crust and Turkish National Soil Pollution Control Regulation (Table 2). The variation of maximum concentration values in sediments revealed the order of elements as Al, Sb, As, W, Hg, Cr, Ag, Mo, Cd, Pb, Zn, V, Co, Mn, Cu, Ni, K and Sn. Sb, Pb, W and Fe concentrations are derived from abandoned mine deposits along Gumusler creek. In this respect, the average Sb concentration in the area is 154.6 lg/g and this value is expected between 6.4– 840.5 lg/g (Table 1) which is quite high when compared to 0.2 and 2 lg/g that are clark concentration of Sb in the earth crust and its abundance in sediments, respectively. Sb is enriched in sediment 77.3 times higher than its average
0.925**
–0.213
0.365*
0.064
0.191
0.399*
0.855**
–0.060
0.410*
–0.079
0.210
0.584**
0.930**
0.111
–0.207
0.035
–0.068
0.302
0.068
0.318
–0.044
–0.031
0.057
–0.068
0.186
W
Ag
Mo
Co
V
Cu
As
Sn
Hg
Ni
Zn
Cd
Pb
Si
Al
Fe
Ca
Mg
S
Na
K
Cl
Ti
Cr
Mn
0.156
0.063
0.191
0.039
–0.028
0.332
0.045
0.305
–0.090
0.132
–0.144
0.177
0.863**
0.405*
0.336
–0.011
0.365*
–0.015
0.772**
0.424*
0.056
0.149
0.385*
–0.029
1
W
0.170
0.271
0.529**
0.316
0.103
0.022
0.036
0.103
–0.164
0.409*
0.365*
0.238
–0.287
–0.426*
0.132
0.270
–0.431*
0.207
–0.305
0.180
–0.235
0.210
–0.195
1
Ag
0.069
–0.181
–0.186
–0.025
–0.314
0.119
0.227
0.074
0.610**
–0.134
–0.319
–0.262
0.323
0.166
0.100
–0.028
0.160
0.218
0.240
0.227
0.137
–0.064
1
Mo
0.635**
0.054
0.176
–0.231
–0.149
–0.297
–0.330
0.681**
0.360
0.391*
0.192
0.489**
0.110
0.115
0.136
0.583**
0.215
–0.061
0.260
0.638**
–0.136
1
Co
0.268
–0.202
–0.138
0.200
–0.377*
–0.072
0.037
0.125
0.207
0.353
0.122
–0.159
0.105
0.428*
0.040
–0.235
0.026
–0.362*
–0.064
0.136
1
V
** Correlations is significant at the 0.01 level
* Correlations is significant at the 0.05 level
1
Sb
Sb
0.719**
0.013
0.323
–0.109
–0.035
–0.021
–0.010
0.808**
–0.232
0.517**
0.285
0.380*
0.395*
0.241
0.215
0.694**
0.059
–0.085
0.451*
1
Cu
0.231
–0.020
0.003
–0.086
0.018
0.269
0.088
0.420*
–0.168
–0.076
–0.245
0.173
0.878**
0.540**
0.296
0.111
0.534**
–0.010
1
As
–0.113
0.012
0.098
–0.080
–0.023
–0.045
0.118
–0.052
0.318
–0.121
–0.022
–0.032
–0.146
–0.293
–0.047
0.032
0.006
1
Sn
0.248
0.085
–0.095
–0.110
–0.082
–0.048
–0.063
0.273
–0.125
–0.020
–0.193
0.009
0.379*
0.415*
0.158
0.033
1
Hg
0.638**
0.010
0.454*
–0.171
0.358
–0.200
0.033
0.599**
–0.301
0.406*
0.584**
0.367*
–0.059
0.004
0.135
1
Ni
Table 3 Coefficient correlation between elements in sediment of Gumusler creek
0.146
0.088
0.071
0.225
–0.094
–0.132
0.398*
0.063
0.026
0.187
0.033
–0.056
0.253
0.096
1
Zn
0.267
–0.414*
–0.168
–0.076
–0.106
–0.093
–0.128
0.234
–0.041
–0.017
–0.207
–0.048
0.528**
1
Cd
0.145
–0.091
0.047
–0.073
0.067
0.363*
0.104
0.313
–0.153
–0.040
–0.207
0.228
1
Pb
0.359
–0.043
0.434*
–0.444*
0.454*
0.166
–0.466**
0.606**
–0.724**
0.288
0.426*
1
Si
0.472**
0.004
0.712**
–0.093
0.532**
0.024
–0.043
0.296
–0.463**
0.662**
1
Al
0.709**
0.180
0.737**
0.039
–0.084
–0.023
–0.129
0.582**
–0.400*
1
Fe
–0.310
–0.078
–0.533**
0.333
–0.521**
–0.122
0.472**
–0.461*
1
Ca
0.755**
0.012
0.392*
–0.294
–0.046
–0.003
–0.275
1
Mg
–0.243
0.166
–0.039
0.418**
0.013
0.114
1
S
–0.291
0.361
0.246
0.086
0.259
1
Na
–0.085
–0.093
0.450*
–0.183
1
K
–0.153
0.271
–0.026
1
Cl
0.447*
0.185
1
Ti
–0.103
1
Cr
1
1
Mn
Environ Geol (2008) 54:1155–1163 1159
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1160
Environ Geol (2008) 54:1155–1163
Table 4 Model summary tables for regression data Model summary Model
R
R2
Adjusted R2
Std. error of the estimate
1
0.996a
0.992
0.944
39.78202
a
Predictors: (constant), Mn, Mo, Cl, Sn, Hg, Na, Zn, K, Cd, S, V, W, Cr, Co, Ag, Ti, Mg, Si, Ni, Cu, Ca, As, Pb, Al, Fe
Table 5 ANOVA tables for regression data ANOVAb Model
1
Sum of squares
df
Mean square
F
Sig.
Regression 81,5706.301 25 32,628.252 20.617 0.005a Residual
6,330.438
Total
822,036.739 29
4
1,582.609
a
Predictors: (Constant), Mn, Mo, Cl, Sn, Hg, Na, Zn, K, Cd, S, V, W, Cr, Co, Ag, Ti, Mg, Si, Ni, Cu, Ca, As, Pb, Al, Fe
b
Dependent variable: Sb
Fig. 4 Principal components analysis loading plots (three components are extracted)
abundance. Sb shows strong positive correlation with W, As, Cd and Pb and moderately positive correlation with Cu and Hg (Table 2). In dendogram that was prepared on the basis of coefitic correlation coefficients of elements, Sb forms a significant group with Pb and is included in the group of W, As, Cd, Hg and V elements (Fig. 2). The average Pb concentration in the area is 49.1 lg/g and this value is expected between 17.5 and 133.8 lg/g (Table 1) which is higher than clark concentration of Pb in the earth
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crust (12.5 lg/g) and its abundance in sediments (17 lg/g). Pb is enriched in sediment three times higher than its average abundance. Pb shows strong positive correlation with Sb, W, As and Cd and moderately positive correlation with Cu and Hg (Table 2). In dendogram that was prepared on the basis of coefitic correlation coefficients of elements, it forms a significant group with Sb and is included in the group of Sb, W, As, Cd, Hg and V elements (Fig. 2). The average W concentration in the area is 19.1 lg/g and this value is expected between 5 and 84.2 lg/g (Table 1) which is higher than clark concentration of W in the earth crust (1.2 lg/g) and its abundance in sediments (1 lg/g). W is enriched in sediment 19.1% times higher than its average abundance. W shows strong positive correlation with As and Pb and moderately positive correlation with Mo, Cu, Hg, Cd (Table 2). In dendogram that was prepared on the basis of coefitic correlation coefficients of elements, it forms a significant group with Sb and Pb and is included to the group of As, Cd, Hg and V (Fig. 2). The average Fe concentration in the area is 35,398.8 lg/g and this value is expected between 2,3790 and 5,6550 lg/g (Table 1) which is higher than clark concentration of Fe in the earth crust (5.4 · 104 lg/g) and its abundance in sediments (2.1 · 104 lg/g). Fe is enriched in sediment two times higher than its average abundance. Fe shows strong positive correlation with Cu and Al and moderately positive correlation with Ag, Co, Ni, Si (Table 2). In dendogram that was prepared on the basis of coefitic correlation coefficients of elements, it forms a significant group with Ti and Al and is included to the group of Cu, Mg, Mn, Co and Ni (Fig. 2). According to hierarchical cluster analysis dendogram, the number of stations was found to be sufficient. In addition, similarities were determined among some stations. Stations with similarities can be categorized into four groups. In this respect, stations with similar characteristics have the same contaminant source (Fig. 3), Table 3. In the regression data on Sb concentrations, Model Summary and Anova tables were prepared (TableS 4, 5). Coefficient of determination of the regression equation for Mode Summary is R2 = 0 99.2% which yields significant correctness. On the basis of Anova, 25 determinant variables (Mn, Mo, Cl, Sn, Hg, Na, Zn, K, Cd, S, V, W, Cr, Co, Ag, Ti, Mg, Si, Ni, Cu, Ca, As, Pb, Al and Fe) moderately determine (Brady 1974) the variation in Sb concentrations (Boyle 1975). According to results of analyses for the sediment samples, high positive correlations (
