Marine Pollution Bulletin 49 (2004) 809–818

www.elsevier.com/locate/marpolbul

Source apportionment of trace metals in surface waters of a polluted

stream using multivariate statistical analyses
Hakan Pekey a,*, Duran Karaka+ b, Mithat Bakogˇlu c
a _
Department of Environmental Protection, University of Kocaeli, P.O. Box 318, 41275 zmit, Kocaeli, Turkey

b ¨ _
I
c
TUBITAK-MRC, Earth and Marine Sciences Research Institute, P.O. Box 21, 41470 Gebze, Kocaeli, Turkey
_
Environmental Engineering Department, University of Kocaeli, P.O. Bo x 318, 41300 zmit, Kocaeli, Turkey

Abstract

Surface water samples were collected from ten previously selected sites of the polluted Dil Deresi stream, during two field surveys,
December 2001 and April 2002. All samples were analyzed using ICP-AES, and the concentrations of trace metals (Al, As, Ba, Cd, Co,
Cr, Cu, Fe, Pb, Sn and Zn) were determined. The results were compared with national and international water quality guide-lines, as well
as literature values reported for similar rivers. Factor analysis (FA) and a factor analysis-multiple regression (FA-MR) model were used for
source apportionment and estimation of contributions from identified sources to the concentration of each parameter. By a varimax rotated
factor analysis, four source types were identified as the paint industry; sewage, crustal and road traffic runoff for trace metals, explaining
about 83% of the total variance. FA-MR results showed that predicted concentrations were calculated with uncertainties lower than 15%.

2004 Elsevier Ltd. All rights reserved.

Keywords: Source apportionment; Statistical analyses; Trace metals; Factor analysis; Factor analysis-multiple regression; ICP-AES
0025-326X/$ - see front matter 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.marpolbul.2004.06.029

1. Introduction

Trace elements, especially the so-called heavy metals,

are a serious pollutant in our natural environment due to
their toxicity, persistence and bioaccumulation prob-lems.
Their occurrence in waters and biota indicate the presence
of natural or anthropogenic sources (Rivail Da Silva et al.,
1996; Fang and Hong, 1999; Klavins et al., 2000; Tam and
Wong, 2000). Trace metals tend to be trapped in the
aquatic environment and accumu-late in sediments and
may be (1) directly available to benthic fauna or (2)
released to the water column through sediment
resuspension, adsorption/desorption reactions,
reduction/oxidation reactions and the degra-dation of
organisms. Such processes enhance the dis-solved
concentration of trace metals in the

* Corresponding author. Tel.: +90 262 3413073; fax: +90 262

3413375.
E-mail address: hpekey@lycos.com (H. Pekey).
environment and threaten the ecosystem (Rivail Da Silva et
al., 1996; Jones and Turki, 1997; Fang and Hong, 1999;
Wright and Mason, 1999). Certain trace elements, Cu and Zn,
are essential biological micronutri-ents required for normal
growth and function of organ-isms. Other trace elements, i.e.,
As, Cd, Hg, Pb and Sn, are considered to be toxic with
respect to human health and aquatic life (Libes, 1992;
Ouyang et al., 2002).
River and estuarine waters contain a range of inor-ganic
and organic components in dissolved and particu-late forms.
(Chester, 2003). Rivers may be the most important source of
heavy metals in the sea (Riley and Chester, 1971; Johnston,
1976; Feng et al., 1998). Water reaches river and estuarine
environments directly from the atmosphere, or indirectly
from surface run-off, underground water circulation and the
discharge of waste solutions. The composition of river water
includes products of mechanical and chemical weathering of
rocks, either in solution or as particles, and components
which are washed from the atmosphere in rainfall, and
810 H. Pekey et al. / Marine Pollution Bulletin 49 (2004) 809–818

may originally have been contained in salt particles of
marine origin or dust particles from the land (Johnston,
1976; Chester, 2003). Many rivers/streams in developing
countries are heavily polluted due to industrial and sew-age
discharges (Jonnalagadda and Mhere, 2001). Increasing
industrialization leads to ever increasing pol-lution of
rivers. The loading of rivers with heavy metals is of
increasing importance (Einax and Geiß, 1994) be-cause
these are sources of drinking water.
Pollution authorities use models to develop optimal
control strategies for environmental pollutants (Olmez et
al., 1994). Receptor models infer contributions from
different source types using multivariate measurements
taken at one or more receptor locations (Olmez et al., 1994;
Park, 1997; Watson et al., 2002). Several types of
mathematical models have been used in the source
apportionment studies. Factor analysis (FA) and factor
analysis-multiple regression (FA-MR) analysis are parts of
the multivariate model (Hopke, 1985; Okamoto et al.,
1990; Watson et al., 2002).
Dil Deresi is a small stream (length of about 20 km, an
_ downstream inputs of each source type on the Dil De-resi
average flow rate of 2 m3 s 1) which flows into Izmit Bay
(Fig. 1), where 2 million inhabitants living around its
catchment area are subjected to pollutant loads including
domestic wastewaters, industrial activities, agricultural
runoff and traffic. It is estimated that about
_ acidified with 10% HNO3, put in an ice bath and brought
60% of the total flow directly enters to the Izmit Bay
(Telli-Karakoc¸ et al., 2002). Some large industrial plants
(paint and metal industries) are located along the Dil
Deresi and are subject to limited treatments. Several
studies worldwide have been done on trace elements in
aquatic ecosystems (Runnels et al., 1992; Trocine and
Trefry, 1996; Pettine et al., 1996; Klavins et al., 2000;
Bakac¸ and Kumru, 2001; Barghigiani et al., 2001). There
is no reported information about the Dil Deresi and its
pollution levels for the trace metals.
Our study was done to identify contributing sources, and
to estimate the contributions of trace metals in the Dil
Deresi stream. For these purposes, we applied the varimax
rotated factor analysis (FA), reviewed by Henry et al.
(1984), Gordon (1988) and Okamoto et al. (1990), and
factor analysis-multiple regression (FA-MR), developed by
Thurston and Spengler (1985), to data sets obtained during
two field surveys.
2. Materials and methods
2.1. Analytical methodology
Two surveys were done on the Dil Deresi stream in
December 2001 and in April 2002. Samples for metal
analysis were collected from 10 sites chosen with regard to
basin (Fig. 2). Surface water samples were collected in
polyethylene bottles (washed with detergent, a second
deionised water, 2.0 M nitric acid (Merck), then deion-ised
water again, and finally surface water). Samples were
to the laboratory, and kept at 20 LC until analysis.
The US-EPA Method, 3010A (US EPA, 1992), and US-
EPA Method 6010B (inductively coupled plasma-atomic
emission spectrometry, ICP-AES, (US EPA,

_
Fig. 1. Map of Izmit Bay and Dil Deresi.
 H. Pekey et al. / Marine Pollution Bulletin 49 (2004) 809–818 811

Fig. 2. Location of ten sampling sites in Dil Deresi stream as shown by aerial photography.

1996)) were used, respectively, to digest and analyze Al, Table 1

As, Ba, Cd, Co, Cr, Cu, Fe, Pb, Sn and Zn. Operating parameters for inductively coupled plasma-atomic emission
spectrometry system
A 100 ml representative aliquot of the well-mixed
RF Generator 27 MHz
sample was placed into an acid washed glass beaker to Forward power 1200 W
which 3 ml of concentrated nitric acid (HNO3, Merck) Gas flow 16 l min 1 (coolant)
were added, and the beaker covered with a watch glass. 1.4 l min 1 (auxiliary)
The sample was heated on a hotplate and evaporated to 0.9 l min 1 (nebulizer)
Nebulizer Cross-flow
approximately 5 ml at 95 LC without boiling. The bea-ker Nebulizer gas flow pressure 3.2 bar
was then allowed to cool, after which, 3 ml of con- Spray chamber Glass
centrated nitric acid (HNO3) were added and the beaker Torch One piece
covered with a watch glass. The solution was again heated Wavelength range 160–820 nm
Flush time 10 s
at 95 LC and refluxed. Additional acid was added and the Integration time 35 s
reflux repeated until the appearance of the digestate was Observation height 15 mm above load coil
unchanged. The digestate was evap-orated to 3 ml at 95
LC, without boiling. After cooling, a small quantity of 1:1
hydrochloric acid, HCl (10 ml/ 100 ml of final solution)
were added to the sample digest and covered with a watch
glass to reflux for an addi-tional 15 min to dissolve any Table 2
precipitate or residue resulting from evaporation. After Spectral lines used in emission measurements and the instrumental
cooling, the digestate was transferred to a 100 ml detection limit for the elements measured by using ICP-AES
volumetric flask, diluted to 100 ml with Milli-Q deionised Element Wavelength (nm) Instrumental detection limit (lg l 1)
water (analytical grade), and the flask transferred to a 125 Al 308.215 100
ml high density poly-ethylene (HDPE) sample bottle for As 193.696 10
storage. Sample solutions were analyzed for trace metals Ba 455.403 2
following the ICP-AES (US EPA, 1996). Cd 228.802 2
Co 228.616 4
Cr 283.563 5
The instrumental parameters used and spectral lines Cu 324.754 7
selected are given in Tables 1 and 2. The detection limit is Fe 259.940 25
defined as the lowest analytical signal to be distin-guished Pb 220.353 10
qualitively at a specified confidence level from the Sn 189.926 10
background signal (Kackstaetter and Heinrichs, Zn 213.856 10
812 H. Pekey et al. / Marine Pollution Bulletin 49 (2004) 809–818

Table 3 use of orthogonal factor space and transformations that

Observed and certified values of elemental concentrations in NIST
yield predictions and/or recognizable factors (Mardia et al.,
standard reference material, SRM 1643d (lg l 1)
1979; Malinowski, 1991). Factor analysis identi-fies
Element Observations Observed Certified % Recovery
groups of elements whose concentrations fluctuate together
± SD ± SD
from one sample to another and separates these elements
Al 10 121.8 ± 5.2 127.6 ± 3.5 95.5
into ‘‘factors’’. Ideally, each extracted factor represents a
As 10 53.9 ± 1.35 56.02 ± 0.73 96.2
Ba 10 521.5 ± 10.4 506.5 ± 8.9 103.0 source affecting the samples (Olmez et al., 1994). In the
Cd 10 6.7 ± 0.54 6.47 ± 0.37 103.6 present study, Factor analysis (FA) and source
Co 10 23.9 ± 0.84 25.00 ± 0.59 95.6 apportionment by multiple regression on factor analysis
Cr 10 19.1 ± 0.35 18.53 ± 0.20 103.1 (FA-MR) were applied to surface water data on 14
Cu 10 21.4 ± 2.06 20.5 ± 3.8 104.4
variables, 11 trace metals (Al, As, Ba, Cd, Co, Cr, Cu, Fe,
Fe 10 89.7 ± 3.2 91.2 ± 3.9 98.4
Pb 10 18.9 ± 0.96 18.15 ± 0.64 104.1
Pb, Sn and Zn) and three dummy variables (Cu/As, Cr/As
Zn 10 70.8 ± 1.2 72.48 ± 0.65 97.7 and Pb/As), in 20 samples. Only the ele-ments having the
number of observations greater than 80% were included in
the factor analysis. For the treat-ment of missing values,
1997). In the ICP-AES analysis, the detection limits of the lower quartiles of elements were used; samples having
measured elements in our study were defined as the factor scores greater than or equal to 7.0 were not included
concentration value which corresponds to an absorbance in FA. Statgraphics Plus soft-ware (Statistical Graphics
value, numerically equal to the three times the standard Corp., 1997) version 3.1 was used for data treatment.
deviation of 10 replicate blank measurements.

Analytical reagent blanks were prepared with each batch

of the digestion set and then analyzed for the same
elements as the samples. The accuracy and precision of the
analytical method was estimated by analyzing fresh-water
Standard Reference Material (SRM 1643d), sup-plied by
the National Institute of Standards and Technology (NIST).
Elemental concentrations of SRM were determined by
ICP-AES and their certified values and observed values
given in Table 3. Analytical preci-sion was in good
agreement, generally better than ±5.0% RSD. Accuracy of
the analytical method was given as percent recoveries for
each of the elements. Re-sults, reported in Table 3, show
that recoveries ranged from 95.5% (Al) to 103.2% (Cu).
2.2. Multivariate statistical methodology
Factor analysis is a multivariate model for reducing
matrices of data to their lowest dimensionality by the
3. Results and discussions
3.1. General characteristics of data
Summary statistics for elemental concentrations at
sampling sites are presented in Table 4, which includes
mean concentration with associated standard deviation,
geometric mean, minimum, maximum and median val-ues.
Each individual element displays a wide variation in
elemental concentration as reflected by the large standard
deviation values. Due to variations within each element,
mean concentration might be significantly af-fected via the
extremely high or low values. Median and/or geometric
mean concentrations, on the other hand, will not be
affected by the extreme values. There-fore, geometric mean
concentrations of elements are used for calculation in our
study, however, results re-ported in literature and
guidelines are generally given

Table 4
Summary statistics (mean, standard deviation (in bracket), geometric mean and minimum, maximum and median values) for surface water data in the Dil
Deresi stream (concentration unit is in lg l 1 except Al, Ba and Fe in mg l 1)
Element Mean ± STD Geometric mean Minimum Maximum Median
Al 8.46 ± 31.2 0.86 0.17 133.5 0.57
As 50 ± 80 30 10 290 30
Ba 1.48 ± 0.9 1.32 0.68 4.41 1.20
Cd 8± 3 7 3 15 7
Co 21 ± 10 19 10 56 19
Cr 42 ± 30 35 16 110 30
Cu 37 ± 20 31 11 94 31
Fe 4.03 ± 11 1.28 0.25 48.0 1.31
Pb 120 ± 110 90 11 370 80
Sn 110 ± 70 80 10 240 90
Zn 700 ± 1100 340 150 4100 220
 H. Pekey et al. / Marine Pollution Bulletin 49 (2004) 809–818 813

as arithmetic means, therefore, we used arithmetic means 15

frequenc
for comparison purposes. Geometric mean con-centrations 12

of trace and major elements are between 7.0 lg l 1 (Cd) and

9

y
6
1.32 mg l 1 (Ba) for the whole data set. The major elements 3
iron (Fe) and Al in water sam-ples have geometric mean 0
concentrations (as mg l 1) of 1.28 and 0.86 for the whole 0 1 2 3 4 5
Al
data matrix, respectively. Trace elements like Ba, Zn, Pb
and Sn have the greatest geometric mean concentrations in 15

frequenc
12
the data set, as shown in the table, and are 1.32, 0.34, 0.09
9
and 0.08 mg l 1, respectively.

y
6
The Kolmogorov–Smirnov (K–S) statistics were used to 3
test the goodness-of-fit of the data to log-normal dis- 0
tribution. In the case of log-normal distribution, the 0 0.05 0.1 0.15 0.2 0.25 0.3
maximum absolute distance between the data and the As

hypothesized distribution is calculated to test the con- 16

formance of the two cumulative distribution functions
(Karaka+ et al., 2002). According to the K–S test, all ele-
ments are log-normally distributed with 95% or higher
confidence. The frequency histograms and associated
distribution curves for a crustal (Al), and anthropogenic
elements (As and Zn) are given in Fig. 3.
Correlations between the element pairs studied are
statistically tested. The Pearson s correlation coefficient
matrix for the elements is given in Table 5. The elements
having high degrees of correlations (0.5 6 r 6 0.9) are Ba,
Co, Cr, Cu, Fe, Pb and Zn. These strong correla-tions
between the elements given above clearly indicate that they
have similar anthropogenic sources, mainly represented by
the paint industry. Values for Al and Fe of the Dil Deresi
stream waters indicate good corre-lations with each other (r
= 0.9); besides, they also cor-relate with Co, Cu and Cr
(0.5 6 r 6 0.9), which are used as markers or tracers of the
metal industry.
3.2. Comparison with literature
The pollution status of Dil Deresi stream is given in
Table 6. The table was generated by comparing meas-ured
concentrations of elements with the water quality
frequency
12
8
4
0
0 1 2 3 4 5
Zn
Fig. 3. Frequency histograms and distribution curves of Al (crustal), and
As and Zn (anthropogenic elements).
standards currently effective in Turkey (Turkish Envi-
ronmental Guidelines, 1988; US EPA, 1999), and results
obtained from similar sites given in literature (Trocine and
Trefry, 1996; Pettine et al., 1996; Klavins et al., 2000;
Bakac¸ and Kumru, 2001; Barghigiani et al., 2001). Water
quality regulation in Turkey divides inland waters into four
classes. Class I refers to clean water that can be used for
domestic purposes after simple disinfec-tion, for
recreational purposes and for irrigation. Class
II refers to fairly clean water that can be used as domes-tic
water after treatment, for recreational purposes, for fishing,
farming etc. Class III includes polluted water which can
only be used as industrial water after treat-
ment. Class IV refers to heavily polluted water that

Table 5
Pearson s correlation coefficient matrix for trace/major elements in surface waters from Dil Deresi stream
Al As Ba Cd Co Cr Cu Fe Sn Pb Zn
Al 1.0
As 1.0
Ba 0.5a 1.0
Cd 0.3 1.0
Co 0.9a 0.7a 1.0
Cr 0.6a 0.7a 0.8a 1.0
Cu 0.5a 0.4 0.9a 0.8a 0.8a 1.0
Fe 0.9a 0.5a 0.9a 0.6a 0.9a 1.0
Sn 0.5 0.4 0.7a 0.7a 0.6a 0.7a 0.5 1.0
Pb 0.5a 0.8a 0.8a 0.8a 0.8a 0.5a 0.7a 1.0
Zn 0.5a 1.0
a Significant at 99% confidence level; all others at 95%.
814 H. Pekey et al. / Marine Pollution Bulletin 49 (2004) 809–818

Table 6
Trace metal concentrations from various sources (concentration unit is in lg l 1)
Location As Cd Cr Cu Pb Zn
a
This study, Range 10–290 3–15 16–110 11–94 11–370 150–4100
(Mean ± STD) (50 ± 80) (8 ± 3.0) (42 ± 30) (37 ± 20) (120 ± 110) (700 ± 1100)
Background concentration, world averageb 1 0.02 0.5 1 0.2 10
Surficial seawaterc 1.1 0.003 0.27 0.034 0.014 0.007

Guidelines
US EPA Water Quality Criteriad
Criteria maximum concentration, CMC 340 4.3 16 13 65 120
Criterion continuous concentration, CCC 150 2.2 11 9 2.5 120

Turkish Environmental Guidelinese

Class I 20 3 20 20 10 200
Class II 50 5 50 50 20 500
Class III 100 10 200 200 50 2000
Class IV >100 >10 >200 >200 >50 >2000
Indian river, Floridaf 0.89 0.006 0.15 1.1 0.025 0.8
Lambro river, Italyg n.d. 0.1–4.8 2–66 1.1–134.4 2.2–138.8 n.d.
Latvia river, Latviah n.d. 0.02 n.d. 0.56 0.10 3.35
Gediz river, Turkeyi n.d. 2–8 1–17 4–84 10–110 3–46
Era river, Italyj n.d. 0.1–7 0.3–30.8 0.2–48.9 0.1–7.4 n.d.
n.d.: not determined.
a This study.

b Salomons and Fo¨rstner (1984). c

Trocine and Trefry (1996).
d US EPA (1999) National recommended water quality criteria. e
Turkish Environmental Guidelines (1988).
f Trocine and Trefry (1996). g
Pettine et al. (1996).
h Klavins et al. (2000).
i Bakac¸ and Kumru (2001). j
Barghigiani et al. (2001).

should not be used at all. If the measured concentration of
an element in the stream is lower than the standards given
for Classes I or II water, the stream is accepted as
unpolluted for that particular element in the table. If the
measured concentration is higher than the standard given
for Class II water, the stream is said to be polluted with
that element. Therefore, the mean concentrations of Cu and
Cr are comparable with the Class II and the mean
concentrations of As, Cd and Zn belong to Class III. The
level of Pb is higher than the value given for fourth Class
water quality.
When compared with the priority toxic pollutants, As,
Cd, Cr, Cu, Pb and Zn (listed in US EPA (1999) water
quality criteria) almost all of the elemental con-centrations
were observed to be greater than the back-ground
concentrations of the elements in the riverine waters. When
similar sites are considered, our results are comparable
with the polluted rivers. However, the mean concentrations
of Cd, Cr, Cu, Pb and Zn are greatest than the criteria
maximum concentrations (CMC) and criterion continuous
concentration (CCC) values of the US EPA Water Quality
Criteria; values for As are lower than the US EPAs CMC
and CCC values.
3.3. Source apportionment and quantification
Factor analysis (FA) and factor analysis-multiple
regression (FA-MR) were used to identify the source types
and to quantify the contributions of each source to the
water quality of the Dil Deresi stream. To differ-entiate
between the industrial and domestic discharges, we used
the method developed by Atgın (2000). In this method,
they generated dummy variables using chro-mium as the
normalizing element due to its high concen-tration levels in
industrial discharges and very low concentrations in
sewages. Similarly, values for As in our study were high in
industrial discharges and low in domestic discharges.
Therefore, As was selected as a normalizing element and
three dummy variables, Cu/ As, Cr/As, Pb/As were
generated for each sampling site and included in the
dataset. In this study, the concentra-tions of Cu, Cr and Pb
were very high at sewers com-pared to the industrially
affected sites. The elements having the similar distributions
of element to As ratios (dummy variables) are expected to
be observed in the same factor. On the other hand, the
elements that are predominantly discharged from the
industries are ex-pected to appear as a separate factor.
 H. Pekey et al. / Marine Pollution Bulletin 49 (2004) 809–818 815

The varimax rotated factor analysis results are pre-
sented in Table 7 with probable source types. In the table,
the eigenvalue was set to 1.0 as a threshold in order to limit
the number of extracted factors. Factor loadings equal to or
greater than 0.3 were presented in the table because those
less than 0.3 were considered as insignifi-cant. Four factors
were obtained which explained about 83% of the total
variance, with the first factor accounting for 37.8%, the
second factor for 21.6%, the third factor for 13.6% and the
fourth factor for 9.4%. The first factor has high loadings of
Co, Cu, Pb, As, Cr, Sn and Ba. All of the elements in this
factor are likely to originate from industrial wastewaters
which are discharged into the stream. Elements like Co,
Cu, Pb, As, Cr, Sn and Ba are known as markers of paint
industries (Aksu et al., 1998; Ya+ar et al., 2001; Lin et al.,
2002) many of which are present in the study area. The
second factor contains only one variable, Cr, with weak
loading and high loa-dings of the three dummy variables.
Elements like Cu, Cr and Pb are likely to come mostly
from sewage (Van Alsenoy et al., 1993; Robson and Neal,
1997; Atgın et al., 2000; Ruiz, 2001; Feng et al., 2002; Liu
et al., 2003). The presence of dummy variables in this
factor suggests that it represents sewage discharge to the
stream. The third factor displays high loadings of Fe and
Al, weak loadings of Cr and Ba. These elements are most
often found in crustal components (Salomons and
Fo¨rstner, 1984; Huang et al., 1994; Zelenka et al., 1994;
Atgin et al., 2000; Kumar et al., 2001). It can, therefore, be
identified as originating from crustal contri-bution. The
fourth factor is characterized by high loa-dings of Zn, Cd
and Pb, which are used as markers or
tracers of motor vehicles (Huang et al., 1994; Qu and
Kelderman, 2001). Since few gasoline-powered automo-
biles in the mideast use unleaded gasoline, Pb remains a
useful tracer element in Turkey. Therefore, this factor is
assumed to be heavily affected by road traffic runoffs.
3.4. Factor analysis-multiple regression (FA-MR)
Although factor analysis applied to the data set pro-
vides qualitative information about the sources of the
contaminant it is not adequate for supplying quantita-tive
information regarding the contributions of each source
type. To overcome this problem, the multiple regression
method was applied to the data set following the factor
analysis.
The accuracy of the FA-MR exercise can be tested by
calculating ‘‘observed to predicted’’ ratios of the ele-
ments, since FA-MR gives the contribution of each source
on the concentration of each element in the same sample.
The observed to predicted ratios (O/P) of the elements
varied between 1.14 (Pb) and 0.85 (Al). It is clearly
indicated in Table 8 that these elements are pre-dicted with
an uncertainty of better than 15%. The per-cent
contribution of each of the sources of the observed Al, As,
Ba, Cd, Co, Cr, Cu, Fe, Pb, Sn, Zn, Cu/As, Cr/ As and
Pb/As concentrations are given in Table 8 and Fig. 4.
Aluminum, Sn and Zn had moderate r values (70 < r < 80)
which means that FA-MR method could not explain the
contributions efficiently. However, the rest of the elements
had higher r values very close to the original communality
values. When the combined percent contributions of the
identified sources were used

Table 7
Varimax rotated factor loading and corresponding possible source type
Variable Factor 1 Factor 2 Factor 3 Factor 4 Communality (factors 1–4)
As 0.76 0.92
Cu 0.82 0.83
Sn 0.65 0.53
Co 0.85 0.74
Cr 0.74 0.44 0.43 0.93
Ba 0.65 0.30 0.41 0.78
Pb 0.77 0.37 0.81
Al 0.68 0.71
Fe 0.93 0.96
Cd 0.46 0.87
Zn 0.94 0.92
Cu/As 0.71 0.80
Cr/As 0.86 0.88
Pb/As 0.89 0.87

Eigenvalue 5.29 3.03 1.91 1.32 11.55a

Percent of variance 37.8 21.6 13.6 9.4
Cumulative percentage 37.8 59.4 73.0 82.4

Possible source type Paint industry Sewage Crustal Road traffic runoff
a Sum of communality.
816 H. Pekey et al. / Marine Pollution Bulletin 49 (2004) 809–818

Table 8
Source contribution (in %) and the observed to predicted ratios (O/P) of elements calculated using FA-MR technique
Variable Paint industry Sewage Crustal Road traffic runoff O/P ratios r
Al 28.6 5.1 62.1 4.2 0.85 78
As 71.4 5.3 13.5 9.8 0.86 93
Ba 60.0 9.9 14.9 15.2 1.06 91
Cd 27.8 11.3 23.5 37.4 1.08 88
Co 72.0 0.6 10.1 17.3 0.98 89
Cr 25.9 18.5 44.8 10.8 0.97 97
Cu 57.8 0.8 31.7 9.7 1.08 93
Fe 31.5 8.1 51.3 9.1 0.94 89
Pb 48.8 9.3 10.2 31.7 1.14 83
Sn 77.1 0.5 12.8 9.6 1.10 73
Zn 33.6 9.4 17.4 39.6 1.13 72
Cu/As 7.1 74.2 11.4 7.3 0.89 89
Cr/As 9.8 64.8 19.9 5.5 0.92 90
Pb/As 4.9 80.3 5.3 9.5 0.91 93
r is the multiple correlation coefficient.

Fig. 4. Percent contributions of the sources on the observed elemental concentrations.

to calculate the elemental concentrations, the estimated
concentrations were observed to be similar to the meas-
ured values (Fig. 4).
4. Conclusions
Concentrations of trace metals in the surface water
samples collected twice along the Dil Deresi stream were
investigated to determine the status of the pollution and the
stream and to estimate the contributions of the pol-lution
sources using multivariate statistical analysis.
Concentrations of almost all of the elements were found to
be log-normally distributed elements having similar origins
showed high inter-elemental correlations. Con-centrations
of the elements, As, Cd, Cr, Cu, Pb and Zn, presented in
the priority pollutant list of the US EPA were higher than
background concentrations in our riverine waters. When
this level of pollution was
compared with similar sites reported in literature, our
results were comparable to results of polluted rivers and
the water was observed to be polluted by most of the
elements defined in the Turkish Water Quality Guidelines.
The multivariate receptor modelling ap-proach based on
FA and FA-MLR was applied to the dataset to apportion
quantitatively the trace metal sources contributing to the
surface water pollution in the stream. Dummy variables
were used to enhance the source identification capability of
the FA and to dif-ferentiate the contributions of the
discharges coming from the industrial and domestic
discharges. FA and FA-MR results showed that the paint
industry and sew-age were the most dominant polluting
sources. This study also demonstrates the value of
multivariate statis-tical analyses in aquatic environment
studies. Further ef-forts should be focused on distribution
and sources of
_
trace metals in Izmit Bay which are affected by the pol-luted
Dil Deresi stream.
 H. Pekey et al. / Marine Pollution Bulletin 49 (2004) 809–818
Acknowledgments
¨ _
This work was done by TUBITAK-Marmara Re-search
Center, grant 5017509, and supported by the Greater
_ Kackstaetter, U.R., Heinrichs, G., 1997. Validity of lowcost labora-tory
Municipality of Izmit . The authors would like to express
our gratitude to Prof. Enis Morkoc¸ and Dr. Leyla Tolun
for assistance in sampling, and Sevim Albayrak and Arzu
Uluta+ for help with analyses. The authors would like to
thank Dr. John Pearce, North American Editor, Marine
Pollution Bulletin, and three anonymous reviewers for
valuable comments which im-proved the quality of the
paper. Also, we thank Clive Naylor for his editing of the
paper.
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