SILVER ANNIVERSARY International Conference on
Heavy Metals in the Environment, 6-10 August, 2000; Ann Arbor, Michigan
An estimation
OF trace METAL EMISSIONS IN
VILNIUS CITY
Darius
Valiulis, Kęstutis
Kvietkus*, Darius Čeburnis and Jonas Šakalys
Atmospheric Pollution Research
Laboratory, Institute of Physics, Goštauto 12, 2600 Vilnius, Lithuania, kvietkus@ktl.mii.lt
Abstract
Daily air samples of heavy metals (HM) were
collected at heights of 10 m, 55 m and 170 m in Vilnius TV tower, during
October 26 - December 20, 1999.
Sampling period was divided between day (8 AM – 21 PM) and night (22 PM
– 7 AM) time. The aerosols were separated into fine and coarse fraction with a virtual
impactor (cut-off diameter - 2.5 μm). Concentration gradients were determined for all metals in both
fractions (Ba, Pb, V, Sb, Zn) with the exception of vanadium on fine particles.
Heavy metals emission rates from Vilnius city were calculated using vertical
gradients of HM concentrations and meteorological measurement data.
Historically
the rate of heavy metals emission has been low because of the low volatility of
most metals (except mercury). However, with the advent of high-temperature
processes (smelting and fossil fuel combustion), the rate of emission for some
metals has substantially increased. With increased emissions have come
increased metal concentrations in the atmosphere and in atmospheric deposition
(Blank et al., 1998).
As in many cities worldwide, the concentrations
of air pollutants in the Vilnius city sometimes exceed the limit values. The
only safe way to avoid air pollution episodes is obviously the reduction of
pollutant emissions. However, it is established that serious pollution episodes
in the urban environment are not generally caused by the sudden increase in the
emission of pollutants, but as a result from a short-term unfavorable
meteorological conditions (Zickus and Kvietkus, 1998).
The
composition and size of the particles vary upon their origin. The ones that are
formed from combustion are small, while the natural ones are quite large
(Williams et al., 1998).
The main
goal of the present work was the investigation of heavy metals emissions using
vertical profile measurement data in Vilnius city.
MATERIALS AND METHODS
Daily air samples
of heavy metals were taken at heights of 10 m, 55 m and 170 m in Vilnius TV
tower, situated in a western part of the city, during October 26 - December 20,
1999. Sampling period was divided between day (8 AM – 21 PM) and night (22 PM –
7 AM) time. Aerosols were collected into fine (<2.5 μm) and
coarse (>2.5 μm) fractions using
virtual impactor (Ulevičius et al., 1999). Aerosol samples were collected
with low volume samplers (1 m3 / h) on Whatman 40 filters. After collection
filters were extracted in 0.2 M HNO3 using ultrasonic bath for 1
hour. Preparation parameters were selected after pilot investigation (Čeburnis et. al., 1999). Concentrations of HM were determined in fine
and coarse aerosol fractions using an atomic absorption spectrophotometer
Zeeman/3030. Elements under consideration were Barium (Ba), Lead (Pb), Antimony
(Sb), Vanadium (V) and Zinc (Zn).
RESULTS AND
DISCUSSIONS
Vertical concentration profiles were obtained for all
studied heavy metals as presented in Figure 1. The concentration gradients were
negative for all elements with an exception of vanadium on fine particles,
during day and night time. The gradient of vanadium concentration on fine
particles during day time was positive near the ground. The concentration of
vanadium was increasing up to the 55 m height. Referring to the main source of
vanadium being stack emissions from the fossil fuel combustion, the vanadium
concentration profile on fine particles corresponds well that assumption. However,
concentration profiles of all other
elements points to the conclusion that
the main source of all other elements, including vanadium on coarse
particles, is the surface. The profile
of lead concentrations on fine and coarse particles (Figure 1) is the typical
one, very similar ones were obtained for other elements.

The concentration gradients of the elements were calculated
at 10 m height using vertical profiles (Table 1). As it was mentioned above the
concentration gradients on fine and coarse aerosols, during day and night time
were negative for all elements with the exception of V on fine particles.
Table 1. Vertical concentration gradients (ng/m4)
of heavy metals in Vilnius city.
|
Element |
day-fine |
night-fine |
day-coarse |
night-coarse |
|
Pb |
-.0776 |
-.0751 |
-.0191 |
-.0301 |
|
V |
.00597 |
-.0162 |
-.0073 |
-.0152 |
|
Ba |
-.0191 |
-.0249 |
-.0215 |
-.0313 |
|
Zn |
-.154 |
-.243 |
-.085 |
-.115 |
|
Sb |
-.0223 |
-.0142 |
-.0183 |
-.013 |
Heavy metals emissions from the surface of Vilnius city
were calculated using following equation:
,
where K is the coefficient of turbulent diffusion; dc/dz is the concentration gradient.
Coefficient of turbulent diffusion was calculated using data of Vilnius air quality meteorological mast. Than emission of heavy metals were calculated and presented in Table 2.
|
Element |
day-fine |
night-fine |
day-coarse |
night-coarse |
|
Pb |
0.0388 |
0.0150 |
0.0096 |
0.0060 |
|
Ba |
0.0096 |
0.0050 |
0.0108 |
0.0063 |
|
Zn |
0.0770 |
0.0486 |
0.0425 |
0.0230 |
|
Sb |
0.0112 |
0.0028 |
0.0092 |
0.0026 |
As it might be supposed the emission of elements during the nighttime were lower. It is clear that emission intensity is very much related with human activity in Vilnius city and most probably originated from a transport traffic. On the other hand the absolute emission values are too low to have significant influence on regional trace metal concentration background.
CONCLUSIONS
The trace metal concentration gradients on fine and coarse aerosols during day and
night time were negative for all elements with the exception of vanadium on
fine particles. This corresponds well to the main source of vanadium being
stack emissions from fossil fuel combustion. Heavy metals emissions, calculated
for the city of Vilnius, are approximately twice higher during daytime than
that during the nighttime.
The obtained results are characteristic for late fall –
winter season and probably do not reflect the annual values.
References
1. Žičkus M. and Kvietkus K. (1998), Proceedings of the Sixth International
Conference on Air Pollution, AIR POLLUTION VI, September 18-21, 1998, Comp.
Mech. Publication, 515-523.
2.
Blank
P., Friedrich R., John C., Obermeier A. and Wickert B. (1998), Proceedings
of the EUROTRAC Symposium 1998.
Editors: P.M. Borrel and P. Borrel.
2000, WIT press, Southampton, 737-740.
3.
Williams
P.I., Gallagher M.W., Choularton T.W., Coe H. and Bower K.N. (1998), Proceedings of the EUROTRAC Symposium 2000. Editors: P.M. Borrel and P. Borrel. 2000, WIT press, Southampton, 822-825.
4.
Ulevičius V., Juozaitis A. and
Šopauskienė, D. (1999), Environmental Physics, 20, (2), 20-27, Vilnius, Lithuania.
5.
Čeburnis D., Valiulis D. and Šakalys J. (1999), Environmental Physics, 21
(1), 31-36, Vilnius, Lithuania.