ENVIRONMENTAL SAMPLES ANALYSIS BY ATOMIC ABSORPTION

SPECTROMETRY (AAS) AND INDUCTIVELY COUPLED

PLASMA-OPTICAL EMISSION SPECTROSCOPY (ICP-AES)

I. V. POPESCU1,2,3, C. STIHI1, GH. V. CIMPOCA1,2, G. DIMA1, GH. VLAICU4,

A. GHEBOIANU2, I. BANCUTA2, V. GHISA5, G. STATE6
1 ValahiaUniversity of Trgovite, Multidisciplinary Research Institute for Science
and Technologies, No. 2, Carol I Street, 130024 Trgovite, Romania,
Email: ivpopes@yahoo.com
2 Academy of Romanian Science
3 Horia Hulubei Institute of Physics and Nuclear Engineering, BucharestMgurele, Romania
4 Special Steel Complex, Physics Laboratories, Trgovite, Romania
5 Ovidius High School, Constana
6 Enchi Vcrescu High School, Trgovite, Romania

Received October 10, 2008

Biological samples are interested from many aspects of environmental

monitoring. Starting from assumption that the pollution factor from environmental
can modify the normal concentration of elements in biological samples, we decided
to control the presence of toxic elements and the deviation from their normal
concentration. The aim of this work is to determine the elemental composition of
some tree leaves situated in the vicinity of an industrial pollution source Special
Steel Trust Trgovite. Also, by this work we analyzed surface water from Ialomia
River from Dmbovia County. We try to demonstrate the applicability of different
atomic methods, like AAS and ICP-AES, for environmental monitoring of
Dmbovia County.
Key words: AAS, ICP-OES, leaves trees, Ialomia River.

1. INTRODUCTION

Environmental pollution remains are important issue for population,

economic and political decision factors in all countries. The small territory of
Romania is affected by pollutants from different pollution sources: chemical
industries, iron and steel smelter, coal mining and thermal power stations,
cement factories, auto traffic, the use of pesticides and fertilizer, so, it is vital to
know the elemental concentration of heavy and toxic elements in flora and fauna
and to quantify these using analytical methods.

Paper presented at the National Conference of Physics, 1013 September, 2008,
BucharestMgurele, Romania.

Rom. Journ. Phys., Vol. 54, Nos. 7 8 , P. 741746, Bucharest, 2009

742 I. V. Popescu et al. 2

In Dambovita zone, the main polluting regional industries are: stainless

steel works, Special Steel Trust Trgovite, cement and related materials
production (Fieni), glass and lighting sources production (Trgovite, Fieni),
chemicals materials production (Trgovite, Doiceti), coal mining and thermal
power station (Doiceti), oil exploration (Trgovite, Moreni, Gieti).
Using the methods of absorption and emission spectroscopy were studied
the concentration of elements in some tree leaves samples collected near Special
Steel Trust Trgovite and surface water samples from Ialomia River.
The Atomic Absorption Spectrometry (AAS) [1] is the most widely utilized
method today for rapid and quantitative elemental analysis. The detection limit
in AAS analysis method is up to 0.1 g/kg under optimum test conditions. A
material sample, in a liquid solution, is atomized through rapid heat application
and placed in the radiation path of several element-specific light source. The
sample atoms absorb ultraviolet or visible light and make transitions to higher
electronic energy levels. The analyte concentration is determined from the
amount of light absorption. The atomic density determine the absorption rate and
the Lambert-Beers law give the value of absorbance from each element of the
sample which is proportional with the concentration of that element. The
Lambert-Beer law is difficult to applying directly in AAS due to variations in the
atomization efficiency from the sample matrix, and nonuniformity of
concentration and path length of analyte atoms (in graphite furnace AA). The
high sensitivity by AAS is obtained using the relative analysis method.
The ICP-AES is an emission spectrometric technique [2, 3], exploiting the
fact that excited electrons emit energy at a given wavelength as they return to
ground state. The fundamental characteristic of this process is that each element
emits light at wavelengths peculiar to its chemical character. The intensity of the
light emitted at the chosen wavelength is proportional to the concentration of
that element in the analyzed sample. ICP-AES is a fast and high sensitivity
(ppb-ppm) multielemental analytical technique which can be applied to a wide
range of sample types: metals, archaeological, biological, and medical samples,
environmental samples (water streams, airborborne particles and coal fly ash,
etc.). The sample analyzed must be in solution.

2. EXPERIMENTAL

The atomic absorption spectrometer used by us is an AAS AVANTA GBC

with hallow cathode lamp (HCL).
The emission spectroscopy analysis were performed using the Baird ICP
2070 Sequential Plasma Spectrometer which consists of a sample introduction
system, a plasma torch, a plasma power supply and an optical measurement
system.
3 Environmental samples analysis 743

Samples: The samples analyzed by AAS and ICP-AES methods were

leaves of different trees: walnut (P1, P2) and apple tree (P3, P4) collected from
ten points of different distances from pollution source, Special Steel Trust,
Trgovite (Table 1). The leaves samples analyzed by AAS experiments were
prepared in the following manner: leaves of trees, collected of approximately in
some position, have been dried at a temperature of 105C in a clean box
preventing further contamination. The dried leaves have been grained and after
powdering 0.25 g powder leaves was digested in 8 ml nitric acid and 10 ml
peroxide. After digestion each solution sample was filtrated and diluted with
50 ml volume of deionized water.

Table 1
Type of samples
Sample code Type of sample
P1 (two samples) Leave of walnut (two samples)
P2 (two samples) Leave of walnut (two samples)
P3 (three samples) Leave of apple (three samples)
P4 (three samples) Leave of apple (three samples)
Collecting point
2 km distance of pollution source
5 km distance of pollution source
2 km distance of pollution source
5 km distance of pollution source

In ICP-AES measurements were analyzed the same leaves samples

prepared in the following manner: after powdering, dry 0.25 g powder leaves
were digested in 5 ml nitric acid. For a good digestion 10 ml perchloric acid
have been added together with 1 ml HCl. The cooled solution was diluted with
deionized water up to 100 ml solution.
The surface water samples were collected from Ialomia River (21 collecting
points). The samples is accurately weighed and then dissolved, often using
strong nitric acid. The resulting solution was diluted with deionized water up to
100 ml solution.

3. RESULTS AND DISCUSSIONS

Leaves of trees samples: The collected samples were analyzed by AAS

method at Atomic Absorption Spectrometry Laboratory of Valahia University of
Trgovite. The mean value of concentrations obtained is given in Table 2 for
elements: Cd, Co, Cu, Cr, Fe, Mn, Zn and Se. In the same samples, the mean
value Ca, Mg and Sr concentrations determined by ICP-AES technique are given
in Table 3.
The concentration values of Cu, Cr, Fe and Mn contained in samples
(Table 2) are slowly decreasing with the distance to pollution source. The
concentrations of Zn and Se (Table 2), Ca and Mg (Table 3) have for the same
samples, in the statistical limits, constant values. The concentration of Cd was
744 I. V. Popescu et al. 4

Table 2
The mean value of elemental concentrations (mg/Kg) in dry leaves tree samples obtained
by AAS method
Sample Cd Co Cu Cr Fe Mn Zn Se
P1 0.0085 0.1251 0.1789 0.4663 1.0932 0.1794 0.1525
P2 0.0261 0.0350 0.5349 0.3482 0.1675 0.1614
P3 0.0068 0.0791 0.4663 0.2987 0.1649 0.2526 0.1253 0.7203
P4 0.0054 0.0791 0.1946 0.1686 0.1238 0.7108

Standard error between 35%.

Table 3
The value of elemental concentrations (mg/Kg) in dry leaves
tree samples determined by ICP-AES method
Sample Ca Mg Sr
P1 47.2 7.89 0.181
P2 48.7 7.67
P3 72.7 8.04
P4 76.4 8.91

Standard error between 35%.

detected in P1 and P3 samples collected at 2 km away of pollution source and Sr

was determined only in P1 sample.
Water samples of Ialomia River: The concentrations of Fe, Mn and Zn
from surface water samples of Ialomia River determined by AAS method are
given in Table 4, with an instrumental error between 35%.
Standard values of surface water for class 1, 2 and 3 are presented in the
Table 5 which means: class 1 very clean fresh surface water, ecosystem
consummation where basic organisms can breed naturally, resources used for
consumption which requires ordinary water treatment processes before use;
aquatic organism of conservation, fisheries an recreation; class 2 medium clean
fresh surface water sources used for: consumption, but passing through and
ordinary treatment process before use and agriculture; fairly clean fresh surface
water resources used for consumption which requires special water; treatment
process before use and industry [4, 5, 7].
Natural water quality problems are caused mainly by Fe, Mn, Zn and
hydrogen sulphite and hardness [6]. When the water quality is investigated,
certain parameters can be used to indicate possible contamination: electrical
conductivity and chemical elements, for instance: K, Cl, S, Fe, Mn, Zn, Ni, Cd,
Cr, Pb and so on.
We can see (Table 4) that, there are important increases of Fe, Mn and Zn
concentrations after the passes of the river from Trgovite city, which is an impor-
5 Environmental samples analysis 745

Table 4
Fe, Mn and Zn concentrations on Ialomia River in different collecting points
Collecting points Fe [mg/L] Mn [mg/L] Zn [mg/L]
Moroieni aval 0.3 0.14 0.04
Moroieni amonte 0.2 0.19 0.04
Pietroia aval 0.41 0.15 0.05
Pietroia amonte 0.42 0.15 0.05
Fieni aval 0.38 0.22 0.05
Fieni amonte 0.35 0.25 0.04
Pucioasa aval 0.4 0.25 0.04
Pucioasa amonte 0.44 0.23 0.04
Braneti aval 0.42 0.18 0.04
Doiceti aval 0.39 0.51 0.07
Doiceti amonte 0.41 0.54 0.06
Trgovite aval 1.62 0.58 0.09
Trgovite amonte 1.43 0.59 0.08
Comiani aval 1.39 0.48 0.09
Comiani amonte 1.3 0.51 0.09
Bilciureti aval 1.32 0.32 0.08
Bilciureti amonte 1.33 0.33 0.09
Dobra aval 1.33 0.26 0.09
Dobra amonte 1.28 0.34 0.09
Bleni aval 1.31 0.38 0.09
Bleni amonte 1.31 0.36 0.08

Table 5
Standard values of surface water for Class1, 2 and 3
Element Class 1 [mg/L] Class 2 [mg/L] Class 3 [mg/L]
Ca 1 3 3
Fe 0.3 1 1
Cu 0.05 0.05 0.05
Ni 0.1 0.1 0.1
Mn 0.1 0.3 0.8
Zn 0.03 0.03 0.03
Cd 0.003 0.003 0.003
Cr 0.5 0.5 0.5
Pb 0.05 0.05 0.05
Na 100 200 200

tant industrial center of Romania. The present recommended limits for Fe, Mn
and Zn in water are respectively 0.3 mg/L, 0.1 mg/L and 0.03 mg/L (Table 5).
746 I. V. Popescu et al. 6

Water with a high Fe, Mn and Zn content is not considered a health problem, but
it can be very objectionable in taste, odor and appearance.

4. CONCLUSIONS

In summary the AAS and ICP-AES analysis methods give the possibility to
determine the elemental composition of environmental samples (flora and fauna)
with a great sensibility. High precision measurements [13, 7] of the
physical-chemical environmental factors are essential but not sufficient to assess
the response of ecosystems to stress. A main goal of environmental monitoring is
to monitories the state of whole ecosystems using bioindicators.

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