Atmospheric Environment 174 (2018) 43–53

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Atmospheric Environment
journal homepage: www.elsevier.com/locate/atmosenv

Characteristics of the trace elements and arsenic, iodine and bromine species T
in snow in east-central China
Yunchuan Gaoa,∗, Chao Yangb, Jin Maa, Meixue Yinc
a
School of Life and Environmental Science, Shanghai Normal University, Guilin Road No. 100, Shanghai, China
b
Suzhou Wujiang District Environmental Protection Bureau, Sports Road No. 501, Wujiang District, Suzhou, China
c
Qingdao Jingcheng Detection Technology Co., Ltd, Ocean Garden, Qiantang River Road, Huangdao District, Qingdao, China

A R T I C L E I N F O A B S T R A C T

Keywords: Fifty-five snow samples were collected from 11 cities in east-central China. These sampling sites cover the areas
Snowfall with the most snowfall in 2014, there were only two snowfalls from June 2013 to May 2014 in east-central
Trace element China. Twenty-three trace elements in the filtered snow samples were measured with inductively coupled
Speciation plasma-mass spectrometry (ICP-MS). Statistical analysis of the results show that the total concentrations of
HPLC-ICP-MS
elements in the samples from different cities are in the order of SJZ > LZ > XA > ZZ >
East-central China region
GD > NJ > QD > JX > WH > HZ > LA, which are closely related to the levels of AQI, PM2.5 and PM10 in
these cities, and their correlation coefficients are 0.93, 0.76 and 0.93. The concentration of elements in snow
samples is highly correlated with air pollution and reflects the magnitude of the local atmospheric deposition.
The concentrations of Fe, Al, Zn, Ba, and P are over 10.0 μg/L, the concentrations of Mn, Cu, Pb, As, Br and I are
between 1.0 μg/L to 10.0 μg/L, the concentrations of V, Cr, Co, Ni, Se, Mo, Cd and Sb are less than 1.0 μg/L in
snow samples in east-central China, and Rh, Pd, Pt, Hg were not detected. Iodine and bromine species in all
samples and arsenic species (As(III), As(V), dimethylarsinic acid (DMA) and monomethyl arsenic (MMA)) in
some samples were separated and measured successfully by HPLC-ICP-MS. The majority of arsenic in the snow
samples is inorganic arsenic, and the concentration of As(III) (0.104–1.400 μg/L) is higher than that of As(V)
(0.012–0.180 μg/L), while methyl arsenicals, such as DMA and MMA, were almost not detected. The con-
centration of I− (Br−) is much higher than that of IO3− (BrO3−). The mean concentration of soluble organic
iodine (SOI) (1.64 μg/L) is higher than that of I− (1.27 μg/L), however the concentration of Br− (5.58 μg/L) is
higher than that of soluble organic bromine (SOBr) (2.90 μg/L). The data presented here shows that SOI is the
most abundant species and the majority of the total bromine is bromide in snow sampled at east-central China.
Using Fe as the reference element to calculate the EFs, the enrichment factors of V, Cr, Co, Ni, Mn, Ba and P are
between 12.3 and 82.8, and the enrichment factors of Cu, Pb, Mo, Zn, Cd, As, Sb, Br, I and Se are between 189.4
and 27667.9, indicating that these elements are contributed by artificial sources. Results of principal component
analysis (PCA) on the elements showed that most of trace elements (e.g. V, Cr, Mn, Co, Ni, Cu, As, Mo, Sb, Se, Br,
I, Ba and P)were from the combustion of fossil fuels, traffic and ocean sources and some other elements (e.g. Zn,
Cd and Pb) were mainly originated from industrial activities.

1. Introduction
Air pollution has become one of the most important concerns in
China in recent years, especially haze. Hazy weather is the most direct
indicator of the air quality in China. In 2013, haze covered twenty-five
provinces and more than one hundred cities, and the national average
days of hazy weather reached 29.9 days, which was the highest re-
corded in more than 52 years. In 2015, there were 11 large-scale and
continuous haze processes in China, which were concentrated at the
end of the last two months, especially from November 27 to December
1, and involved North China, Shandong, Henan. Hazy days have the
characteristics of strong intensity, wide range, and low visibility and
have great influence. They are the most severe hazy days in 2015. Haze
is intrinsically caused by a high load of fine particulate matter (PM).
Trace elements are important constituents in particulate matter (PM)
and of great public concern due to their toxic characters (Chen and
Lippmann, 2009; Niu et al., 2015). Trace elements, especially heavy
metal elements, can accumulate in human tissues through the food
chain and cause damage to the human nervous system and internal
organs (An et al., 2008). They also act as potentially derivational factors

∗
Corresponding author.
E-mail address: gaoyc@shnu.edu.cn (Y. Gao).

https://doi.org/10.1016/j.atmosenv.2017.11.015
Received 12 June 2017; Received in revised form 11 October 2017; Accepted 12 November 2017
Available online 14 November 2017
1352-2310/ © 2017 Elsevier Ltd. All rights reserved.
Y. Gao et al.
of cardiovascular diseases, reproductive impairments, and cancers
(Dockery and Pope, 1996). In recent years, many studies have been
conducted in megacities of east-central China region addressing the
chemical characteristics and potential sources of PM and associated
trace elements (Waheed et al., 2011; Song et al., 2012; Yang et al.,
2013; Niu et al., 2015; Zhang et al., 2015; Tan et al., 2017; Feng et al.,
2016). These studies revealed that the trace elements favoring in fine
particles, such as Pb, Zn, Ni, Cu, Mn, etc., were mainly from anthro-
pogenic sources. Air pollution in this area is greatly affected by human
activities.
The snow (chemistry) reflects the chemical composition of its parent
aerosol, dry fallout and surface adsorbed material. Atmospheric pollu-
tion information can be stored in snow and ice in high altitude regions.
Snow cover has the chemical composition of the atmosphere during
formation and subsequent accumulation (Osada et al., 2010). There-
fore, snow cover is widely used as a reliable indicator to judge the type
of the air pollution and is used to trace the relative contribution of
different sources of atmospheric pollutants (Hiromitsu et al., 1988;
ELİK, 2002). Thus, analysis of the content and distribution of trace
elements in snow cover can provide information on the behaviors and
sources of atmospheric pollutants. Therefore, various studies have been
carried out on the chemical composition of snow around the world,
especially on polar snow and mountain snow. Research carried out on
trace elements in snow and ice from South America, Arctic, Greenland,
Antarctic, Alps and Himalayas has allowed us to obtain important in-
formation to identify their source attributions, on the other hand, the
data of the research documented the atmospheric pollution for various
trace elements and also provided distinct evidence that atmospheric
pollution of various trace elements exists on regional, hemispheric and
global scales, as a result of long-range transport and dispersion. These
data play an important role to assess with great clarity the ancient and
modern atmospheric pollution for trace elements at a regional scale
(Boutron et al., 1995; Van et al., 1998; Rosman et al., 2000; Barbante
et al., 2003; Schwikowski et al., 2004; Hong et al., 2004; Hegg et al.,
2009; Liu et al., 2011; Dong et al., 2015; Wang et al., 2015). However,
there were a few studies in the experiments of measuring the trace
elements in snow from cities (An et al., 2008; Hu et al., 2012; ELİK,
2002; Kazuhiko et al., 2000), and there is almost no information
available from the published literature surveying chemical species in
snow from east-central China region.
As one of the most industrialized and densely populated areas, the
atmospheric quality in the east-central China region is strongly influ-
enced by human activities, such as industrial production. From June
2013 to May 2014, snow samples were collected in eleven cities in the
east-central China region. During this period, there were only two
snowfalls in this region. Therefore, 55 snow samples were collected
from 11 cities in east-central China, and 23 trace elements (e.g., Al, Mn,
Fe, Zn, Ba, P, Cu, Pb, Br, V, Cr, Co, Ni, As, Se, Mo, Cd, Sb, I, Pt, Pd, Rh
and Hg) and the arsenic, iodine and bromine species in the filtered
snow samples were measured. The main purpose of the present work is
to expand the knowledge of the spatial characterizations of trace ele-
ments in east-central China to evaluate trace element pollution related
to anthropogenic sources, and to explore relationships between the
concentration of trace element and Air Quality Index (AQI) that are less
commonly considered, and to identify the forms of atmospheric arsenic,
bromine and iodine, and finally to evaluate that the snow chemistry in
east-central China region atmosphere probably reflects the magnitude
of the local atmospheric deposition and the influence of atmospheric
pollution of trace elements.
2. Methodology
2.1. Snowfall events and sample site
There were only two snowfalls in east-central China from 2013 to
winter of 2014. The first snowfall, with a depth of 5–16 cm, occurred on
44
Atmospheric Environment 174 (2018) 43–53
February 4-5, 2014, covering northwest of Hubei, northern Jiangsu and
Anhui, southern Shandong, most of Henan, southeast of Shanxi, Shanxi
and other places. Among these areas, there were heavy snowfalls, with
a depth of 10–16 cm, in northern Jiangsu and Anhui, southern
Shandong and eastern Henan. The second snowfall, with a depth of
3–10 cm, occurred on February 17-18, 2014, covering southern Shanxi,
eastern Hubei, northeast of Hunan, south-central Anhui, northwest of
Zhejiang, north-central Jiangxi, eastern Guizhou and northeast of
Yunnan. Among these areas, there were heavy snowfalls, with a depth
of 10–16 cm, in southeastern Hubei, southern Anhui, northwestern
Zhejiang, and northwestern and northeastern Jiangxi.
This study selected 11 representative cities (almost all cities, except
for Lanzhou and Xi'an, are in east-central China, including Zhengzhou,
Shijiazhuang, Jiaxiang, Qingdao, Hangzhou, Wuhan, Nanjing, Lin'an,
Guangde) to sample. These sample sites cover areas that had snowfall in
east-central China during the winter of 2014. These 11 cities include
five cities in the areas of the first snowfall, Zhengzhou (ZZ),
Shijiazhuang (SJZ), Qingdao (QD), Jiaxiang (JX) and Lanzhou (LZ) (see
the left side of Fig. 1), and six cities in the areas of the second snowfall,
Nanjing (NJ), Wuhan (WH), Hangzhou (HZ), Guangde (GD), Lin'an (LA)
and Xi'an (XA) (see the right side of Fig. 1).
2.2. Sample collection
Fifty-five snow samples were collected from these 11 cities, 5 areas
for each city, including the central business district, residential areas,
cultural areas, industrial areas and suburbs (Junge and Scheich, 1971).
Sampling points were set in each area. All the samples from one area
were mixed to obtain the final sample for each area, and thus, there
were 5 snow samples for each city. The sampling points were set in
open spaces, far away from pollution sources, such as traffic arteries
and chimneys, and from tall buildings and trees. The snow at the
sampling sites should be as deep as possible. The surface and the bottom
of the snow were removed, and only the middle section was collected in
a new 250 mL low-density polyethylene (LDPE) bottle. Each bottle was
washed by the middle-section snow three times before use. When the
snow was fully compacted, the LDPE bottles were put into shading bags
and stored in incubators. The incubators were kept outdoors in the cold
environment.
2.3. Sample analysis
After dissolution, the snow water samples were first filtered through
a 0.45 μm cellulose acetate filter to remove suspended matter and were
then transferred to ultraclean 50 mL bottles. The sample was divided
into two parts. In one part, ultrapure HNO3 was added, and the sample
was acidified to pH < 2.0 to inhibit microbial activities and reduce the
adsorption of heavy metals. The sample was stored in the dark under
4 °C and was used to analyze the metal elements. The other part was
kept at under 4 °C in the refrigerator and was used to analyze the
nonmetal elements, i.e., the arsenic, bromine and iodine species.
The trace elements, total soluble arsenic (TSAs), total soluble iodine
(TSI) and total soluble bromine (TSBr) were analyzed by inductively
coupled plasma-mass spectrometry (PerkinElmer, NexION 300D,
America), arsenic species (As(III), As(V), DMA and MMA) were ana-
lyzed by HPLC-ICP-MS (PerkinElmer, Flexar and NexION 300D,
America), where a PRP-X100 column (150 mm × 4.6 mm, 10 μm)
(Hamilton) was used as the anion exchange column, the mobile phase
was 10 mM/L (NH4)2HPO4, and the flow rate was 1.0 mL/min. Analysis
of the trace elements and arsenic species was completed within 2
months. The iodine and bromine species (I−1, IO3−, Br− and BrO3−)
were analyzed by HPLC-ICP-MS (PerkinElmer, Flexar and NexION
300D, America), where a Dionex IonPac AS14 (4 mm × 250 mm)
+AG14 (4 mm × 50 mm) column was chosen as the chromatographic
column, the mobile phase was 50 mM/L NH4NO3 gradient elution, and
the flow rate was 1.2 mL/min. The analysis of iodine and bromine
Y. Gao et al.
species was completed within 10 months. SOI (SOBr) was calculated as
SOI (SOBr) = TSI (TSBr) – [(I−1+ IO3−) (Br− + BrO3−)].
As mentioned above, the instrument parameters were optimized
daily to obtain high-intensity signals and minimize the possibility of
interference. The values were quantified using a calibration curve, and
the linear correlation coefficients for the 23 elements, four arsenic
species, and two iodine and bromine species were all higher than 0.99.
The relative standard deviations (RSDs) at the 5 ng/mL level for de-
termination of the elements were less than 6%. The RSDs at the 2 ng/
mL level for As(III), As(V), dimethylarsinic acid (DMA) and mono-
methyl arsenic (MMA) were 1.9%, 10.9%, 7.5% and 5.4% (n = 7),
respectively. The RSDs at the 0.5 ng/mL level for I−1, IO3−, Br− and
BrO3− were 1.15%, 3.86%, 3.03% and 2.17% (n = 7), respectively.
The detection limits, defined as three times the standard deviation of 7
measurements of the blank, were shown in Table 1.
2.4. Meteorological data
The air quality index (AQI) is a dimensionless index for quantitative
description of air quality. AQI values intuitively reflect the air quality.
The higher the AQI, the more serious the air pollution. The data of AQI,
PM2.5 and PM10 in the sampled cities were obtained from the China
National Environmental Monitoring Center website (http://113.108.
142.147:20035/emcpublish/) (Except for JX, GD and LA, the data of
these three county-level cities was from the Internet), which the
average values of the seven days’ forecast data before snowfall in each
city were took into use.
3. Results and discussion
3.1. Concentrations of elements in snow from different cities
Fig. 2 shows the mean concentrations and standard deviations of 19
elements (23 elements were analyzed, but Pt, Pd, Rh and Hg were not
detected) in snow from the 11 cities in east-central China. From Fig. 2,
we can see that the mean concentrations of the elements varied greatly
for different cities. For different elements in the same cities and the same
elements in different cities, the mean concentrations varied greatly. As to
the source of the element, the mean concentrations of the crustal ele-
ments P, Al, Fe and Ba were much higher than those of other elements
and were high in most of the sampled cities, while the mean con-
centrations of the pollution elements As, Cd, Se, Cr, Mo and Sb were low
and had little difference in the different cities. The concentrations of total
elements in snow from the 11 sampled cities were in the order of
SJZ > LZ > XA > ZZ > GD > NJ > QD > JX > WH > HZ >
LA, and the values were 353.34, 254.67, 224.49, 148.19, 115.83,
107.98, 80.07, 75.34, 62.84, 38.35 and 34.55 (μg/L) (GD, JX and LA are
county-level cities, QD is a fast-growing city and others are provincial
capital cities). The above order clearly shows that the concentrations of
total elements in the northern cities (SJZ, LZ, XA and ZZ) are higher than
those in the southern cities (NJ, WH, HZ and LA). The concentrations of
almost all elements (except Cd and Pb) in the snow were high in SJZ, and
the concentrations of most of the elements in snow from XA and LZ were
high as well. Compared to the concentration of Ni, Cu, Cd, Pb, Mn and Zn
in PM2.5 in large cities of this region, such as SJZ, LZ, XA, ZZ, NJ, WH,
HZ and QD (Bao et al., 2010,; Geng et al., 2013; Zhang et al., 2015, 2017;
Lu et al., 2016; Tan et al., 2017; Wu et al., 2017; Wang et al., 2017), as
the same results with the snow samples of these cities, SJZ has the
highest concentration of total element in PM2.5, and the data also reflect
that concentrations of total elements in the northern cities (SJZ, LZ, XA
and ZZ) are higher than those in the southern cities (NJ, WH and HZ).
This shows that the concentrations of trace elements in PM2.5 and snow
can reflect atmospheric pollution.
Table 2 shows the minimum and maximum concentration, the ratio
of maximum to minimum, the mean concentration and the standard
deviation of the elements in snow from the 11 sampled cities in east-
45
Atmospheric Environment 174 (2018) 43–53
central China. As shown in Table 2, the mean concentrations of the
elements are in the order of Al > Fe > Zn > P > Ba > Mn > Br >
Cu > Pb > I > As > Ni > V > Cr > Se > Sb > Mo > Co >
Cd, and the mean concentrations of the elements varied greatly in these
areas. It can be divided into three cases: 1) For Fe, Al, Zn, Ba and P, the
mean concentrations are more than 10.0 μg/L. Most of these high-
concentration elements are crustal elements, indicating that particu-
lates from the soil have great influence on the elemental composition of
snow; 2) For Mn, Cu, Pb, As, Br and I, the mean concentrations are
between 1.0 μg/L to 10.0 μg/L. These elements come from smelting
industry sources and ocean sources, respectively, indicating that the
particulates from the two sources have great influence on the elemental
composition of snow; 3) For V, Cr, Co, Ni, Se, Mo, Cd and Sb, the mean
concentrations are less than 1.0 μg/L, the concentration of Cd
(0.102 μg/L) is the lowest. All these elements are pollution elements
and trace elements which come from the processes of fuel combustion
and the smelting industry. Compared with the data of glaciers and
mountain snow, the concentrations of Mn, Al and Ba in snow from the
east-central China region were higher than the data of the snow water
collected from the Franz Josef Glacier and the Tasman Glacier on the
Southern Alps (Purdie et al., 2010); the concentrations of Himalaya and
Wasatch Mountain (Liu et al., 2011; Gregory et al., 2012) are lower
than this study, which shows that the snow element concentration is
effected by the altitude: the higher the altitude, the lower the con-
centration. Compared with the data of city snow, the concentrations of
Cu, Ni, Cd, Pb, Cr, As and Zn in Poznan, Inner Mongolia and Hei-
longjiang (Patrycja et al., 2015; Wang et al., 2015) is similar to this
study, concentrations in Tianjin and Jilin (Wang et al., 2015; Wu et al.,
2016) are slightly higher than that of this study, but in Beijing and
Tukey (ELİK, 2002; Jia et al., 2013), the concentrations of Cr, Ni, Cu,
Zn, Cd, Pb and Mn were higher than those in this study. This phe-
nomenon may be the results of the accumulation and mixing of the
various pollutants.
3.2. Correlation between the element concentration and AQI
The snow (chemistry) reflects the chemical composition of its parent
aerosol, dry fallout and surface adsorbed material. Snow cover has the
chemical composition of the atmosphere during formation and sub-
sequent accumulation (Osada et al., 2010). Therefore, snow cover is
widely used as a reliable indicator to judge the type of the air pollution
and is used to trace the relative contribution of different sources of
atmospheric pollutants (Hiromitsu et al., 1988; ELİK, 2002). In order to
further explore the relationship between the element concentrations
and haze, the correlation between the concentrations of total elements
and AQI, PM2.5 and PM10 was shown in Fig. 3. Excluding the data of JX
and LZ (the data is not complete), the AQI values and PM10 are in order
of SJZ > XA > ZZ > GD > WH > QD > NJ > LA > HZ, but
for PM2.5, XA is slightly higher than SJZ. As a whole, AQI, PM2.5, PM10
and the concentrations of total elements have the same order. Calcu-
lated the correlation coefficients between the concentrations of all
elements and AQI, PM2.5 and PM10, their correlation coefficients are
0.93, 0.76 and 0.93. The high correlation coefficients suggest that the
concentration of elements in snow samples is highly correlated with air
pollution and reflects the magnitude of the local atmospheric deposi-
tion. Similar result was also found in Turkey (ELİK, 2002), which de-
monstrated that snow chemistry successfully reflects the magnitude of
the local atmospheric deposition and the measurement of heavy metal
concentrations in snow is important in monitoring environmental pol-
lution. The correlation coefficient between concentrations of elements
and PM2.5 is lower than that of PM10, the most abundant elements in
snow samples are mainly distribute in the coarse fraction of atmo-
spheric aerosol, suggesting that the coarse fraction is easier to deposite
in the snowfall (Sailesh et al., 2015). Zhao et al. (2015) explained that
scavenging effect of snow on coarse mode particles (1000-10 000 nm)
was more unobvious than other modes.
Y. Gao et al.
3.3. Concentrations of element species in snow from different cities
In this study, the species of elements As, I and Br were separated and
detected by HPLC-ICP-MS. The HPLC-ICP-MS spectra of the As, I and Br
species in the snow are shown in Fig. 4 and the results are displayed in
Table 3. It can be seen form Fig. 4(a) that there are two peaks in most of
the snow samples from the three cities SJZ, ZZ and GD. As (III) is eluted
at 2 min, and the peak value is large. As (V) is eluted at 7.8 min, and the
peak value is small. No peaks corresponding to DMA and MMA ap-
peared in any of the samples, which indicates that there may be no
organic As in the samples. The element As mainly exists in the form of
inorganic As, such as As(III) (0.104–1.400 μg/L) and As(V)
(0.012–0.180 μg/L), while there was almost no detection of methyl
arsenicals, such as DMA and MMA (Table 3). The sampled cities are
ordered from highest to lowest concentration of inorganic As: JX >
SJZ > ZZ > GD > WH > HZ, which indicates that the As con-
centrations of the northern cities (JX, SJZ and ZZ) are higher than those
of the southern cities (GD, WH and HZ). In the northern cities, the in-
organic As concentrations are 1.007–1.400 μg/L, mainly because As
particle pollution was aggravated due to coal combustion in winter in
the northern cities. The concentrations of TSAs are 0.13–1.47 μg/L in
snow of different cities, The ratios of As(III)+ As(V) to TSAs are 61.1%-
95.0% in different cities, suggesting that there are other forms of As,
which may be the organic As, although the organic As such as DMA and
MMA were not detected.
The concentrations of As(V) in the all snow samples are much lower
than those of As(III), which is different from previous study in which
the concentration of As(V) (0.16 μg/L) was higher than that of As(III)
(0.00 μg/L) in snow (Döker et al., 2013). Atmospheric As is mainly
bound to fine aerosol particles (less than 2.5 μm), which can be
transported over a relatively long distance and can penetrate deeply
into the human respiratory system. Almost all As is contained in par-
ticles < 10 μm (Doušová et al., 2007). Compared with the data of the
inorganic arsenic species in the atmospheric particles, the concentration
of As(V) was almost higher than that of As(III). Gong et al. (2014) have
summarized the research progress of occurrence and speciation of ar-
senic in atmospheric particles, in which only two of the 18 As(V)/As(III)
data from the 13 cited papers were less than 1.0, suggesting that As(V)
is the main form in atmospheric particulates. This is different from our
results of snow samples. The toxicity and the physicochemical proper-
ties of arsenic are highly depend on its chemical form, inorganic arsenic
species, As(III) and As(V) exhibit high toxicity having been classified as
carcinogenic agents (Tsopelas et al., 2008). Of the two inorganic species
cited, As(III) is more toxic than As(V). So, it is very necessary to further
identify the form of atmospheric As, to determine whether arsenic exists
in environmental medium is oxidation or reduction environment, to
better assess the risk of arsenic on the health of the population.
Fig. 4 (b) and (c) shows I and Br species in the snow samples from
the 11 cities (only one sample in each city). In Fig. 4 (b), the peak of I−
appears at 1.25 min, the peak value is large, and the peaks of I− appear
in all the samples. The peak of IO3− appears at 0.5 min, the peak value
is small, and it appears only in the samples from the cities LZ, NJ, QD
and SJZ. In this study, there is no organic iodine peak between the IO3−
peak and the I− peak, which is different from the study of Gillfedder
et al. (2008), which showed several unknown peaks between the IO3−
peak and the I− peak in the snow samples, and the maximum peak
value is larger than that of the IO3− peak. These peaks were thought to
represent the existence of organic iodine (Gillfedder et al., 2008). In
Fig. 4 (c), only one Br− peak is detected in all the snow samples, which
appears at 2 min, and BrO3− peaks and organic bromine peaks are not
detected. The concentration sequences of TSI and TSBr are similar. The
concentration of TSI(TSBr) is ordered as follows: SJZ > ZZ (QD) >
QD (XA) > XA (GD) > GD (ZZ) > LZ > NJ > JX > WH > YL >
HZ > LA. The results showed that the concentrations of TSI (TSBr) in
the northern cities are higher than those in the southern cities, and the
concentrations of TSBr are significantly higher than those of TSI, mainly
46
Atmospheric Environment 174 (2018) 43–53
because iodine and bromine partly result from the combustion of coal
and oil, and the content of bromine (0.12–69.99 μg/g) (Peng and Wu,
2014) in coal and oil is much higher than that of iodine (0.04–29.5 μg/
g) (Wu. et al., 2008). For inorganic iodine and bromine, BrO3− was not
detected, and IO3− was detected only in some samples at very low
concentrations, which the concentrations of I− were much higher than
those of IO3−. Table 3 also shows that the mean concentration of SOI
(1.64 μg/L) is higher than that of I− (1.27 μg/L), composing up to
40.9–80.3% of TSI with the mean of 58.7%, while the mean con-
centration of SOBr (2.90 μg/L) is lower than that of Br− (5.58 μg/L),
composing up to 6.3–66.6% of TSBr with the mean of 33.5%, indicating
that the concentrations of inorganic iodine are lower than that of or-
ganic iodine in the samples, but the concentrations inorganic bromine
are higher than those of organic bromine.
The data presented here shows that SOI is the most abundant spe-
cies in snow sampled at east-central China. The data in Baker (2005)
has, to a large extent, shown that SOI is of global importance in aero-
sols, and the data in Gillfedder et al. (2007,2008) has shown that iodine
oxides are the least abundant iodine species in accumulation and course
mode aerosols, rain and snow with soluble organic iodine (SOI) species
being the dominant fraction. This suggests that these species are
transferred from the aerosols into precipitation and that they have ei-
ther a relatively long lifetime or are rapidly recycled. It is thought that
SOI is formed by reactions between HOI or I2 and organic matter de-
rived from the ocean surface layer. SOI may then photolytically de-
compose to yield iodide and the unidentified species. The majority of
the total bromine is bromide. The organically bound bromine in snow
(max. 32%) may be derived from the ocean surface layer as discussed
above for iodine or between reactive bromine species such as BrCl and
organic material (Gillfedder et al., 2007, 2008).
3.4. Element source analysis in snow water
The main possible natural sources of elements in snow from the
east-central China region are rock and soil dust, sea-salt spray, con-
tinental and marine biogenic activity and anthropogenic activities, in-
cluding coal combustion, fuel combustion, traffic emission and in-
dustrial discharge. To further explore the sources of the elements, the
element enrichment factors (EFs) were analyzed. The EFs of the ele-
ments in the snow relative to crustal material (e.g., Al, Fe and Ti mainly
come from rock and soil dust) are often used to evaluate the anthro-
pogenic influence (Kaspari et al., 2009).
In this study, the EFs are defined as the ratio of two ratios: one is the
concentration ratio of a given chemical substance to Fe in the snow, and
the other is the concentration ratio of the same given chemical sub-
stance to Fe in the soil. Data for the comparable elements were mainly
obtained from the research results of Taylor (1964). If the EFs are no
more than 10 times the average crustal abundance, the element is not
enriched (Poissant et al., 1994; Kaya and Tuncel, 1997) and instead
primarily results from continental rock and soil dust. If the EFs are
greater than 10, there is an important contribution from other natural
sources or anthropogenic sources (Dasch and Wolff, 1989).
The EFs of the elements in snow samples from the 11cities are
shown in Table 4. The EF for Al is less than 10, while the EFs for V, Cr,
Co, Ni, Mn, Ba and P ranged from 12.3 to 82.8, which indicates that
these elements were enriched relative to the crust and thus result from
anthropogenic sources instead of crustal sources. The EFs for Cu, Pb,
Mo, Zn, Cd, As, Sb, Br, I and Se are in the range of 189.4–27667.9,
which indicate that these elements are highly enriched relative to the
crust, and apparently, these elements result from anthropogenic
sources. The result is similar to the study of the physicochemical
properties of snow in the southern Qinghai-Tibet Plateau and Daqing
(Tang et al., 2012; Huang et al., 2013), in which the EFs for Zn, Cd, Hg
and Pb were greater than 10. In the study of snow in Tehran, Iran
(Hossein et al., 2014), Zn, Cd and Pb were also highly enriched. It can
be seen from Table 4 that the EFs for the northern cities (SJZ, LZ, XA, JX
Y. Gao et al.
and ZZ) are higher than those for the southern cities (HZ, LA, NJ, WH
and GD). In addition, for the same elements, the EFs are quite different
in different cities; for example, for Pb, the maximum EF is 83 times the
minimum EF, which indicates that the difference among the different
cities is quite great.
To determine the elemental pollution sources exactly, principal
component analysis (PCA) with varimax normalized rotation was ap-
plied to the data set. The variance contribution rate reflects the weight
of the original pollution information extracted from a principal com-
ponent, and the greater the variance contribution rate, the greater the
pollution contribution of the principal component (Chen et al., 2010).
In this study, the 19 elements are calculated under four cases: (1) After
the removal of elements Br and I, which are mainly from ocean sources
(marine EFs for Br and I are 1.0 ± 0.7 and 426 ± 169 (Gao et al.,
2010)), and calculation. Three principal factors were obtained, and the
accumulation formation rate of the original variables reached 91.8%.
The variance contribution rate of the first factor is 65.7%, it was
characterized by V, Cr, Mn, Co, Ni, Cu, Mo, Sb, Se, Ba and P. The EFs of
these elements are in the range of 12.3–27667.9, which indicates that
these elements are mainly contributed by anthropogenic factors. Ag and
Co are the characteristic elements for dust emission during coal com-
bustion (Duan et al., 2012), Se, V, Cr, Mo and Ni are also closely related
to the combustion of coal and oil. During the analysis of the chemical
composition and morphology of tire dust conducted by Kouji and
Yoshiaki (2004), it was found that braking provides a certain con-
tribution of Cu and Ba. Thus, factor 1 was a mixed source of the com-
bustion of fossil fuels and traffic. The second factor was loaded with As,
Al and Fe, EF of Al was less than 10 (Table 4) and Fe is the reference
element, Al and Fe were thought to be a crustal component, this source
was interpreted as the crust. The loads of Zn, Cd and Pb in the third
factor were high, and their EFs are 860.1, 1446.6 and 545.9, they were
contributed to anthropogenic sources. Among them, Zn and Pb are
closely related to emissions from refineries and industrial metallurgy
(Hu and Balasubramanian, 2003; Loranger et al., 1996), while Cd is
mainly emitted by power plants and industrial activities, factor 3 was
mainly originated from industrial sources. (2) After removal of the
crustal elements Fe, Al, P and Ba and calculation, two principal factors
were obtained, and their variance contribution rates were 64.7% and
19.6%. The first factor was largely associated with V, Cr, Mn, Co, Ni,
Cu, As, Mo, Sb, Se, Br and I, which were similar to the first case. Ac-
cording to the results of case (1) and section 3.3, elements Br and I were
mainly from ocean sources and burning coal, elements V, Cr, Mn, Co,
Ni, Cu, Mo, Sb and Se were mainly from the combustion of fossil fuels
and traffic, and burning of fossil fuels is an anthropogenic source of As
in urban atmospheres (Talovskayal et al., 2014). Therefore, factor 1 was
a mixed source of the combustion of fossil fuels, traffic and ocean
sources. The loads of Zn, Cd and Pb in the second factor were high, this
factor was mainly originated from industrial sources. (3) After the re-
moval of Br, I (mainly from ocean sources) and Fe, Al (mainly enriched
in the crust) and calculation, two principal factors were obtained, and
the elements associated with the first factor were V, Cr, Mn, Co, Ni, Cu,
As, Mo, Sb, Se, Ba and P. Factor 1 was a mixed source of the combustion
of fossil fuels and traffic sources. The elements related to factor 2 were
Zn, Cd and Pb, and this factor was mainly originated from industrial
sources. (4) After the removal of Br and I (mainly from the ocean) as
well as Fe, Al, P and Ba (mainly from the crust) and calculation, two
principal factors were obtained. The first factor was characterized by V,
Cr, Mn, Co, Ni, Cu, As, Se, Mo and Sb, and this factor mainly represents
47
Atmospheric Environment 174 (2018) 43–53
a mixed source of the combustion of fossil fuels and traffic sources. The
second factor was loaded with Zn, Cd and Pb which the source is mainly
from industrial. Based on the above analysis, elements can be divided
into the following four categories: (1) Elements were mainly originated
from the crust, including Fe, Al, Ba and P, but for elements Ba and P,
their EFs were moer than 10, so they were also affected by burning coal
and traffic. (2) Elements were from the ocean sources, including Br and
I, but they were also affected by burning coal because of their high EFs.
(3) Elements were typically associated with the combustion of fossil
fuels and traffic, including V, Cr, Mn, Co, Ni, Cu, As, Mo, Sb and Se. (4)
Elements were mainly from industrial activities, including Zn, Cd and
Pb.
4. Conclusions
This study describes the distribution and source attributions of the
trace elements and species of arsenic, iodine and bromine in snow
across east-central China in February 2014. The data of concentration
of elements in different cities shows that concentrations of total ele-
ments in the northern cities are higher than those in the southern cities,
and SJZ is the city which the concentrations of elements is the most
abundant. The concentration of Al is the highest, followed by Fe, Zn, P
and Ba, with concentrations greater than 10.0 μg/L, those abundant
elements in snow are also mainly distributed in the coarse fraction of
atmospheric aerosol, suggesting that the main air-snow transfer process
is dry deposition. The high EFs values of chemical species such as V, Cr,
Co, Ni, Mn, P, Ba, Cu, Pb, Mo, Zn, Cd, As, Sb, Br, I and Se in our snow
samples also suggest that they were likely derived from anthropogenic
sources, including metal smelting, fossil fuel combustion and combus-
tion of gasoline. Results of PCA on the elements showed that most of
trace elements (e.g. V, Cr, Mn, Co, Ni, Cu, As, Mo, Sb, Se, Br, I, Ba and
P)were from the combustion of fossil fuels, traffic and ocean sources
and some other elements (e.g. Zn, Cd and Pb) were mainly originated
from industrial activities. The high correlation coefficients between the
concentrations of elements and AQI, PM2.5 and PM10 suggest that the
concentration of elements in snow samples is highly correlated with air
pollution and reflects the magnitude of the local atmospheric deposi-
tion, the result of comparison with concentrations of elements in PM2.5
also come to that conclusion. The data of arsenic, bromine and iodine
species presented here shows that SOI is the most abundant species, the
majority of the total bromine is bromide, and the concentrations of I−,
Br− and As(III) is much higher than that of IO3−, BrO3− and As(V) in
snow sampled at east-central China. This suggests that arsenic, bromine
and iodine in high valence are less than that in low valence state in
snow sampled at east-central China, although arsenic, bromine and
iodine in high valence state are stable. So this study demonstrated that
the snow chemistry in east-central China region atmosphere probably
reflects the magnitude of the local atmospheric deposition, the degree
of local pollution and the characteristics of oxidation-reduction in at-
mospheric media.
Acknowledgments
We are grateful for the help of Min Zhu and Xifeng Lu from
PerkinElmer. We also acknowledge the generous instrument support
from PerkinElmer at the Zhangjiang Hi-Tech Park in Pudong, Shanghai.
This work was funded by the National Natural Science Foundation of
China (project number: 21377087).
Y. Gao et al. Atmospheric Environment 174 (2018) 43–53

Appendix 1

Fig. 1. Sampling sites. The gray regions represent snowfall areas, and the green regions represent sleet areas. The deeper the color, the greater the intensity of the snowfall and sleet. (The
above three graphs are the forecast trend graphs.)

Appendix 2

Table 1
Detection limits of elements and species.

Element Detection limit (μg/L) Element Detection limit (μg/L) Element/Species Detection limit (μg/L)

V 0.003 Zn 0.994 AsIII 0.081

Co 0.003 Se 0.093 AsV 0.180
Cr 0.078 Mo 0.004 DMA 0.212
Mn 0.009 Rh 0.001 MMA 0.067
Pb 0.009 Pd 0.002 I 0.10
Fe 3.948 Cd 0.002 I−1 0.023
Ni 0.019 Pt 0.002 IO3− 0.073
Hg 0.015 P 1.461 Br 1.891
Cu 0.015 Ba 0.005 Br− 0.241
As 0.010 Sb 0.022 BrO3− 0.213
Al 0.052

48
Y. Gao et al. Atmospheric Environment 174 (2018) 43–53

Appendix 3

Fig. 2. . Concentrations and standard deviations in the snow samples from different cities. The vertical ordinate represents the concentration (μg/L), and the horizontal ordinate
represents the city (HZ, SJZ, LA, LZ, NJ, XA, WH, GD, JX, QD and ZZ). For Fe and Al, 5 snow samples were mixed together so that each city has only one data point.

49
Y. Gao et al. Atmospheric Environment 174 (2018) 43–53

Appendix 4

Table 2
Concentration characteristics of elements in east-central China.

Element Number of samples Min (μg/L) Max (μg/L) Ave ± σ(μg/L) Max/Min

V 51 0.034 4.913 0.605 ± 1.028 144.5

Cr 51 0.086 3.432 0.529 ± 0.624 39.907
Mn 51 0.465 54.109 9.608 ± 11.200 116.363
Fe 11 3.209 68.612 21.605 ± 20.048 21.381
Al 11 6.689 106.053 40.842 ± 36.261 15.855
Co 51 0.003 1.448 0.156 ± 0.251 482.667
Ni 51 0.067 5.094 0.722 ± 1.055 76.030
Cu 51 0.343 23.974 3.548 ± 4.648 69.895
Zn 51 4.541 64.468 20.238 ± 14.488 14.197
As 50 0.020 6.587 1.083 ± 1.118 329.350
Se 51 0.094 1.903 0.499 ± 0.396 20.245
Mo 51 0.004 1.091 0.391 ± 0.625 272.750
Rh 51 ND ND ND ND
Pd 51 ND ND ND ND
Cd 51 0.003 0.497 0.102 ± 0.099 165.667
Sb 51 0.029 4.064 0.471 ± 0.658 140.138
Ba 51 0.855 68.378 12.078 ± 13.788 79.974
Pt 51 ND ND ND ND
Hg 51 ND ND ND ND
Pb 51 0.014 28.35 2.356 ± 4.596 2025.000
P 49 1.479 91.761 17.606 ± 19.238 62.043
Br 50 1.969 35.532 6.711 ± 7.023 18.046
I 50 0.052 6.239 2.218 ± 1.677 119.981
Sum of the average concentration of all elements: 141.4 ± 138.8 μg/L.

Appendix 5

400 400

PM10 PM2.5 Concentrations of elements AQI

300 300
Concentrations

AQI

200 200

100 100

0 0
HZ LA NJ QD WH GD ZZ XA SJZ

Fig. 3. Correction between the concentration of all elements and AQI. Vertical ordinate on the left represents the concentrations of elements (μg/L) and PM (μg/m3), vertical ordinate on
the right represents the AQI values, and the horizontal ordinate represents the city.

50
Y. Gao et al. Atmospheric Environment 174 (2018) 43–53

Appendix 6

Fig. 4. HPLC-ICP-MS chromatograms of the As, I and Br species in snow samples.

51
Y. Gao et al. Atmospheric Environment 174 (2018) 43–53

Appendix 7

Table 3
Concentration characteristics of each form of elements As, I and Br (μg/L).

City As I Br

AsIII AsV DMA MMA TSAs I− IO3− SOI TSI Br− BrO3− SOBr TSBr

GD 0.304 0.18 0 0 0.792 1.154 ND 2.008 3.162 3.694 ND 3.169 6.863

HZ 0 0 0 0 0.064 0.089 ND 0.356 0.445 0.372 ND 0.74 1.112
JX 1.4 0 0 0 1.474 1.047 ND 1.028 2.0759 3.377 ND 2.006 5.383
SJZ 1.0295 0.067 0 0 1.482 3.07 0.067 4.488 7.625 20.74 ND 12.377 33.117
WH 0.1044 0.015 0 0 0.133 1.112 0.026 0.786 1.924 3.661 ND 0.681 4.342
ZZ 0.9944 0.012 0.004 0 0.913 2.277 ND 2.575 4.852 4.704 ND 1.972 6.676
LA – – – – 0.767 0.025 ND 0.1 0.125 0.799 ND 0.054 0.853
LZ – – – – 2.357 0.978 0.177 1.362 2.517 4.371 ND 2.157 6.528
NJ – – – – 0.569 1.18 0.037 1.289 2.5063 4.128 ND 1.636 5.764
QD – – – – 0.388 1.874 0.051 1.623 3.549 10.976 ND 3.41 14.386
XA – – – – 2.746 1.114 ND 2.406 3.52 4.546 ND 3.649 8.195

Appendix 8

Table 4
Crustal enrichment factors (EFs) of elements using Fe as the reference element.

City V Cr Mn Al Co Ni Cu Zn Se As Mo Cd Sb Ba Pb P Br I

HZ 1.5 13.2 3.1 0.4 12.5 4.1 44.2 505.1 7882.3 109.3 65.5 136.0 1363.8 42.6 121.4 11.4 1442.8 2969.8
SJZ 65.5 59.4 113.0 4.0 98.9 104.0 676.8 1060.1 69620.7 2542.8 2890.9 521.7 28373.4 340.0 93.6 173.3 29548.6 33434.8
LA 1.0 15.4 3.5 0.3 3.8 4.6 365.3 453.3 ND 1316.5 64.0 110.3 1677.0 8.1 80.0 9.5 823.9 605.5
LZ 36.5 17.1 42.3 3.7 28.0 50.3 204.4 401.1 38761.5 3262.3 1788.1 1384.9 10559.6 100.8 125.6 93.7 8299.9 10805.6
NJ 10.5 11.6 15.4 0.7 9.6 14.0 164.6 1304.6 11439.3 976.7 356.8 1372.1 2842.4 50.3 466.3 46.1 5481.6 11916.0
XA 8.5 25.4 21.2 2.8 16.5 59.1 252.0 1527.8 43917.7 4710.2 1554.2 3743.6 10485.8 126.5 2599.6 34.2 5849.1 11192.4
WH 2.2 7.2 12.2 0.3 2.2 10.2 59.3 1228.4 35008.6 229.0 165.4 2013.4 2590.6 21.2 445.2 12.1 5501.1 7914.9
GD 2.5 8.2 12.3 1.2 5.6 11.3 113.0 1103.7 26154.8 1359.4 395.5 1948.9 3273.6 18.8 1549.8 26.7 7119.0 16194.6
JX 2.5 8.3 39.0 0.4 7.9 10.2 31.9 463.8 19570.2 2528.1 161.2 1142.1 4843.4 64.4 74.3 13.1 4820.0 8376.6
QD 2.5 4.3 22.7 0.6 5.3 10.7 74.4 691.1 27265.8 666.1 218.4 1551.2 3045.2 47.4 292.7 41.6 12881.1 14505.8
ZZ 2.5 4.5 36.3 2.5 10.1 18.3 97.8 722.2 24726.1 1566.9 269.2 1988.5 4137.1 90.1 156.0 41.9 6205.7 19870.5
Average 12.3 15.9 29.1 1.5 18.2 27.0 189.4 860.1 27667.9 1751.6 720.8 1446.6 6653.8 82.8 545.9 45.8 7997.5 12526.1

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