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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
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-
http://dx.doi.org/10.1016/j.scitotenv.2014.03.026
0048-9697/ 2014 Elsevier B.V. All rights reserved.
28
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.
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
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
Background
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.
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
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
31
32
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.
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.
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
34
Fig. 4 (continued).
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.
35