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Science of the Total Environment 484 (2014) 2735

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Science of the Total Environment


journal homepage: www.elsevier.com/locate/scitotenv

Metal contamination in campus dust of Xi'an, China: A study based on


multivariate statistics and spatial distribution
Hao Chen a, Xinwei Lu a,, Loretta Y. Li b,, Tianning Gao a, Yuyu Chang a
a
b

School of Tourism and Environment, Shaanxi Normal University, Xi'an 710062, PR China
Department of Civil Engineering, University of British Columbia, Vancouver V6T 1Z4, Canada

H I G H L I G H T S

Metal content in dust from schools was determined by XRF.


Spatial distribution of metals in urban dust was focused on campus samples.
Multivariate statistic and spatial distribution were used to identify metal sources.
Pb, Zn, Cu, Co and Cr mainly originate from anthropogenic sources.
As, Mn, Ni, V and Ba were mainly inuenced by natural sources.

a r t i c l e

i n f o

Article history:
Received 21 December 2013
Received in revised form 8 March 2014
Accepted 8 March 2014
Available online 28 March 2014
Editor: Xuexi Tie
Keywords:
Metals
Multivariate statistics
Spatial analysis
Source
Dust

a b s t r a c t
The concentrations of As, Ba, Co, Cr, Cu, Mn, Ni, Pb, V and Zn in campus dust from kindergartens, elementary
schools, middle schools and universities of Xi'an, China were determined by X-ray uorescence spectrometry.
Correlation coefcient analysis, principal component analysis (PCA) and cluster analysis (CA) were used to
analyze the data and to identify possible sources of these metals in the dust. The spatial distributions of metals
in urban dust of Xi'an were analyzed based on the metal concentrations in campus dusts using the geostatistics
method. The results indicate that dust samples from campuses have elevated metal concentrations, especially for
Pb, Zn, Co, Cu, Cr and Ba, with the mean values of 7.1, 5.6, 3.7, 2.9, 2.5 and 1.9 times the background values for
Shaanxi soil, respectively. The enrichment factor results indicate that Mn, Ni, V, As and Ba in the campus dust
were deciently to minimally enriched, mainly affected by nature and partly by anthropogenic sources, while
Co, Cr, Cu, Pb and Zn in the campus dust and especially Pb and Zn were mostly affected by human activities. As
and Cu, Mn and Ni, Ba and V, and Pb and Zn had similar distribution patterns. The southwest high-tech industrial
area and south commercial and residential areas have relatively high levels of most metals. Three main sources
were identied based on correlation coefcient analysis, PCA, CA, as well as spatial distribution characteristics.
As, Ni, Cu, Mn, Pb, Zn and Cr have mixed sources nature, trafc, as well as fossil fuel combustion and weathering
of materials. Ba and V are mainly derived from nature, but partly also from industrial emissions, as well as
construction sources, while Co principally originates from construction.
2014 Elsevier B.V. All rights reserved.

1. Introduction
Atmospheric pollution constitutes a major challenge in many densely populated cities in many countries, in particular those under rapid industrialization and urbanization which face poor air quality and heavy
dust deposition (Hien et al., 1999; Tanner et al., 2008; Schleicher et al.,
2011). Dust, containing trace metals, is released to the atmosphere
during combustion of fossil fuels and wood, as well as from high-

Corresponding author. Tel.: +86 29 85310525; fax: +86 29 85303883.


Corresponding author. Tel.: +1 604 822 1820; fax: +1 604 822 6901.
E-mail addresses: luxinwei@snnu.edu.cn (X. Lu), lli@civil.ubc.ca (L.Y. Li).

http://dx.doi.org/10.1016/j.scitotenv.2014.03.026
0048-9697/ 2014 Elsevier B.V. All rights reserved.

temperature industrial processes, waste incineration and trafc (Allen


et al., 2001; Thakur et al., 2004). Dust particulates have been well recognized to inuence human health (Li et al., 2008; Ruiz-Jimenez et al.,
2012), in particular due to trace metals (Chillrud et al., 2004; Khairy
et al., 2011; Lu et al., 2014) which are toxic to humans through ingestion
or inhalation. For example, As, Cd and their chemical compounds are
highly carcinogenic, while low concentrations of Pb in blood can affect
children's mental development, an effect that persists into adulthood
(Needleman, 1990; Laidlaw and Tayor, 2011). Mn is considered toxic
if taken up through inhalation, causing movement disorders, respiratory
effects and reproductive dysfunction (WHO, 2000; USEPA, 2003).
Although Zn is an essential nutrient for human organs, it is toxic at
high concentrations (Adamson et al., 2000).

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H. Chen et al. / Science of the Total Environment 484 (2014) 2735

Numerous studies on street dust have been conducted on metal concentrations, distribution, and source identication in the past decade
(Bennett et al., 2006; Tanner et al, 2008; Lu et al., 2010; Laidlaw and
Tayor, 2011; Glorennec et al., 2012). While there has been some recent
information related to dust in the workplace and in residential houses
(Abdul-Wahab and Yaghi, 2004), very few studies have been reported
within sensitive environments such as nursery schools (Tong and
Lam, 1998; Lu et al., 2014). Xi'an, the biggest city in northwestern
China, has experienced rapid urbanization and industrialization in
recent decades causing metal contamination in urban soil and street
dust (Han et al., 2008; Chen et al., 2012). Despite these serious effects
on health development, especially for children and young adults, studies in these areas are lacking, and information about metal contamination in the academic urban environment is limited. Our work was
carried out to assess pollution of metals in dust sampled from a wide
range of educational campuses including kindergartens, elementary
schools, middle schools and universities of Xi'an. The main objectives
were to determine the campus concentrations of Cu, Pb, Zn, As, Ba, Co,
Cr, Mn, Ni and V (metals which are potentially harmful to the environment and human health); to investigate the spatial distribution of
metals in urban dust of Xi'an; and to identify the sources of metals in
campus dust based on multivariate statistical methods and spatial
analysis.

2. Materials and methods


2.1. Area Description
Xi'an, the capital of Shaanxi province, is located in the central Wei
River valley (1074010949E and 33393445N). It has a typical
temperate continental semi-arid climate, with a monthly average temperature of 0.9 C in January, 26.4 C in July and an annual average temperature of ~13 C (Cao et al., 2011). Xi'an is located in a loess plateau
that is the major source of Asian dust (Zhang et al., 2001), with serious
contamination from airborne particulate matter (PM), especially in the
spring when frequent dust storms occur (Han et al., 2008). Xi'an has a
history of more than two thousand years. With its rapid industrialization, urbanization and high-tech development in recent decades, this
city is the center of the economy, culture, manufacturing and education
in northwest China (Chen et al., 2012). The total urban area of Xi'an city
is ~3580 km2, and its population was 6,470,000 in 2009. The motorized
vehicle density has grown from 0.52 million in 2004 to 0.98 million in

2009 (XAMBS, 2011). Presently, Xi'an has 1004 kindergartens, 1531 elementary schools, 660 middle schools and 50 universities, hosting
700,000 nursery and primary school students, 779,000 middle-school
students and 733,000 university students (XAMBS, 2011).
2.2. Dust sampling and analytical method
A total of 157 kindergartens, primary schools, middle schools and
universities of Xi'an were selected for the collection of dust samples
(Fig. 1). Sampling was conducted during the dry season between
October 2011 and October 2012. Dust samples in each campus were collected in the same dry season by sweeping, using a clean plastic dustpan
and a brush (Akhter and Madany, 1993; Lu et al., 2009) from window
sills, balconies, doorsteps and school playgrounds most accessible to
students. The collected dust samples were stored in sealed polyethylene
bags for transport and storage. All samples were air-dried in the laboratory for two weeks and then sieved through a 1.0 mm nylon mesh to
remove large particles such as tree leaves, refuse and small stones,
before splitting the samples by halving and mixing. 50 g of each sieved
dust sample was quartered and then ground with a vibration mill and
sieved through a 0.075 mm nylon mesh.
X-ray uorescence (XRF) samples were prepared by weighing 4.0 g
of milled dust sample and 2.0 g of boric acid, placed in a mold, and
pressed into a 32 mm diameter pellet under 30 t pressure. The concentrations of As, Ba, Co, Cr, Cu, Mn, Ni, Pb, V and Zn in dust samples were
then measured by wavelength dispersive X-ray uorescence spectrometry (XRF, PANalytical PW2403 apparatus) (Lu et al., 2010).
For quality assurance and control (QA/QC), duplicate samples and
standard reference materials (GSS1 and GSD12) (Lu et al., 2010),
purchased from the Center of National Standard Reference Material of
China, were prepared and analyzed using the same procedure. The
precision, calculated from the relative standard deviation of duplicate
samples, was routinely 35%. The accuracy, based on the relative error
of standard reference materials, was b 5%.
2.3. Outlier detection
Outliers, often observed in environmental geochemical datasets
(Zhang et al., 1998), arise due to human error, instrument error, natural
deviations in populations, fraudulent behavior, changes in behavior of
systems or faults (Hodge and Austin, 2004). Outliers are dealt with
before statistical analysis by the most common method the range

Fig. 1. Sketch indicating sampling sites in Xi'an.

H. Chen et al. / Science of the Total Environment 484 (2014) 2735

method: Values lower than the average values minus three standard
deviations and those higher than the average plus three times the standard deviation are considered to be outliers. Here, the outlying values
were deleted and then replaced by the highest values in datasets after
deletion (Zhang et al., 1998).
2.4. Enrichment factor analysis
To assess the degree of anthropogenic inuence, enrichment factors
(EFs) were calculated. They provide a measure of the extent to which
trace elements are enriched or reduced relative to a specic source
(Odabasi et al., 2002). They can be used to differentiate between metals
originating from human activities and those from natural sources
(Meza-Figueroa et al., 2007). The EF of an element in a studied sample
is based on the standardization of a measured element against a reference element. The reference element is often characterized by low
occurrence variability, with the most commonly used elements being
Al, Fe, Ti, Si, Sr, and K (Tasdemir and Kural, 2005; Han et al., 2006;
Turner and Simmonds, 2006; Hao et al., 2007; Meza-Figueroa et al.,
2007). EF is calculated by
h
i
EF C x =C ref

sample

h
i
= C x =C ref

29

given multidimensional system by displaying the correlations among


the original variables (Lu et al., 2010). PCA was applied in this study to
identify the possible sources of metals in the dust by applying varimax
rotation with Kaiser Normalization (Lu et al., 2010). The Kaiser
MeyerOlkin (KMO) measure of sampling adequacy is used to compare
the magnitudes of the observed correlation coefcients with the magnitudes of the partial correlation coefcients. Large KMO (01) values are
useful because correlations between pairs of variables can be explained
by the other variables (Yuan et al., 2014). Bartlett's test of sphericity is
used to test the hypothesis that the correlation matrix is an identity
matrix with suitable signicance (P b 0.05) (Yuan et al., 2014). In this
study, the KMO (0.747) and Bartlett's test (P b 0.001) show that the
measured metal concentrations for campus dust from Xi'an are suitable
for PCA (Chen et al., 2012; Yuan et al., 2014).
CA is often coupled to PCA to check results and to help group individual parameters and variables (Facchinelli et al., 2001). CA was developed according to Ward's method. Euclidean distance was employed
to measure the distance between clusters of similar metal contents.
The purpose of CA is to organize observations where a number of
groups/variables share observed properties (Lu et al., 2010). Statistical
analyses were performed with SPSS 19.0 for Windows.

Background

2.6. Spatial analysis

where Cx is the concentration of the element of interest and Cref is the


concentration of the reference element for normalization. EF analysis
can assist in differentiating anthropogenic sources from natural ones.
A value of EF close to 1 indicates natural origin, whereas values N10
are considered to originate mainly from anthropogenic sources (Han
et al., 2006; Turner and Simmonds, 2006). EF analysis can also assist in
determining the degree of metal contamination (Meza-Figueroa et al.,
2007). EF 2 means decient to minimal enrichment, 2 b EF 5 corresponds to moderate enrichment, 5 b EF 20 signies signicant enrichment, 20 b EF 40 indicates very high enrichment, and 40 b EF means
extremely high enrichment (Lu et al., 2009).

The spatial distributions of metals in urban dust of Xi'an were analyzed based on the metal concentrations in campus dusts using the
geostatistics method. Geostatistics is a tool for studying and predicting
the spatial structure of geo-referenced variables, focused on spatial
objects and spatial correlation (Chen et al., 2008). Kriging is based on
the assumption that the parameter being interpolated can be treated
as a regionalized variable (Xie et al., 2011). It is regarded as the best spatial covariance interpolation method, providing optimal interpolation
(Chen et al., 2008). The spatial distribution maps of all metals studied
in Xi'an urban dust were generated by the Kriging interpolation of
geostatistics method with ArcGIS software.

2.5. Statistical analysis


3. Results and discussion
Experimental data were analyzed by correlation coefcient analysis,
principal component analysis (PCA) and cluster analysis (CA) to determine the relationship among the metals investigated in the dusts.
They are widely used in environmental studies (Han et al., 2006;
Tokalolu and Kartal, 2006; Lu et al., 2010). Pearson's correlation coefcient, a measure of the strength of a linear relationship between two
quantitative variables (Tokalolu and Kartal, 2006), was applied.
PCA is widely used to reduce the data and to extract a small number
of latent factors (principal components, PCs) for analyzing the relationships among the observed variables (Han et al., 2006). In PCA, the principal components are calculated based on the correlation matrix.
Varimax with Kaiser Normalization was used as the rotation method
(Lee et al., 2006). PCA can reduce the number of correlated variables
to a smaller set of orthogonal factors, making it easier to interpret a

3.1. Metal concentrations in campus dust


The descriptive statistical results of metal concentrations in campus
dust of Xi'an after outlier treatment, as well as background values for
Shaanxi soil (CNEMC, 1990), are shown in Table 1. This table shows
that the arithmetic means of As, Ba, Co, Cr, Cu, Mn, Ni, Pb, V and Zn in
the studied dust samples are 11.5, 958.9, 39.6, 154.2, 62.1, 546.2, 32.2,
151.6, 68.7 and 390.7 mg kg1, respectively. Compared with the background values of Shaanxi soil, the arithmetic means, geometric means
and medians of all analyzed metals in campus dust are clearly higher
than the corresponding background values of Shaanxi soil, except for
As, Mn, Ni and V. The maximum concentrations of Cu, Pb, Zn, Cr, Co
and Ba in the dust are 6.5, 23.1, 26.5, 6.4, 7.7 and 4.3 times the

Table 1
Metal concentrations in campus dust of Xi'an and reference values (mg kg1).
Element

As

Ba

Co

Cr

Cu

Mn

Ni

Pb

Zn

Max
Min
Mean
GM
Median
SD
CV(%)
Skewness
Reference valuea

29.7
1.4
11.5
10.2
10.3
5.8
50
1.2
11.1

2195.9
542.7
958.9
914.6
869.5
336.8
35
2.0
516.0

81.1
19.3
39.6
37.5
37.6
13.4
34
0.8
10.6

402.4
77.4
154.2
145.4
134.4
64.0
41
2.5
62.5

138.3
22.3
62.1
57.4
59.2
24.9
40
1.0
21.4

795.8
349.5
546.2
538.9
527.6
94.7
17
0.7
557

64.2
16.8
32.2
31.2
31.5
8.2
26
0.6
28.8

494.1
37.2
151.6
131.8
132.4
93.2
61
2.1
21.4

99.3
50.2
68.7
68.0
67.6
10.0
15
0.9
66.9

1838.3
65.9
390.7
319.5
319.1
299.3
77
2.8
69.4

CNEMC (1990).

30

H. Chen et al. / Science of the Total Environment 484 (2014) 2735

background values of Shaanxi soil, respectively, and their mean values


in the dust are 2.9, 7.1, 5.6, 2.5, 3.7 and 1.9 times the corresponding
background values, respectively. The mean values of metals in campus
dust divided by the corresponding background value of Shaanxi soil decrease in the order Pb N Zn N Co N Cu N Cr N Ba N Ni N As N V N Mn. The
range and the mean of Cu, Pb, Zn, Cr and Mn in the studied dust samples
are all lower than their ranges and means in the road dust of Xi'an (Han
et al., 2008), while the concentration of As in the campus dust is similar
to that in the road dust (Han et al., 2008). This may be because most
schools are far from main streets.
3.2. Enrichment factor analysis results
Enrichment factors (EFs) of all analyzed metals were calculated for
each dust sample relative to the background value of the local soil
(CNEMC, 1990), with Al chosen as the reference element (Turner and
Simmonds, 2006). Fig. 2 shows the cumulative frequency distribution
analysis of EF of metals in the dust. The EF values of As, Ba, Co, Cr, Cu,
Mn, Ni, Pb, V and Zn are in the ranges of 0.092.35, 0.603.73,
1.295.37, 0.975.26, 0.755.28, 0.401.17, 0.401.82, 0.8818.98,
0.521.12 and 0.4823.22, with averages of 0.74, 1.32, 2.66, 1.76, 2.08,
0.70, 0.80, 5.08, 0.73 and 4.05, respectively. EF of Mn, Ni and V in all
dust samples, As in 98% of the samples and Ba in 92% of the dust samples
are b2, showing the lack of pollution of these metals in Xi'an campus
dust. The mean EF and the nding of 73% of EF values for Co in the
range of 25 reveal that Co of campus dust corresponds to moderate
pollution. For Cr 83% of EF values and 16% of EF values were b2 and in
the range 25, respectively, with a mean EF b 2, indicating that Cr corresponds to decient to moderate pollution. The mean EF and 46% of EF
values of Cu are in the 25 range, indicating moderate pollution, while
53% of EF values are b 2 showing decient to minimal enrichment. Pb
has 57% EF and 37% EF in the ranges of 25 and 520, respectively,
with a mean EF N 5, indicating moderate to signicant pollution. The
variation of EF is comparatively larger for Zn than for the other metals
analyzed. The mean EF and 57% of EF values for Zn are in the range 2
5 showing moderate pollution, while 22% of EF values were N5 and
21% b 2, indicating signicant pollution and decient to minimal enrichment respectively. The above results indicate that Mn, Ni and V in the
campus dust of Xi'an were affected by natural sources, Ba and As were
mainly caused by nature and partly inuenced by human activities,
while Co, Cr, Cu, Pb and Zn in the campus dust and especially the latter
two, were mostly affected by human activities. Compared with the EF
values of Cu, Pb, Zn, Cr and As in street dust of Xi'an, reported by Han
et al. (2006), the mean EF and maximum EF values of Cu, Pb, Zn and
Cr in the campus dust are well below their levels in street dust of
Xi'an, implying that their enrichment degrees and contamination levels
in campus dust are lower than in the Xi'an street dust.
3.3. Correlation coefcient analysis results
Pearson's correlation coefcients of metals in the campus dust are
presented in Table 2. A signicantly positive correlation at the P b 0.01
signicance level was found for As, Ba, Cu, Mn, Ni, Pb and Zn. V is significantly positively correlated with As, Ba, Mn, Ni and Zn at P b 0.01
whereas, Cr is signicantly positively correlated with Cu, Mn and Ni at
P b 0.01, and is positively correlated with Pb at P b 0.05. Co is only positively correlated with Ba and negatively correlated with Pb at a P b 0.05
signicance level. Inter-element relationships provide interesting information on the sources and pathways of the metals (Lu et al., 2010).
3.4. Multivariate statistical analysis
In order to gain some insight into the sources of metals and major
correlations among them, PCA and CA were applied to each set of
data. PCA results shown in Table 3 display factor loadings with a
varimax rotation, as well as eigenvalues and commonalities calculated

using the software package SPSS 19.0. The results show that there are
ve eigenvalues N 1 and that these ve factors explain 80% of the total
variance. The rst factor explains 24.4% of the total variance, heavily
loaded on As, Cu, Mn and Ni. Factor 2 is loaded primarily by Ba and V,
and also moderately by Mn, accounting for 17.6% of the total variance.
The Mn loading (0.442) is not as high as for V and Ba (0.878 and
0.814, respectively), which may imply quasi-independent behavior
within the group (Lu et al., 2010). Factor 3, dominated by Pb and Zn,
accounts for 14.3% of the total variance. Factors 4 and 5 explain 12.5%
and 11.2% of the total variance and loading of Cr and Co, respectively.
Results for CA are shown in Fig. 3 as a dendrogram. The metal concentration data were standardized by means of z-scores before CA and
Euclidean distances for similarities in the variables were calculated
(Tokalolu and Kartal, 2006; Lu et al., 2010). The hierarchical clustering
by applying Ward's method was then performed on the standardized
dataset. Fig. 3 displays ve clusters: (1) AsNiCuMn; (2) PbZn; (3)
Cr; (4) BaV; (5) Co, which is in close agreement with the PCA results.
It is observed, however, that Clusters 1, 2 and 3 join together at a relatively higher level, implying a possible common source.
3.5. Spatial distribution of metals in urban dust
The spatial distributions of all analyzed metals in urban dust of Xi'an
are presented in Fig. 4. Fig. 4a shows that the concentrations of As in the
urban dusts from the southwest and the middle zones extending from
north to south of the study area were 12.0 to 29.7 mg kg1, 1.1 to 2.7
times the background value of local soil, while in other areas, As concentrations were lower than, or close to, the background value. The southwest high-value area is a high-tech industrial area, and the middle highvalue area includes commercial centers and residential areas. The
southwest high-tech industrial area was built during the 1990s. Before
the 1990s, that area consisted of agricultural land and a village. The
high-value areas of Ba concentrations (N2 times the background
value) were found in the southwest, south and east of the study area
(Fig. 4b). The east high-value area is an old industrial zone of Xi'an
where steel mills, railway signal factories and machinery plants are
located.
The concentrations of Co (19.3 to 81.1 mg kg1) in the urban dust
are signicantly higher than the background value of Shaanxi soil
(10.6 mg kg1), with the highest concentration of Co (N4.1 times the
background value) in the southwest high-tech industrial area and
southeast Qujiang new district (Fig. 4c). Qujiang new district, built
after 2000, is designed as a tourism, cultural, commercial and residential
zone, with many construction sites. Before the 2000s, this area was also
agricultural land and a village. Fig. 4d indicates that the higher concentration areas of Cr (N149.3 mg kg1 = 2.4 times the background value
of Shaanxi soil) are located in the north between the inner ring road and
second ring road and the south area around the second ring road. A bus
station and auto repair factories are located in the north high-value area.
The south high-value area is a commercial and residential area, with
dense roads and heavy trafc. The spatial distribution of Cu in the
urban dust (Fig. 4e) is similar to that of As (Fig. 4a). The concentrations
of Cu in the dusts of the southwest and the middle zones, extending
from north to south of the study area, are N3.1 times the background
value of Shaanxi soil, while in other areas they are 1.03.1 times the
background value.
The concentrations of Mn in the dusts of the south and southwest
are higher than in other areas (Fig. 4f). The Ni concentrations in the
dusts of most study areas are lower than, or close to, the background
level for Shaanxi soil. Ni high-value areas (N1.2 times the background
value, Fig. 4g) are similar to those for Mn (Fig. 4f). The concentrations
of Pb in the dusts of the study area are signicantly higher than its background value. There is one high-value zone (N143.4 mg kg1) in the
middle region, extending from north to south of the study area, especially in the north between the inner ring road and second ring road
and in the south around the second ring road, the concentrations of Pb

H. Chen et al. / Science of the Total Environment 484 (2014) 2735

Fig. 2. Cumulative frequency distribution of EF of metals in campus dust.

31

32

H. Chen et al. / Science of the Total Environment 484 (2014) 2735

Table 2
Pearson's correlation matrix for metal concentrations.
As
As
Ba
Co
Cr
Cu
Mn
Ni
Pb
V
Zn

Ba

Co

0.004

0.229
0.023
0.155
0.579
0.409
0.630
0.356
0.332
0.465

0.773
0.045

0.160
0.110
0.256
0.385
0.252
0.251
0.573
0.350

Cr

Cu

Mn

Ni

Pb

Zn

0.052
0.170
0.840

0.000
0.001
0.859
0.000

0.000
0.000
0.617
0.000
0.000

0.000
0.001
0.780
0.000
0.000
0.000

0.000
0.002
0.023
0.013
0.000
0.000
0.000

0.000
0.000
0.453
0.330
0.066
0.000
0.000
0.002

0.000
0.000
0.561
0.291
0.000
0.001
0.000
0.000
0.005

0.016
0.014
0.040
0.023
0.182

0.354
0.321
0.369
0.197

0.528
0.653
0.447

0.060
0.047

0.078
0.085

0.147
0.348

0.548
0.368
0.407
0.269

0.450
0.472
0.322

0.241
0.396

0.255

The left lower part is correlation coefcient; the right upper part is signicant level.
Correlation is signicant at P b 0.01 level (2-tailed).
Correlation is signicant at P b 0.05 level (2-tailed).

were 177.6 to 494.1 mg kg1, 8.3 to 23.1 times the background level
(Fig. 4h). The concentrations of V in the dusts of most area are less
than, or close to, the background value of Shaanxi soil, with its highvalue areas (1.11.5 times the background value, Fig. 4i) similar to
those for Ba (Fig. 4b). It can be seen from Fig. 4j that the high-value
area (N 386.6 mg kg1) of Zn is located in the southwest to the middle
where there is a high-tech industrial and commercial area with dense
roads and heavy trafc.

3.6. Metal source identication


Three main sources can be identied according to correlation coefcient analysis, PCA, CA and the spatial distribution characteristics of
metals in the dust: (1) As, Ni, Cu, Mn, Pb, Zn and Cr have mixed sources
of nature, trafc, as well as fossil fuel combustion and weathering of materials; (2) Ba and V mainly originate from natural sources, but partly
also from industrial activities, as well as construction; (3) Co comes
from construction.
As, Ni, Cu, Mn, Pb, Zn and Cr have signicantly positive correlation in
the correlation coefcient analysis. As, Ni, Cu and Mn belong to Factor 1
in PCA and are classied together in CA (Cluster 1). Pb and Zn belong to
another principal component (Factor 3) in PCA and are classied together in CA (Cluster 2). Cr belongs to Factor 4 in PCA and Cluster 3 in
CA. Elements in the As, Ni, Cu and Mn cluster, elements in the Pb and
Zn cluster, and cluster Cr join together at a relatively higher level in
CA, implying a possible common source. The coefcients of variation
of these metals are relatively large except for Mn, revealing the inuence of human activity on their concentrations. The concentrations of
As, Mn and Ni in most dust samples are lower than, or close to, their corresponding background levels, indicating that they largely originated
naturally (from local soil). The higher-value (N 1.2 times the background
value) areas for As, Mn and Ni are distributed in a similar manner, i.e.

centered in the southwest high-tech industrial area and the south


commercial and residential areas.
The pre-1990 agricultural activities (sewage irrigation, chemical
pesticide usage, etc.) in the southwest high-tech industrial area caused
metal accumulation in the local soil, which is the main source of the
high-value of As, Mn and Ni concentrations in this area's dust. The
higher concentrations of As, Mn and Ni in the south commercial and residential areas mainly relate to fossil fuel combustion. The concentrations
of Cu, Pb and Zn exceed 1.5 times the corresponding background value
in 95% of dust samples. Their higher-value areas are concentrated in the
southwest high-tech industrial area and the middle part where there
are dense roads and heavy trafc. Zinc alloy and galvanized components
are widely used in motor vehicles. Zinc compounds are also employed
extensively as antioxidants and as detergent/dispersant improvers for
lubricating oils (De Miguel et al., 1997). Zn, added to tires during the
vulcanizing process, comprises from 0.4% to 4.3% of the resulting tire
tread (Chen et al., 2012). The wear and tear of vulcanized vehicle tires
and corrosion of galvanized automobile parts are the main sources of
Zn in urban environments (Han et al., 2006; Lu et al., 2010).
Although the use of leaded petrol has been banned in Xi'an since
2000, the content of Pb in urban soil still reects the signicant degree
of historical Pb contamination and the long half-life of Pb in soil (Yang
et al., 2011). Pb in the bare soil could enter the urban dust by resuspension. In addition, Pb contained in paints and coatings of buildings and
some urban facilities could enter the urban dust due to the effects of

Table 3
Rotated component matrix for data of Xi'an campus dust (PCA loadings N0.4 are shown in
bold).
Element

As
Ba
Co
Cr
Cu
Mn
Ni
Pb
V
Zn
Eigenvalue
% of variance
% of cumulative

Component

Commonalities

0.845
0.015
0.005
0.169
0.742
0.515
0.816
0.269
0.275
0.260
2.44
24.4
24.4

0.115
0.814
0.029
0.023
0.004
0.442
0.268
0.132
0.878
0.149
1.76
17.6
42.0

0.267
0.334
0.022
0.024
0.102
0.102
0.100
0.677
0.010
0.828
1.43
14.3
56.3

0.117
0.114
0.010
0.908
0.345
0.386
0.247
0.249
0.061
0.084
1.25
12.5
68.8

0.007
0.220
0.956
0.008
0.057
0.069
0.070
0.330
0.135
0.130
1.12
11.2
80.0

0.812
0.837
0.915
0.855
0.759
0.625
0.813
0.719
0.868
0.799
Fig. 3. Dendrogram results from Ward's method of hierarchical cluster analysis for 10
elements.

H. Chen et al. / Science of the Total Environment 484 (2014) 2735

weather (rain, sun, etc.) on the buildings and urban facilities (Chen
et al., 2012).
Copper alloy is a material used in mechanical parts due to its desirable qualities, such as corrosion resistance and strength (Chen et al.,
2012). Cu is also used in Cubrass automotive radiators due to its high
corrosion resistance and high thermal conductivity (Yang et al., 2011).
It is also often used in car lubricants (Lu et al., 2010). The deterioration
of the mechanical parts in vehicles over time results in Cu being emitted
to the surrounding environment (Li et al., 2004). Oxidation of lubricating oils upon exposure to air at high temperature results in the formation of organic compounds which are corrosive to metal (Chen et al.,
2012). Cu can be released to the urban environment as a result of
wear of automobile oil pumps or corrosion of metal parts which come
into contact with the oil (Lu et al., 2010).
The concentrations of Cr in the dust are signicantly higher than the
background value of Shaanxi soil and its coefcient of variation is greater, showing that Cr concentration in the dust was mainly caused by
human activities. Elevated concentrations of Cr were reported in the

33

dusts collected around the coal-red power plant (Ren et al., 2011). Cr
is extensively used in automobile parts, aluminum alloys and titanium
alloys. Considering the concentration, coefcient of variation and
high-value area distribution, one can conclude that Cr in the dust mainly
originates from trafc emissions and fossil fuel combustion.
The second group of elements consisting of Ba and V is strongly
positively correlated in PCA and correlation coefcient analysis, and is
classied together in CA. The coefcient of variation of V concentration
in the dusts is smaller and its concentrations in the dusts from most
areas are lower than, or close to, the background value for Shaanxi
soil, indicating that V in the urban dust mainly originated from local
soil. V is often incorporated in stainless steel and alloys. The highvalue area distribution of V concentration indicates that V in the dust
partly originated from industrial sources. The enrichment factor results
indicate that Ba was mainly affected by nature, but also partly inuenced by human activities. Ba is widely used in alloys, paints, ceramics,
plastic cements, and glass (Monaci and Bargagli, 1997). From the spatial
distribution characteristics of Ba concentration in the dust, it can be

Fig. 4. Spatial distribution of metal concentrations in urban dust of Xi'an.

34

H. Chen et al. / Science of the Total Environment 484 (2014) 2735

Fig. 4 (continued).

concluded that Ba in the dust mainly originated from natural sources,


but with some contribution from industrial emissions, as well as construction. Element cluster Ba and V, and element cluster Co join together
at a relatively higher level in CA, indicating Ba and V in the dust partly
originated from construction.
The third group of element is Co. The coefcient of variation of Co is
relatively large, and its concentrations in the urban dust are clearly
higher than the corresponding background value for Shaanxi soil, demonstrating that Co in the urban dust is mainly governed by human activities. Co is extensively used in coating materials, paints and pigments.
These Co-containing materials are widely used in modern buildings
due to their gloss, faultless color and visual impact. This is true for the
southwest high-tech industrial area and southeast Qujiang new district
construction the high-value areas of dust Co concentration. This suggests that Co in urban dust of Xi'an predominantly originated from
building construction or renovation, leading to weathering and corrosion of building materials.

4. Conclusions
The content measurement results of As, Ba, Co, Cr, Cu, Mn, Ni, Pb, V
and Zn show that kindergarten, elementary school, middle school and
university dusts of Xi'an have elevated metal concentrations, especially
of Pb, Zn, Co, Cu, Cr and Ba, these being 1.723.1, 0.926.5, 1.87.7, 1.0
6.5, 1.26.4 and 1.14.3 times the corresponding background values for
Shaanxi soil, respectively. The mean concentrations of metals in the dust
divided by the corresponding background Shaanxi soil values decrease
in the order Pb N Zn N Co N Cu N Cr N Ba N As N Ni N V N Mn. Enrichment
factor analysis indicates that Mn, Ni, V, As and Ba in campus dust of Xi'an
were decient as a whole, while Co, Cr, Cu, Pb and Zn in the campus
dust, especially Pb and Zn, were mostly caused by human activities. Spatial distributions of metals in Xi'an urban dust were determined based
on the campus dust samples using the geostatistics method. Different
distribution patterns were found among the investigated metals. As
and Cu, Mn and Ni, Ba and V, Pb and Zn had similar distribution patterns.

H. Chen et al. / Science of the Total Environment 484 (2014) 2735

The southwest high-tech industrial area and south commercial and


residential areas were high-value areas for most metals. Three main
sources of metals in urban dust of Xi'an were identied according to
correlation coefcient analysis, PCA and CA, coupled with the spatial
distribution characteristics of metals. As, Ni, Cu, Mn, Pb, Zn and Cr
have mixed sources from nature, trafc, as well as fossil fuel combustion
and weathering of materials. Ba and V are mainly natural in origin, but
also partly from industrial emissions, as well as construction, while Co
principally arises from construction.
Conict of interest
Work on this manuscript was supported by the funding of the
second author (Xinwei Lu) and the research results by Dr Lu's group.
There is no conict among the authors, and there is also no conict
between the authors and the organizations.
Acknowledgments
The research was supported by the National Natural Science
Foundation of China through Grant 41271510 and the Fundamental Research Funds for the Central University through Grants GK201305008,
GK201104002 and GK201101002. Guang Yang and Caifeng Zhao
assisted with sample preparation. We also thank local school authorities
for their cooperation. Appreciation is expressed to Associate Editor PhD
Xuexi Tie and the anonymous reviewers for insightful suggestions and
critical reviews of the manuscript. The authors sincerely thank local
school authorities for their cooperation and Dr. J.R. Grace for editorial
assistance.
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