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Air Pollution and Climate Change

SEM-EDX IDENTIFICATION OF PARTICLES FROM FOG IN AN


INDUSTRIALLY POLLUTED REGION OF CZECH REPUBLIC
Assoc. Prof. Dr. Valeria Stoyanova1, Dr. Annie Shoumkova1,
Eng. Dr. Jaroslav Fisak2, Tsenka Tsacheva1
1

Institute of Physical Chemistry Rostislaw Kaischew, BAS, Bulgaria


2
Institute of Atmospheric Physics, AS CR, Czech Republic

ABSTRACT
The properties of individual particles, rather than bulk aerosol characteristics, determine
the environmental and health impact of the atmospheric pollutants. Single particles have
been sampled during 30 fog episodes at the mount Milesovka (837 m a.s.l.) located in
the industrially polluted area of north Bohemian brown coalfield. More than 2000 of
these solid, water insoluble particles, collected from May 2006 till July 2007, have been
analyzed by SEM-EDX and classified according to their shape, size and elemental
composition. Here we summarize results related to the presence of some heavy metals
and other trace elements and their correlation to wind speed and direction, t given
meteorological conditions. Particles, rich of Cu, Zn, Ba, Pb, Co, Ni, Fe, Ag, Au, Ce, Gd,
etc., have been detected. Most of the identified heavy metals present in particles smaller
than 5 m. It has been established that some elements exist separately or in specific
combinations that, along with the information for particles backward trajectory, could
be used for recognition of the atmospheric pollution sources.
Keywords: SEM-EDX, solid atmospheric pollutants, trace elements, heavy metals,
Czech Republic.
INTRODUCTION
The changes in chemical composition of the atmosphere have important contribution to
air quality and climate changes [1,2]. Solid aerosols play a central role in adverse health
and visibility. They are associated with a variety of anthropogenic activities (traffic,
industry, power plants, mining, combustion, etc.) and/or natural processes (volcanoes,
forest fires, sea spray, etc.) [3]. Ejection of giant amounts of anthropogenic heavy
metals in atmosphere is still an unsolved problem bothering the European community.
Knowledge about the nature of such pollutants is essential not only for their monitoring
but also for the modeling of atmospheric processes.
It is well known that the properties of the individual particles, rather than the bulk
aerosol characteristics, determine the optical, environmental and health effects of one
aerosol. Scanning electron microscopy (SEM), coupled with Enegry Dispesive X-ray
Spectrometer (EDX), has proven to be an ideal tool for characterization of individual
particles [4-7], providing simultaneously precious information for their composition,
shape, structure and size that cannot be obtained by any bulk analytical approach.
In this paper we pay attention to the usage of the solid atmospheric pollutants as tracers
for specific emission sources, especially when they are of inhalatory size and have
specific morphology and composition.
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International Multidisciplinary Scientific Geo-Conference SGEM 2010


SAMPLING AND ANALYSIS
Solid particles, known as PM10 or PM2.5 (particulate matter, smaller than 10 or 2.5
m), transported by fog water droplets have been studied. They have been collected at
Milesovka observatory, located in North Bohemian brown coalfield one of the most
polluted areas of the Czech Republic till the nineties. Several large conurbations (Most,
Usti nad Labem, Litvinov, Teplice, etc.), power plants and intensive chemical industry
are concentrated there and additionally a high traffic road for trucks passs along.
In total 30 fog samples were gathered during fog episodes from May 2006 till July 2007
by using of special active and passive devices. The insoluble particles have been caught
by filtering of fog water through nitrocellulose filters (pore sizes 0.45 m), dried,
covered with carbon coating (onto the filter) and studied. The soluble constituent of
some of these fog water samples has been previously analyzed [8]. The comparison of
water-soluble and insoluble contents in fog samples is an authors aim in progress [910]. The aim of the current investigation is to provide information about composition
and properties of atmosphere solids that, along to the data for the meteorological
conditions, will contribute for the identification of the air pollution sources, which is our
final goal.
All analysis of fog particles (FP) has been carried by mean of JEOL JSM 6390. The
elemental spectrum of each particle was collected for 30 s at 20 KeV. The size and
shape of each particle were determined manually during its observation by SEM (using
SEI- and BEI- mode) and from the microphotographs. Most of the morphological
characteristics (shape, size, surface, axis relation, etc.) are better visible in SEI- mode,
formed by secondary electrons. At appropriate conditions, the FP rich of iron and/or
other heavy metals could be easily detected in backscattering mode (BEI), formed by
back-scattered electrons. In this mode, particles (or pieces of them), enriched in
element/s, having atomic number bigger than that of the iron, are represented as bright
spots on dark background. All non-ferrous heavy metal FP have been identified in BEImode, because of their low frequency and small sizes. More details for the used
apparatus and methods of analysis of micro- and nano-size FP are given in our previous
publications [6,7].
EXPERIMENTAL RESULTS
Between 50 and 150 particles have been analyzed in each of the 30 fog samples, and
totally more than 2200 FP have been studied. FP collected from one single wind
direction have been classified into groups: East (97), South (188), West (1192) and
North (289) (see Table 1, Fig. 1). FP collected from more than one wind sector are
included in the data, presented in Fig. 2. All carbon-rich particles (organics, soot, etc.)
are excluded from data reprocessing in this presentation. In Table 1 some
meteorological conditions measured during fog samples collection are given together
with the electron-microscope data for the studied FP from each sample and their
distribution in the four main groups. Each wind direction main group is divided into
three principal (vertical) groups: particles enriched in Fe (Fe > 50 wt.%), particles of
non-ferrous transition and heavy metals, and particles enriched in Al+Si > 50wt% (the
rest of particles, not fulfilling these criteria, are excluded from this table). The percent
of spherical particles (indicative for high-temperature processes) is shown in breaks
after the number of analyzed FP for every sample and group of particles. An averaged
value of the mean particle size is added in the last column of Table 1.
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Table 1. Meteorological conditions and electron-microscope data for the studied FP,
their distribution in the four main wind sectors and in three principal groups FP
enriched by Fe, by Al+Si and by heavy metals, together with the mean particle size.
Sample

Fog
sampling
date

East
1
28/05/07
South
2
23/10/06
3
28/11/06
West
4
30/08/06
5
06/09/06
6
21/10/06
7
24/10/06
8
12/12/06
9
09/01/07
10
17/01/07
11
15/05/07a.m.
12
16/05/07
13
25/06/07
14
02/07/07
15
05/07/07
16
29/07/07
North
17
04/04/07
18
29/04/07
19
15/05/07p.m.
20
03/06/07

Wind
Sampling
Wind
Studied
speed, direction,
time,
FP/spheres
m/s
degrees
hours
10.5

9577

7.25

10
6

19237
183.532.5

3
12

12
9
11
13
11
14.5
19
9
10
5
7.5
8.5
8

2966
304.512.5
238+12
23617
27125
2524
2506
292.54.5
2943
244.59.5
245.511.5
2878
273.542.5

4.75
5
5.5
1.5
16
8.5
25
4.5
7
8.5
29.25
4
7.25

6.5
8
12.5
9.5

354.516.5
349.57.5
330.519.5
35834

3.5
3
6.25
7.25

Fe-rich
FP

97 (17%) 15%(40%)
97 (17%)
15 (40%)
188 (30%) 24%(41%)
92(39%)
22(45%)
96(21%)
24(42%)
1192 (22%) 18%(31%)
79(43%)
11(54%)
77(29%)
18(28%)
79(39%)
34(38%)
89(43%)
23(35%)
99(14%)
9(44%)
97(5%)
10(10%)
107(14%)
20(25%)
91(12%)
9(33%)
102(15%)
11(36%)
84(20%)
9(11%)
75(7%)
11(9%)
96(11%)
16(12%)
117(37%)
35(43%)
289 (13%) 9%(19%)
53(26%)
13(38%)
73(5%)
9(0%)
83(16%)
8(12%)
80(7%)
6(17%)

Other
heavy
metal
FP
3%(30%)
3(30%)
16%(47%)
15(47%)
15(47%)
9%(24%)
6(0%)
5(0%)
17(71%)
9(55%)
10(20%)
20(0%)
7(14%)
7(0%)
9(22%)
3(33%)
5(20%)
6(50%)
2(100%)
9%(12%)
7(0%)
9(11%)
6(33%)
3(0%)

Alumosilicate
FP

Mean
size,
m

66%(14%)
64(14%)
58%(28%)
59(41%)
50(12%)
54%(25%)
76(37%)
57(28%)
49(29%)
85(32%)
53(11%)
38(0%)
72(12%)
36(14%)
83(11%)
68(21%)
36(8%)
46(9%)
94(27%)
53%(14%)
26(31%)
29(10%)
42(17%)
57(7%)

1.6
2.2

3.8

4.2

Cr

Mn

Ni

Cu

Zn

Ag

Ba

Pt

Au

Pb

Fe

Cr

Mn

Ni

Fe

Cr

Mn

Co

Ni

Zn

Zr

Fe

Cr
Ni
Zr
Sb
W
Pb

Mn
Cu
Ag
I
Ce
Fe

Co
Zn
Sn
Ba
Au

Figure 1. Normalized data for heavy metal FP according to the main wind sectors.

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International Multidisciplinary Scientific Geo-Conference SGEM 2010

Figure 2. Elemental composition of all (2206) particles studied microscopically.

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Air Pollution and Climate Change


Fig. 1 presents in broad outline the distribution of the studied FP enriched of iron and
non-iron heavy metals according to the main four wind sectors. The elemental spectra
obtained from more than 2200 FP, including samples covering more than one wind
sector (that are not presented in Table 1 and Figure 1), are illustrated in Fig.2. The
legends in the Fig. 1 and Fig. 2 mark the elements by different colors or patterns.
Typical FP shapes (faceted, rounded, dendritic) and surfaces (smooth or rough) are
presented in Fig. 3. Their macro composition is given in weight percents up-left on each
photo, while up-right is indicated the first letter of the corresponding wind sector. The
FP size is in the micrometer scale and indicated by marker line below each photograph.

Figure 3. Heavy metal FP (looking as white spots in BEImode) with different


composition, given in weight percent up-left on each photo. The FP size is indicated by
the corresponding marker line below each photograph.

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DISCUSSION AND CONCLUSIONS
Every atmospheric particle brings its own valuable information that, after statistical
accumulation of data, contributes the clarifying of pollution status. For example, NaCl
particles (10 found in this study) can direct our attention to the salting of the roads
during winter period. Other typical markers appear to be carbon-rich particles that are
born due to the intensive anthropogenic activity (coal and other fuels burning) in
heating periods from autumn to spring. (The analyses of carbon-rich FP are not included
here, although they represent a significant part of the investigated fog particles.)
Similar is the role of particles enriched in specific combinations of heavy metals is
indicative for the source of pollution, especially if the transport history of FP can be
evaluated. The information for the shape, size and surface peculiarities of the studied FP
is also important for their identification. For example, the spherical shape of micro- and
nano- particles usually results from high-temperature processes, and therefore could be
almost directly correlated to an anthropogenic origin. Nevertheles, an explicit
conclusion, must be supported by data for the chemical composition of the particle.
Almost all FP studied represent PM10, more than 60% of them are even PM2.5 (mean
particle size 3.6 m). As such fine particles have been in contact with acidic water (pH
~ 4) for a long time (from hours to days) [8], they probably have passed through various
physicochemical transformations (dissolution, pre-crystallization, etc.), and actually
represent not primary (as emitted) but secondary particles. This note should be taken
into account when a FP and PM from industrial sources are compared.
The small number of FP collected in some sectors additionally hampers the statistical
processing of data for evaluation of the mean FP size. Nevertheless, a tendency has been
established (Table 1, last column), showing that in general the smaller particles belong
to the South-East and the bigger - to the North-West group. Most probably this result is
related to the more intensive wind flows from West, lifting bigger particles from the
crust and soils in atmosphere. The relation size-pollution source is less probable.
Some of the detected elements (Fe, Cr, Mn, Ni) present in all studied samples,
independently on the wind direction during the respective fog episode. Others FP are
common for two wind sectors, e.g. Cu, Ag, Ba, Au and Pb (North-West) and Co and Zr
(South-West). Third elements have been encountered in a single sector only, e.g. Sn, W,
Ce (West), Pt (North), Y (South). One quarter of all non-ferrous heavy metal FP are rich
of Zn, a fact corresponding to the recently published reports for the absence of clear
tendency for Zn-pollution decreasing in European Union since the beginning of the
nineties [11,12]. Analyzing rain waters, one of these authors [12] has confirmed the
decrease in Cu, Pb and Cd pollution that use to be a serious environmental problem in
Czech Republic [13,14].
The West sector is the most abundant in heavy metals (without Fe) as number of
elements (16), distributed in 9% of all studied 1192 FP. This result is expected, having
in mind the prevailing west winds, located in this direction intensive industry, including
several power plants, and heavy traffic. According to [15,16], traffic appears to be
responsible for particles enriched in Ba, Cu, Cr, Pb, Sb and Zn, while Ni and Sn are
being emitted most probably by the industry. This result is supported by the typical
microstructure (rounded shape and small sizes) of some FP from West direction (see
Figure 3).

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Air Pollution and Climate Change


The number of Fe-rich FP in North sector is relatively low and equal to that of heavymetals-rich FP. The percent of spherical particles in all types of FP is the lowest (1219%), indicating smaller contribution of industrial high-temperature burning processes
to the atmosphere pollution. Eleven different heavy metals (except Fe) have been
detected in four samples analyzed.
The East sector is characterized by the lowest amount and variety of heavy metal FP (3,
excluding Fe-rich ones, 3% of 97 studied FP). This concentration is up to 3-5 times
lower than in the other sectors. Only 3 particles (enriched in Cr, Mn and Ni) have been
found there. Although on the base of one analyzed sample only it is difficult to conclude
that pollution episodes from East are rare, it seems so.
The most interesting results have been obtained from the analysis of FP from the South
sector, where heavy metal FP (excluding Fe-rich ones) cover 16% of all studied FP
(188) (see Table 1), and seven different heavy metals have been detected (see Fig. 1) in
only two samples. This fact is supported by the greatest concentration of spheres (30%)
found in all types of FP in the South samples (see Table 1). The spherical particles in
Fe-rich FP reach 41%, and 47% in heavy - metals bearing particles. These
microspheres, resulting usually from high-temperature combustion processes, often
contain toxic elements, condensed on their surfaces [17,18] that could be readily
extracted in acidic soil solutions or in the lung.
In conclusion, solid particles, caught by fog, could be used successfully in air pollution
monitoring especially those, enriched in heavy metals that can act as valuable markers
for industrial contamination of the atmosphere.
ACKNOWLEDGEMENTS
The participation in SGEM-2010 has been realized with the financial support of Project
TK-X-1713 funded by Bulgarian Ministry of Education and Science.
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