IDENTIFICATION OF AIR POLLUTION ELEMENTS IN LICHENS USED

AS BIOINDICATORS, BY THE XRF AND AAS METHODS*

GABRIEL STATE1, ION V. POPESCU2,3,4, ANCA GHEBOIANU3, CRISTIANA RADULESCU3,

IOANA DULAMA3, IULIAN BANCUTA3, RALUCA STIRBESCU5
1
National College “Ienăchiţă Văcărescu” Târgovişte, Romania, cristigabi@yahoo.com
2
Academy of Romanian Scientists 54 Bucharest 05009, Romania
3
Valahia University of Târgovişte, Romania
4
National Institute of Physics and Nuclear Engineering, Bucharest-Magurele, Romania
5
Doctoral School of Physics, Faculty of Physics, University of Bucharest
Received September 14, 2009

The aim of this work was the monitoring of the air quality in the Târgovişte
town and its surroundings by using of the lichens as biomonitors. The methods used
were Energy Dispersive X-Ray Fluorescence (EDXRF) and Atomic Absorption
Spectroscopy (AAS). The measurements were performed in the laboratories of the
Faculty of Sciences and Arts from Valahia University of Târgovişte. We have studied
the presence of heavy metals such as Cd, Co, Cr, Cu, Fe, Pb and Zn. The EDXRF
method has been used mainly as a qualitative analysis, the precise determination of
concentrations of the elements being done by the AAS method. Since samples have
been also taken from places less exposed to the pollution factors, the study allowed the
comparative analysis of air quality between high and low polluted areas.
Key words: Lichen, AAS, EDXRF, air pollution.

1. INTRODUCTION

The presented study is referring to a problem of great national and international

importance, which is represented by the air quality control. In particular, we have
chosen Târgovişte and the places around it, for the evaluation of air pollution with
heavy metals resulted from the social-economical activities such as: the production
of steel, stainless steel, energy in power stations, the oil exploitations and traffic.
We have chosen the lichens as biomonitors to accomplish our study. There have
been some advantages of their using [1–4]: slowly growing, insignificant change of
their morphology, long life during the year, higher area contact with atmosphere,

*
Paper presented at the 10th International Balkan Workshop on Applied Physics, July 6–8,
2009, Constanţa, Romania.

Rom. Journ. Phys., Vol. 56, Nos. 1–2, P. 240–249, Bucharest, 2011
2 Identification of air pollution elements 241

etc. These are the reasons for which they have been used in many air quality studies.
The lichen species collected in our work were: Xanthoria Parietina (in most of the
cases), Parmelia Furfuracea and Peltigera Canina. Taking into consideration the
fact that these species of lichens have different absorption properties for the air
pollutants, we tried to collect samples of one species from all places; in some of the
cases, when this was not possible, we made the necessary corrections, taking into
account the absorption properties of each element for every species [1].
The element concentrations from lichen samples were determined by Energy
Dispersive x-ray Fluorescence (EDXRF)[5] and Atomic Absorption Spectroscopy
(AAS) [6, 7] methods. Moreover, in order to achieve the elemental analysis with a
high sensitivity and precision for the environmental samples, there can be used the
Neutron Activation Analysis (NAA) [8], Chlorophyll Fluorescence(CF) [9] Electron
Spectroscopy (ES) [10,11], Particle Induced X Ray Emission (PIXE) [12–14],
Total Dissolved Solids(TDS) [15] and Inductively Coupled Plasma – Atomic Emission
Spectroscopy (ICP-AES) [7, 13].
The results to be presented in this work were obtained from samples collected
in the interval 16th–28th April 2009. The trees for the lichen sampling were chosen
from the areas with different pollution levels: some were collected near the
economical units which produce gaseous pollutants, others were taken near the
roads which had different traffic values and the others were also collected from the
forest, far away from any sources of pollution (Fig. 1). Thus we can have the
possibility to make a comparative analysis between heavy metal air pollution in
those places.
For each sample we recorded the following characteristics: the moment of
sampling, the day, the name of the place and the GPS coordinates.

2. SAMPLE PREPARATION

The samples were first washed with water then dried for 2 hours at 60ºC.
After that, a quantity of about 5g of every sample was powdered and put in clean
testing chambers covered with 2.5 µm Fluxana TF-125-345 Mylar thin film to be
studied by the EDXRF method. The data acquisition time was set to 30 min.
For AAS testing we used the same samples that had been used for EDXRF.
Therefore we put a quantity of about 0.3 g from each sample in teflon cylinders and
then we added 2 ml of nitric acid (HNO3) and 3 ml of hydrogenperoxide (H2O2).
The cylinders were heated in a microwave oven with the following temperature
program: raising to 145ºC in 10 min and maintaining it for 5 min; raising to 180ºC
in 5 min and maintaining it for 10 min; cooling to 100ºC in 1 min and maintaining
it for 10 min. The digested sample was then filtered and filled to 50 ml with
deionized water.
242 Gabriel State et al. 3

Fig. 1. The places of lichens sampling from Târgoviste and localities around it
(the map was exported from Google Earth).

3. INSTRUMENTS

The x-ray fluorescence analysis was done by the Elvax EDXRF spectrometer
which has the energy resolution of 165 eV at 5.9 keV (55Fe isotope).The software
of the instrument provides the qualitative and quantitative analysis of the samples
by quadratic stepwise multiple regressions.
The GBC Avanta AAS with flame and GBC Avanta Ultra Z with graphite
furnace spectrometers were used for atomic absorption analysis. They can detect
concentrations of ppm order, respectively of ppb order from each sample. The
instruments came with specialized software for calibration and for providing the
results with associated errors.
For the preparation of the samples we used a Berghof SpeedWave MWS2
microwave oven pressure digestion installation.
4 Identification of air pollution elements 243

4. RESULTS AND DISCUSSION

Figs. 2–8 evidences the concentrations obtained by AAS or EDXRF methods

for Cd, Co, Cr, Cu, Fe, Pb and Zn from places referred by its GPS coordinates. In
each graph the maximal and the minimal concentration as well as the ratio between
them is included. We have chosen this way of interpreting the results because the
allowed maximal concentration isn’t published. An Index of Air Pollution (IAP) or
an modified Index of Air Pollution (mIAP) [16–18] can be determined, after
collecting a large number of samples; we have not been able to do this due to the
small number of trees on which the lichens grow, especially in Targoviste. Graphs
were made using Microsoft Excel 2007 [19].
Studying the obtained results it can see that near steel and stainless steel
factories from Targoviste, respectively the power plant from Doicesti, the values of
the element concentrations c are maximal, exceeding the minimal ones from 11.9
times (for Cd) to 31.2 times (for Zn). The minimal values correspond to the
samples collected at distances greater than 15 km of Targoviste or Doicesti, deep in
the forest (Table 1).

Table 1
The extreme values of the element concentrations and the sampling places
Maximal value
Element Minimal value (ppm) Error (ppm) Error (ppm) Max/Min
(ppm)
c(ppm) 0.1 0.005 1.19 0.05
Cd Between Cobia and Dragodana, 11.90
Place Steel factories Targoviste
inside the forest
c(ppm) 0.13 0.03 2.61 0.62
Co 19.92
Place Dragodana, inside the forest Steel factories Targoviste
c(ppm) 5.08 0.6 64.47 7.73
Cr 12.69
Place Dragodana, inside the forest Doicesti power plant
c(ppm) 2.66 0.14 34.08 2.3
Cu Between Cobia and Dragodana, inside the 12.81
Place Steel factories Targoviste
forest
c(ppm) 412 28 6071 473
Fe 14.73
Place Ungureni, inside the forest Steel factories Targoviste
c(ppm) 5.00 0.45 75 7
Pb 15.01
Place Cobia, inside the forest Steel factories Targoviste
c(ppm) 5 0.22 156 7.02
Zn Between Cobia and Dragodana, inside the 31.20
Place Steel factories Targoviste
forest

The heavy metal air pollution in the two of residential areas that were the
subject of this study is presented in Table 2, where we calculated the ratio between
the local values of elements concentrations and their minimum values that were
244 Gabriel State et al. 5

listed in Table 1. National College “Ienachita Vacarescu” of Targoviste is located

about 2 km from the industrial area, in the other side of the town; Vacaresti is a
locality situated at 8 km from the steel factories. It can see that in these places the
heavy metals concentrations from air exceed the minimum values from the areas
less polluted from 1.66 to 14.26 times.

Table 2
The ratios between elements concentrations from two of residential areas and
the minimum ones listed in Table 1
National College “Ienachita
Element/Place Vacaresti
Vacarescu”
Cd (max/min) 1.66 1.67
Co (max/min) 6.58 2.75
Cr (max/min) 4.63 2.21
Cu (max/min) 6 5.86
Fe (max/min) 3.01 2.26
Pb (max/min) 3.28 2.77
Zn (max/min) 14.26 8.36

Fig. 2. Concentrations of cadmium (Cd).

6 Identification of air pollution elements 245

Fig. 3. Concentrations of cobalt (Co).

Fig. 4. Concentrations of chromium (Cr).

246 Gabriel State et al. 7

Fig. 5. Concentrations of copper (Cu).

Fig. 6. Concentrations of iron (Fe).

8 Identification of air pollution elements 247

Fig. 7. Concentrations of lead (Pb).

Fig. 8. Concentrations of zinc (Zn).

4. CONCLUSIONS

The EDXRF as a multi-elemental analysis method, allows the qualitative

analysis of elements with Z>13 in lichen samples; if element concentrations are
greater than 10 ppm, the EDXRF method also provides a good quantitative analysis.
248 Gabriel State et al. 9

The AAS, as a single element analysis method provides a much more precise
quantitative analysis of every element than EDXRF; contrary to EDXRF, which is
nondestructive and fast, the AAS is destructive and slower.
By using these two methods, an accurate quantitative assessment of the level
of environmental pollution in a given area can be obtained.
For our study, these two methods allowed us to identify the heavy metals as
pollutants of the air, with concentrations that are much higher in industrial zones
than in the ones placed in less polluted places, highlighting the need for further
studies of the other air pollutants, and their possible presence in water and soil.

REFERENCES

1. J.E. Sloof and B.Th. Wolterbeek, Interspecies comparison of lichens as biomonitors of trace-
element air pollution, Interfaculty Reactor Institute, Delft University of Technology, December
1991.
2. S.F. Heller-Zeisler, R. Zeisler, E. Zeiller, R.M. Parr, Z. Radecki, K.I. Burns, P.De Regge, Report
on the intercomparison run for the determination of trace and minor elements in lichen material,
International Atomic Energy Agency, Vienna, Austria, June 1999.
3. Quality Assurance Handbook for Air Pollution Measurement Systems Volume II: Part 1: Ambient
Air Quality Monitoring Program Quality System Development, august 1998.
4. http://www.lichens.ie/.
5. V. Ghisa, I.V. Popescu, M. Belc, A. Ene, Study of Some Roman Brooches Discovered at Tomis -
Constanta, by X-Ray Fluorescence Technique, Romanian Journal of Physics 53 (3–4), 557–562,
ISSN 1221–146x, 2008.
6. G. Dima, I.V. Popescu, C.Stihi, C. Oros, S. Dinu, Laur Manea, Gh. Vlaicu, Fe, Mn and Zn
concentration determination from Ialomita river by atomic absorbtion spectroscopy, Rom. Journ.
Phys. 51 , No 5–6, 633–638, 2008.
7. I.V. Popescu, C. Stihi, Gh.V. Cimpoca, G. Dima, Gh. Vlaicu, A. Gheboianu, I. Bancuta, V. Ghisa,
G. State, Environmental samples analysis by atomic absorption spectrometry (AAS) and inductively
coupled plasma-optical emission spectroscopy (ICP-AES), Romanian Journal of Physics, vol. 54 ,
No. 7–8, p. 741–746, 2009.
8. A. Ene, I.V. Popescu, V. Ghisa, Study of Transfer Efficiencies of Minor Elements during Steel-
making by Neutron Activation Technique, Romanian Reports in Physics 61(1), 165–171, ISSN
1221–1451, 2009.
9. S. Apostol, C.Stihi, C.Oros, The use of the chlorophyll fluorescence for estimation of photo-
synthetic electron transport flow in water stressed pea plants, Journal of Optoelectronics and
Advanced Materials, 9,9 p. 2912–2925, 2007.
10. V. Andrei, R. Cristescu, Gh. Vlaicu, E. Andrei, C. Oros, C. Stihi, G. Dima, S. Dinu, Electron
spectroscopy studies of the diamond like carbon thin films, Journal of Optoelectronics and
Advanced Materials, 9,7, p. 2288–2290, 2007.
11. V. Andrei, E. Andrei, Gh. Vlaicu, C. Stihi, G. Dima, C. Oros, S. Dinu, Chemical binding and structure
of carbonic thin films with advanced properties studied by electron spectroscopy, Journal of
Optoelectronics and Advanced Materials, 9,7, p. 2295, 2007.
12. C. Stihi, I.V. Popescu, G. Busuioc, T. Badica, A. Olariu, G. Dima, Particle Induced X-Ray
Emission (PIXE) analysis of Basella Alba L leaves, Journal of Radioanalytical and Nuclear
Chemistry, Vol. 246, No 2 (2000), 445–447.
10 Identification of air pollution elements 249

13. C. Stihi, A. Bancuta, I.V. Popescu, M. Virgolici, Gh.V. Cimpoca, M. Gugiu, Gh. Vlaicu, Air
pollution studies using PIXE and ICP-AES methods, IoP Journal of Physics: Conference Series 41
(2006), 565–568.
14. I.V. Popescu, A. Ene, C. Stihi, A. Bancuta, G. Dima, T. Badica, V. Ghisa, Analytical applications
of particle-induced X-ray emission (PIXE), Six International Conference of the Balkan Physical
Union Book Series: AIP Conference Proceedings, vol. 899, p: 538, 2007.
15. C. Stihi, I.V. Popescu, S. Apostol, Gh. Vlaicu, Water quality monitoring using Total Dissolved
Solids measurements, Revista de Chimie, 58, nr. 12, p. 1335–1336, 2007.
16. F. Leblanc, J. De Sloover, Relation between industrialization and the distribution and growth of
epiphytic lichens and mosses in Montreal, Canadian Journal of Botany48 (8): 1485–1496, 1970.
17. S.D. Zelenko, S.Y. Kondratyuk, The lichens of Darnitsa forest park (Kiev), Ukrayinskyi
Botanichnyi Zhurnal 51, 104–16, 1994.
18. L. Dymytrova, Epiphytic lichens and bryophytes as indicators of air pollution in Kyiv city
(Ukraine), Folia Cryptog. Estonica, Fasc. 46: 33–44, 2009.
19. www.microsoft.com, the official website of Microsoft.