Spectrochimica Acta Part B 55 2000.

16431657

Determination of barium, chromium, cadmium,

manganese, lead and zinc in atmospheric particulate
matter by inductively coupled plasma atomic emission
spectrometry ICP-AES/
Iv. Boevski, N. DaskalovaU , I. Havezov
Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, BG 1113 Sofia, Bulgaria
Received 8 June 2000; accepted 29 June 2000

Abstract
The present paper has shown that the Q concept, as proposed by P.W.J.M. Boumans, J.J.A.M. Vrakking,
Spectrochim. Acta Part B 43 1988. 69, can be used as a basic methodology in the determination of Ba, Cr, Cd, Mn,
Pb and Zn in pairs of atmospheric particles by inductively coupled plasma atomic emission spectrometry ICP-AES..
The data base of Q values for line interference w Q I j a.x and Q values for wing background interference w QWJ a.x
were obtained in our former work wN. Daskalova, Iv. Boevski, Spectral interferences in the determination of trace
elements in environmental materials by inductively coupled plasma atomic emission spectrometry, Spectrochim. Acta
rtB 54 1999. 10991122x. The samples of atmospheric particles were collected by the Bergerhoff method. The
ICP-AES determination was performed after sample digestion with aqua regia. Q values were used for the
calculation of both the total interfering signal under the analysis lines and the true detection limits, depending on the
matrix constituents in the different samples. Comparative data for the concentration of analytes were obtained by
flame atomic absorption spectrometry FAAS. and direct current arc atomic emission spectrographic method dc
arc-AES.. 2000 Elsevier Science B.V. All rights reserved.
Keywords: ICP-AES; Q-concept; Atmospheric particulate matter; Trace elements; Correction procedure; True
detection limits

Corresponding author. Tel.: q3592-979-2543; fax: q3592-70-50-24.

E-mail address: banchem@bas.bg N. Daskalova..
0584-8547r00r$ - see front matter 2000 Elsevier Science B.V. All rights reserved.
PII: S 0 5 8 4 - 8 5 4 7 0 0 . 0 0 2 6 5 - 2

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I . Boe ski et al. r Spectrochimica Acta Part B: Atomic Spectroscopy 55 (2000) 16431657

1. Introduction

At present at least, accurate analysis of environmental materials other then natural or waste
waters requires dissolution of the samples. There
are a large number of possible objectives for this
type of analysis, including verification that a
material is legally defined as hazardous waste:
soils, sediments, sludges, atmospheric particulate
matter, mine tailing, industrial wastes, etc. The
most commonly used procedure for this analysis
is to solubilize the samples in question using an
acid digestion procedure and analyze the resulting liquid digestate by flame atomic absorption
spectrometry FAAS., electrothermal atomic absorption spectrometry ETAAS., inductively coupled plasma atomic emission spectrometry ICPAES. or inductively coupled plasma mass spectrometry ICP-MS.. Less common techniques such
as glow discharge and laser-induced breakdown
spectrometry have been used in the analysis of
gaseous species w16x
Instrumental methods are used to monitor airborne particulates outdoors w6x and in industrial
workplaces to safeguard occupational health w79x.
The coarse atmospheric aerosol fraction particles with aerodynamic diameter above 100 m.
determines dry sedimentation. The routes of this
type of aerosol exposure may involve skin deposition, the food chain after deposition on soils,
waters, plants, etc.. and inhalation w8x. The nature
and magnitude of the hazards in a given situation
depend on a complex combination of many factors, including particle size distribution, windspeed range, airborne concentration, particle
morphology, mineralogy and chemical composition. The chemical analysis of atmospheric particles is of great interest in order to estimate the
source and trend of atmospheric pollution. The
content of toxic pollutants of atmospheric particles is of interest for industrial hygiene chemistry.
The main functions of industrial hygiene chemistry are screening for chemical stressors during
the recognition phase and monitoring of specific
hazard concentrations during the evaluation w10x.
The application of the ICP-AES to air quality

monitoring is now widespread w6x. It is common

knowledge that spectral interference is the most
severe problem. However, the question of what it
actually is, why it is such a severe problem, and
what progress has been made in recent years to
cope with it, remains. The matrix may substantially worsen the accuracy and true detection
limits, and affect line selection, chiefly because of
spectral interference w11x.
A detailed experimental study of spectral interferences in ICP-AES in the analysis of a variety
of complex environmental materials has been
shown in a previous paper. Spectral data for Al,
Ca, Mg, Fe, Ti, K and Na as interferents for
200-pm wide windows centered "100 pm. around
the prominent lines of As, B, Ba, Be, Cd, Cr, Cu,
Hg, Mn, P, Pb, Sb, Se, Sn, Tl, U and Zn and a
quantitative data base of Q values for line interference w Q I a .x and for wing background interference w QW a .x were obtained w12x. The Qconcept, as proposed by Boumans and Vrakking,
was used for the quantification of the spectral
interferences w13,14x.
The purpose of this work was to demonstrate
experimentally the possibilities of ICP-AES by
using a data base of Q values w12x in the determination of Ba, Cr, Cd, Mn, Pb and Zn in atmospheric particulate matter. Comparative data for
the concentration of the above-mentioned elements will be obtained by the flame atomic absorption spectrometry FAAS. and the direct current arc atomic emission spectrographic method
dc arc-AES..

2. Experimental
2.1. Instrumentation
The Jobin Yvon Longjumeau, France. equipment and the operating conditions used in the
ICP-AES experiments are specified in Table 1.
The FAAS measurements were performed with
Pye Unicam SP 192 spectrometer, using the most
sensitive lines of the elements under the operat-

I . Boe ski et al. r Spectrochimica Acta Part B: Atomic Spectroscopy 55 (2000) 16431657

1645

Table 1
Specification of the spectrometer, ICP source and operating conditions
Monochromator
Mounting
Grating
Wavelength range
Dispersion
Entrance slit
Exit slit
Resultant spectral slit
Practical spectral band width
Photomultiplier

JY 38 Jobin Yvon, France.

CzernyTurner, focal length 1 m
Holographic, 2400 grooves mmy1
170700 nm first order.
0.38 nm mmy1
0.02 mm
0.04 mm
15.2 pm
15.6 pm
Hamamatsu TV, R 446 HA

Rf generator
Frequency
Oscillator
Power output
Nebulizer
Pump

Plasma Therm, model HFP 1500 D

27.12 MHz " 0.05%.
Crystal controlled at 13.56 MHz
0.51.5 kW
Meinhard, concentric glass
Peristaltic, ten-roller, Gilson Minipuls
Gilson Medical Electronics, France.

Operating conditions
Incident powerrkW
Outer argon flow raterl miny1 .
Carrier flow raterl miny 1 .
Liquid uptake raterml miny1 .
Nebulizer pressure flowrlbf iny2 .
Transport efficiency of ICP systemr%
Excitation temperature
of ICP plasmarK

ing conditions recommended in the manuals, including deuterium background correction.

Table 2 shows the specification of the spectrograph, dc power generator and operating conditions.

1.0
15
0.4
1.3
20 1.38 bar.
3
7200

method w15x from four separate spots around a

metallurgical company in Sofia, Bulgaria. The
samples were air dried and ground in a rotating
plastic drum and were delivered for analysis to
the Institute for Hygiene and Occupational
Health, Sofia.

2.2. Reagents
2.4. Digestion procedure
Reagents of the highest purity grade were used:
30% HCl Suprapur, Merck.; 65% HNO 3
Suprapur, Merck.; and tridistilled water from a
quartz apparatus. Stock solutions of the analyte 1
mg mly1 . were prepared from Merck Titrisols.
PTFE ware was used throughout.
2.3. Sampling
The samples were collected by Bergerhoffs

The extraction of trace elements soluble in

aqua regia wISO 11466:1995 E.x was used as a
decomposition method for reasons outlined in
our previous paper w12x.
A 0.5-g sub-sample was weighed in a reaction
vessel; 0.5 ml of tri-distilled water was added to
obtain a slurry, followed by 4.5 ml of HCl 12 mol
ly1 . and 1.5 ml HNO3 15.8 mol ly1 .. Then 10 ml
of 0.5 mol ly1 HNO3 were added to the absorp-

1646

I . Boe ski et al. r Spectrochimica Acta Part B: Atomic Spectroscopy 55 (2000) 16431657

Table 2
Specification of the spectrograph, dc power generator and operating conditions
Spectrograph
Grating
Registered spectrum
Illumination system
Slit width
Hartmanns diaphragms
D.C. power generator
Operating conditions
Current
Exposure time

Electrodes
Electrode shape

Electrode spacing
Amount of sample
Spectral plates
Wavelength of analysis
Prominent lines

tion vessel and connected with the reflux condenser. Both apparatus were placed on the top of
the reaction vessel and the sample was allowed to
stand for 16 h at room temperature for slow
oxidation of the organic matter and reduction of
the gases produced during the subsequent heating
cycle. They were heated under reflux until boiling
for 2 h and allowed to cool slowly at room temperature. The contents and the subsequent rinses
of the absorption vessel were passed through the
condenser into the reaction vessel. The content of
the reaction vessel was transferred quantitatively
to a 25-ml graduated flask and filled up to the
mark with 0.5 mol ly1 HNO3 . After the undissolved material had settled, the supernatant solution was subjected to analysis by ICP-AES or
FAAS. A blank sample containing the acids used
for digestion was prepared in the same way
All glass and plastic ware were kept in 10% vrv
HNO3 for at least one night and then rinsed with
1% vrv HNO3 , and subsequently with distilled
water before use.

PGS-2 Jena, GDR.

Ruled, 650 groves mmy1
-blaze 570 nm
In the second order
One lens, quartz condenser,
f s 80
20 m
S-10 7, 3, 2.
Three phase rectifier, 280 V, 20 A
10 s
30 s Cd, Zn.
60 s Cr.
80 s Ba, Mn.
RW-0 Ringsdorf-Werke GMBH,
Mehlem.
Crater 3. 5 mm diameter,
4. 0 mm depth the electrode with
Sample set as anode.; half-sphere
upper electrode.
4 mm
10 mg
WU-2 ORWO.
Ba I 307 159 pm ; Cd I 326 106 pm
Cr II 283 563 pm ; Mn II 293 930 pm
Pb I 283 306 pm ; Zn I 328 233 pm

2.5. Calibration procedures

2.5.1. ICP-AES and FAAS
The reference solutions for the determination
of the analytes were prepared on the basis of a
blank containing the acids used for digestion and
a complex matrix. The number of reference solutions for any particular analyte ranged from 5 to
20, depending on the necessary concentration
range. It was not necessary to run all 20 reference
solutions for each calibration.
2.5.2. dc Arc-AES
Certified standard reference materials: IAEAr
marine sediment SD-N-1r2; IAEArlake sediment SL-1; IAEArSOIL-5; and IAEArSOIL-7
were used for calibration. These reference materials could be used for calibration for the following reasons:
1. they were of approximately the same mineral
composition;

I . Boe ski et al. r Spectrochimica Acta Part B: Atomic Spectroscopy 55 (2000) 16431657

2. the reference materials were ground to 100

m in a rotating plastic drum. Such grinding
is designed to give a homogeneous sample
from which a sub-sample is taken; and
3. the concentration level of the analytes
permitted the analysis of samples in a wide
concentration range.

3. Results and discussion

1647

tion of the true detection limits in the case of a

multicomponent system by using Eq. 1. w23x:
CL ,true s 2r5 J Q I J a . = CI J q CL ,conv
s 2r5 J BEC I J q CL ,conv

1.

where the conventional detection limit can be

written as:
CL ,conv s 2'2 = 0.01= RSDBL= w BEC
q jQ I J a . = CI J q J QW J a . = CI J x

3.1. ICP-AES method

3.1.1. Data base of Q- alues
Spectral interferences, especially line overlaps,
are a major problem in atomic emission radiation
sources, but it is emphasized with the ICP because of the richness of the spectra. The ICP
emits lines which do not appear in the classical
tables w16,17x. The relative intensities of the spectral lines emitted by the classical sources w16,17x
and the ICP w18x are different. These are the
reasons why various groups of workers have embarked upon the compilation of new data relevant
to ICP w12,1923x. A detailed experimental study
of spectral interferences in ICP-AES encountered
with environmental materials was shown in our
previous work w12x. Table 3 lists the prominent
lines of analytes: Ba, Cd, Cr, Mn, Pb and Zn,
Q w a . values for wing background interference
and Q I a . values for line interference in the
presence of 2 mg mly1 Al, Ca, Mg, Fe and Ti,
respectively, as interferents. The term Q I a . is
expressed as the ratio SI a .rSA , where S I a . is
the partial sensitivity of the interfering line, defined as the signal per unit interferent concentration produced by the interfering line at the peak
wavelength of the analysis line a , and SA is the
sensitivity of the analysis line signal per unit
analyte concentration .. The term Q w a . is expressed as the ratio S w a .rSA , where Sw a .
is the wing sensitivity of the interfering line in the
spectral window a and S A is as stated above.
The best analysis lines in the presence of a
complex matrix are printed in bold.
These data were used for: a. the determina-

s 2'2 = 0.01= RSDBL

= w BEC q J BEC I J q J BEC W J x

2.

and b. calculation of the interfering background

signals w J BEC I J q J BEC W J x under the prominent analysis lines for the samples with different
matrix concentrations.
The total background signals under the best
analysis lines included the background equivalent
concentration in the solvent blank due to source
and solvent., i.e. BEC Total s BEC q J BEC I J q
J BEC W J .
Table 4 shows the interferent matrix concentrations CI J for which Q I J a . s 0 by using equation
Q I J a . = CI J s CL w23x. Table 5 lists the wavelengths of all prominent lines of analytes, the
background equivalent concentration BEC, g
mly1 . and the detection limits CL , g mly1 . in
the pure solvent acids used for digestion.
obtained under our experimental conditions Table 1. by using Eq. 3. w23x:
CL s 2'2 = 0.01= R.S. D. B = BEC

3.

where R.S.D.Bs 1% is the relative standard deviation of the background; and BEC is the background equivalent concentration in g mly1 ..
3.1.2. Analysis of samples of atmospheric particulate
matter
Four samples of atmospheric particles were
collected by the Bergerhoff method from separate
spots around a metallurgical company Section
2.3..

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I . Boe ski et al. r Spectrochimica Acta Part B: Atomic Spectroscopy 55 (2000) 16431657

3.1.2.1. Determination of major components. The

ICP-AES determination of matrix components Al,

Ca, Fe, Mg and Ti was performed after digestion

with aqua regia Section 2.4.. The accuracy was

Table 3
Values of QW a . and Q I a . for prominent lines of Ba, Cd, Cr, Mn, Pb and Zna
Analysis lines
pm.

Interferents

QW a .

QI a .

Ba II 455 404

Al
Ca
Fe
Mg
Ti

0
9.0= 10I6
0
4.5= 10I5
2.6= 10I6

0
0
0
0
0

Ba II 493 409

Al
Ca
Fe
Mg
Ti

2.0= 10y6
7.4= 10y6
5.0= 10y7
4.0= 10y7
3.3= 10y6

0
0
4.0= 10y5
0
0

Ba II 233 527

Al
Ca
Fe
Mg
Ti

2.6= 10y6
5.2= 10y5
5.6= 10y5
1.7= 10y5
4.4= 10y5

0
0
6.1= 10y5
0
0

Ba II 230 424

Al
Ca
Fe
Mg
Ti

0
7.2= 10y5
2.9= 10y5
2.3= 10y5
5.0= 10y5

0
0
4.1 = 10y5
0
0

Cd II 214 438

Al
Ca
Fe
Mg
Ti

0
1.3= 10I4
6.0= 10I4
0
8.5= 10I4

0
0
0
0
0

Cd I 228 802

Al
Ca
Fe
Mg
Ti

6.6= 10y5
7.0= 10y4
6.3= 10y4
4.8= 10y4
4.7= 10y4

0
0
0
0
0

Cd II 226 502

Al
Ca
Fe
Mg
Ti

6.0= 10y6
4.0= 10y4
9.1= 10y5
4.7= 10y4
7.0= 10y4

5.7= 10y5
0
0
0
0

Cr II 205 552

Al
Ca
Fe
Mg
Ti

3.4= 10y4
3.6= 10y4
7.0= 10y5
2.5= 10y4
2.0= 10y4

0
0
1.1= 10y4
0
0

I . Boe ski et al. r Spectrochimica Acta Part B: Atomic Spectroscopy 55 (2000) 16431657
Table 3 Continued.
Analysis lines
pm.

Interferents

QW a .

QI a .

Cr II 206 149

Al
Ca
Fe
Mg
Ti

0
4.2= 10y4
2.2= 10y4
3.2= 10y4
1.9= 10y4

0
0
0
0
1.8= 10y4

Cr II 267 716

Al
Ca
Fe
Mg
Ti

0
1.2= 10I5
6.7= 10I5
3.7= 10I5
1.2= 10I5

0
0
0
0
2.7= 10I5

Cr II 283 563

Al
Ca
Fe
Mg
Ti

0
2.8= 10y6
5.7= 10y6
1.3= 10y4
0

0
0
1.0= 10y3
0
2.7= 10y5

Mn II 257 610

Al
Ca
Fe
Mg
Ti

4.7= 10I6
5.5= 10I6
1.1= 10I5
9.5= 10I6
4.7= 10I6

0
0
0
0
0

Mn II 259 373

Al
Ca
Fe
Mg
Ti

0
4.7= 10y6
1.7= 10y5
8.8= 10y6
3.5=10y6

0
0
6.9= 10y40

Pb II 220 353

Al
Ca
Fe
Mg
Ti

9.7= 10I4
5.3= 10I4
4.1= 10I4
4.5= 10I4
5.2= 10I4

4.0= 10I4
0
0
0
5.510I5

Pb I 216 999

Al
Ca
Fe
Mg
Ti

2.8= 10y3
2.1= 10y3
6.9= 10y4
1.7= 10y3
1.3= 10y3

4.0= 10y3
0
1.0= 10y3
0
0

Pb I 261 418

Al
Ca
Fe
Mg
Ti

9.1= 10y5
4.1= 10y4
6.3= 10y3
3.2= 10y4
2.8= 10y4

0
0
1.1= 10y2
0
1.4= 10y4

3.7= 10y5

1649

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I . Boe ski et al. r Spectrochimica Acta Part B: Atomic Spectroscopy 55 (2000) 16431657

Table 3 Continued.
Analysis lines
pm.

Interferents

QW a .

QI a .

Pb I 283 306

Al
Ca
Fe
Mg
Ti

0
3.5= 10y4
0
3.8= 10y3
3.3= 10y4

0
0
3.6= 10y3
0
5.3= 10y4

Zn I 213 856

Al
Ca
Fe
Mg
Ti

4.1= 10y5
2.7= 10y5
0
0
1.7= 10y5

0
0
1.1= 10y4
0
3.0= 10y5

Zn II 202 548

Al
Ca
Fe
Mg
Ti

1.4= 10y4
2.2= 10y4
9.8= 10y5
3.1= 10y4
1.2= 10y4

0
0
0
4.0= 10y4
0

Zn II 206 200

Al
Ca
Fe
Mg
Ti

3.0= 10I4
1.8= 10I4
7.4= 10I5
1.5= 10I4
1.1= 10I4

0
0
0
0
0

Interferents: aluminium 2 mg mly1 ., calcium 2 mg mly1 ., iron 2 mg mly1 ., magnesium 2 mg mly1 . and titanium 2 mg
ml .
a

y1 .

improved by using two selected analysis lines for

each element: Al I 237 324 pm; Al I 394 401 pm;
Ca I 422 673 pm; Ca II 315 887 pm; Fe II 238 204
pm; Fe II 239 562 pm; Mg II 279 806 pm; Mg II
285 213 pm; Ti II 334 941 pm; and Ti II 336 121
pm w11x.
The basic sample solutions were diluted dilution factor s 4. in order to eliminate the multiplicative interferences due to the matrix constituents w12x. The reference solutions were prepared on the basis of an acid blank Section
2.5.1..
The results obtained in g mly1 are presented
in Table 6. The R.S.D. is 5%.
3.1.3. Determination of impurities of Ba, Cd, Cr,
Mn, Pb and Zn
3.1.3.1. Determination of contaminations in sol ent blank solutions. Random errors, which, due to
contaminations of the solvent blank with a given
analyte, can be eliminated by the determination

of Ba, Cd, Cr, Mn, Pb and Zn in solvent blank

samples. The blank samples, containing the acids
used for digestions was prepared following the
digestion procedure Section 2.4.. The background was corrected for by a simple off-peak
background measurement.
3.1.3.2. Calculation of the total background signals under the best analysis lines. By using the
Q I J a . and QW J a . values Table 3. for the
best analysis lines, the interferent concentrations in sample solutions CI J . Table 6. the background equivalent concentration for line interference w J BEC I J s J Q I J = C I J . s BEC IAl q
BEC ICa q BEC I Mg q BEC I Fe q BEC I Ti Table 7,
column 2., the background equivalent concentration for wing interference w J BEC W J s J
Q I W = CI J . s BEC WAl q BEC W Ca q BEC W Mg q
BEC W Fe q BEC W Ti x Table 7, column 3. and the
background equivalent concentrations in pure
solvent Table 5., the total background signals
wBEC q J BEC I J q J BEC W J x at the peak wave-

I . Boe ski et al. r Spectrochimica Acta Part B: Atomic Spectroscopy 55 (2000) 16431657

1651

Table 4
Interferent concentrations C I J for which Q I J a . s 0 for aluminium, iron and titanium as a matrix elements
Analysis lines
pm.

Interferent concentrations CI J , g ml y 1
for which QI J a . s 0
Aluminium

Iron

Titanium

Ba II 455 403
Ba II 493 409
Ba II 233 527
Ba II 230 424

20
70
140

Cd II 214 438
Cd I 228 802
Cd II 226 502
Cr II 205 552
Cr II 206 149

100

120

120

Cr II 267 716
Cr II 283 563

710

200
260

Mn II 257 610
Mn II 259 373

35

Pb II 220 353
Pb I 216 999
Pb I 261 418
Pb I 283 306

125
40

150
20
60

900

1300
4100

Zn I 213 856
Zn II 202 548
Zn II 206 200

50

150

length a of the analysis lines were measured

Table 7, column 4.. For a given matrix composition Table 6. the following should be noted:
1. The interferent Ti concentrations for the
best analysis lines of Cr and Pb for which
Q I Ti a . s 0 were significantly higher Table
4. in comparison with the corresponding values in sample solutions Table 6.: CI Ti ranged
from 4.8 to 6.6 g mly1 .. Hence, in both
cases BEC I Ti < BEC q J BEC W J , i.e.
BEC I Ti could not influence both the total
background correction factor and the true
detection limit CL,true s CL,conv ..
2. The interferent Al concentrations for the
best analysis line of Pb for which Q IAl s 0
Table 4. were lower in comparison with the
interferent concentrations in sample solutions

Table 6.: CIAl ranged from 183 to 265 g

mly1 . Hence, in the determination of Pb in
atmospheric particulate matter the background under a prominent line varied with
the sample composition. These values ranged
from 0.07 to 0.11 g mly1 Table 7, column
2., whereas the total background signals
BEC total . varied from 2.41 to 2.93 g mly1
Table 7., i.e. BEC IAl < BEC total . Due to the
high total background signals, the lower interferent signals BEC IAl could not be distinguished, i.e. CL,true s CL,conv .. Fig. 1 presents
examples of spectral scans over a spectral
region around the analysis line Pb II 220 353
pm: 1. 10 g mly1 lead in pure solvent; and
2. matrix blank s 270 g mlyl Al, 1250 g
mly1 Ca, 170 g mly1 Mg, 1300 g mly1 Fe,
7 g mly1 Ti. This was a real situation in the

1652

I . Boe ski et al. r Spectrochimica Acta Part B: Atomic Spectroscopy 55 (2000) 16431657

should be noted that the contamination from Mn

and Zn was registered in solvent blank samples
and its concentration determined Section 3.1.3.1..
The analytical results for Mn and Zn were
obtained by correction of both the spectral interferences and analyte concentrations in solvent
blank samples.
3.1.3.3. Detection limits. In Section 3.1.3.2, it was
shown that J BEC I J s 0 for the samples 14.
Hence, the true detection limits s conventional
detection limits. By using Eq. 2. in combination
with Q-values Table 3. and interferent concentrations for Al, Ca, Fe, Mg and Ti Table 6., the
conventional detection limits in ng mly1 , column
2. and the same detection limits with respect to
the dissolved solid in g gy1 , column 3. were
calculated Table 9..
Table 5
The wavelengths of all investigated prominent lines in this
work, the background equivalent concentration BEC, g
mly1 . and the detection limits in the pure solvent CL , ng
mly1.

Fig. 1. Example of spectral scans over a spectral region around

the analysis line of lead: 1. central wavelength 222 353 pm
Pb line. 10 g mly1 Pb in pure solvent; and 2. complex
matrix bland s 270 g mly1 Al q 1250 g mly1 Ca q 170 g
mly1 Mgq 1300 g mly1 Fe q 7 g mly1 Ti.

determination of lead in sample 3 the concentration of matrix elements was higher in

comparison with the concentration of the
same elements in samples 13 Table 6.. The
background enhancement could be corrected
for by a simple off-peak background measurements.
By using the total background correction factor, the content of Ba, Cd, Cr, Mn, Pb and Zn in
g gy1 were obtained Table 8, column 1.. It

Analysis lines
pm.

BEC g mly1 .

CLng mly1 .

Ba II 455 403
Ba II 493 409
Ba II 233 527
Ba II 230 424

0.02
0.03
0.14
0.20

0.65
0.79
4
5.7

Cd II 214 438
Cd I 228 802
Cd II 226 502

0.30
0.20
0.20

8.3
5.7
5.7

Cr II 205 552
Cr II 206 149
Cr II 267 716
Cr II 283 563

0.40
0.70
0.20
0.25

12
21
5.7
7.1

Mn II 257 610
Mn II 259 373

0.04
0.04

1.2
1.2

Pb II 220 353
Pb I 216 999
Pb I 261 418
Pb I 283 306

1.30
5.00
6.30
7.60

Zn I 213 856
Zn II 202 548
Zn II 206 200

0.16
0.30
0.40

37
140
180
216
4.5
8.5
12

I . Boe ski et al. r Spectrochimica Acta Part B: Atomic Spectroscopy 55 (2000) 16431657

The results from Tables 8 and 9 showed the

following:

1653

accuracy and precision of an analytical determination.

1. By using the best analysis line, the concentrations of Cd in samples 1 and 2 were in the
vicinity of the detection limit concentration
levels and could be determined with a desired
level of precision.
2. In most cases, the analyte concentration determined by the best analysis lines substantially exceeded the detection limits Tables 8
and 9.. When the analyte concentration substantially exceeded the detection limits as in
the case of Ba, Cr, Mn, Pb and Zn. the use of
a second analysis lines with Q I J s 0 was justified. In such cases the equation Q I J = CI J s
CL was used. The interferent concentration
CI J for which Q I J s 0 Table 4. and the dilution factor of the sample solution were determined. When necessary, more than two
analysis lines could be used for improving the

3.2. FAAS method

ICP-AES and FAAS are principally intended
for the determination of impurities in liquids. The
greatest contrast between ICP-AES and FAAS
lies in the domain of inter-element interferences.
The type of interferences most commonly encountered in each of the two techniques is virtually mutually exclusive. In FAAS, inter-element
interferences are mostly chemical in nature,
whereas spectroscopic interferences such as line
overlaps are virtually non-existent. In ICP-AES,
the opposite is true. With an appropriate choice
of plasma operating conditions, chemical interferences are reduced to negligible proportions, but,
in turn, the spectral interferences are the basic
problem w6x. The characterization of, and correc-

Table 6
Content of Al, Ca, Mg, Fe and Ti in solution g mly1 . derived after dissolution of the different samples a
Analysis
lines,
pm.

Concentrations g mly1 .
Sample 1
Xi

Al I 237 324

Sample 2
X

Xi

204

200

Ca I 422 673

1120
1110

Mg II 279 806

150

Mg II 285 213

146

Fe II 238 204

980

Fe II 239 562
Ti II 334 941
Ti II 336 121
a

6.0

615
620

6.5
5.5

5.6

610
1275

1270

5.4

103
106

1280
1046

5.9

100
169

166

1042

1051
1054

172

1050

5.8

1048
1249

161
162

183
186

1248

160

1000

180

1250
1049

1053

265
270

1045

990

Xi

260

218

148

Sample 4
X

219

1115
Ca II 315 887

Xi

220
202

Al I 394 401

Sample 3

5.0
6.6

6.7

4.8
4.6

Notes: X i is the mean of three replicates by using a given analysis line; X is the mean values of two concentrations, obtained by
using two analysis lines of each analyte.

1654

I . Boe ski et al. r Spectrochimica Acta Part B: Atomic Spectroscopy 55 (2000) 16431657

Table 7
The background equivalent concentration for line interference wBEC I J , g mly1 x column 2., background equivalent concentration
for wing background interference wBEC W J , g mly1 x column 3. and total background signal at the peak wavelength a wBEC Total,
g mly1 x column 4. for the best analysis lines
The best
analysis lines
pm.

Sample
No

J BECI J ,
g mly1

J BECW J ,
g mly1

BECTotal ,
g mly1

Ba II 455 403

1
2
3
4

0
0
0
0

0.017
0.017
0.019
0.014

0.25
0.25
0.25
0.24

Cd II 214 438

1
2
3
4

0
0
0
0

0.75
0.78
0.94
0.51

1.05
1.08
1.24
0.81

Cr II 267 716

1
2
3
4

0
0
0
0

0.120
0.12
0.15
0.09

0.37
0.37
0.40
0.34

Mn II 257 610

1
2
3
4

0
0
0
0

0.02
0.04
0.06
0.02

0.06
0.08
0.10
0.06

Pb II 220 353

1
2
3
4

0.08
0.09
0.11
0.07

1.27
1.28
1.52
1.04

2.65
2.67
2.93
2.4

Zn II 206 200

1
2
3
4

0
0
0
0

0.36
0.34
0.43
0.30

0. 76
0.74
0.83
0.70

tion for, various spectroscopic interferences encountered in the determination of Ba, Cd, Cr,
Mn, Pb and Zn in atmospheric particulate matter
has been shown in Section 3.1. Comparative data
for the concentration of above-mentioned analytes were obtained by FAAS as an alternative
method for the analysis of the same sample solutions Table 8, column 2..
3.3. dc Arc-AES method
The dc arc-AES method for the analysis of
solid samples of atmospheric particulate matter
was used. The specification of the spectrograph,

dc power generator and operating conditions for

the direct spectral determination of Ba, Cd, Cr,
Mn, Pb and Zn in samples 14 are listed in Table
2. The concentrations of the analytes are shown
in Table 8 column 3..
Using Students criterion, no statistical differences between the results obtained by the ICPAES, FAAS and dc arc-AES methods was found.
It followed from the results that Ba, Cd, Cr, Mn,
Pb and Zn are soluble in aqua regia, and Q-values provided a realistic estimation of the interference effects and could be used for the calculation
of the total interfering background signals under
the prominent analysis lines.

I . Boe ski et al. r Spectrochimica Acta Part B: Atomic Spectroscopy 55 (2000) 16431657
Table 8
Element determination in couples of atmospheric particulate
matter mean of three replicates.
Sample Element Concentrations, g gy1
No
ICP-AES
FAAS

dc Arc-AES

1.

Ba
Cd
Cr
Mn
Pb
Zn

695 " 10
1.52" 0.05
250 " 5
355 " 8
165 " 5
495 " 10

707 " 10
1.53" 0.05
242 " 5
356 " 6
176 " 5
495 " 10

690 " 25
1.58" 0.1
245 " 20
360 " 15
169 " 10
510 " 25

2.

Ba
Cd
Cr
Mn
Pb
Zn

2000 " 5
2.15" 0.05
475 " 10
1800 " 6
265 " 5
715 " 8

2010 " 5
2.16" 0.05
470 " 10
1805 " 5
270 " 5
710 " 6

2025 " 20
2.18" 0.1
465 " 20
1810 " 20
275 " 20
698 " 25

3.

Ba
Cd
Cr
Mn
Pb
Zn

2148 " 5
33.0" 0.05
85.0" 5
790 " 5
288 " 5
1280 " 5

2152 " 5
32.5" 0.05
88.0" 5
790 " 5
285 " 5
1285 " 5

2150 " 20
34.0" 0.1
84.0" 10
788 " 15
282 " 10
1278 " 15

4.

Ba
Cd
Cr
Mn
Pb
Zn

1600 " 5
8.70" 0.05
138 " 5
385 " 5
176 " 5
1170 " 5

1605 " 5
8.68" 0.05
138 " 5
390 " 5
178 " 5
1165 " 5

1598 " 15
8.65" 0.1
140 " 10
383 " 10
170 " 10
1162 " 12

3.4. Conclusion

The background under a spectral line cannot

be directly determined and, in addition, it varies
with the sample composition Table 6.. It might
appear from the literature that a variety of instrumental background correction procedures exist.
All approaches are based on the visual inspection
of wavelength scans of samples, standards, and
blanks to make a judicious choice of the wavelengths at which the background is measured.
The ideal background correction requires the simultaneous collection of accurate data on analytical and background signals under the prominent
analysis lines. The Q-concept ensures a possibility

1655

for the quantification of the spectral interferences

in the presence of Al, Ca, Fe, Mg and Ti as a
basic interferents in environmental materials for
a relevant set of analysis lines Table 3.. These
data were used for:
1. quantitative line selection: the best analysis
lines are free or negligibly influenced by line
interference Table 3.;
2. calculation of the interfering background signals w J BEC I J q J BEC W J x under the
prominent analysis lines for the samples with
different matrix concentrations Table 7.. The
total background signals under the best
analysis lines includes the background equivalent concentration in the solvent blank due
to source and solvent., i.e. BEC Total s BEC q
J BEC I J q J BEC W J ; and
3. calculation of the true detection limits in this
case CL , true s CL , conv.; Table 9, column 1.
which can determine the vicinity of the detection limit concentration levels Table 8, samples 1 and 2, content for Cd..
The results obtained in the determination of
Ba, Cd, Cr, Mn, Pb and Zn in samples of atmospheric particulate matter by ICP-AES method
agree well with the corresponding values obtained
by both FAAS and dc arc-AES methods Table
8.. It should be noted, however, that the dc arcAES method is a direct method for the analysis of
solid samples. In this way, the efficiency of extraction of Ba, Cd, Cr, Mn, Pb and Zn from samples
of atmospheric particulate matter in aqua regia
was experimentally demonstrated. Hence, the
selected digestion procedure provides enough information about the hazardous waste contribution, such as Ba, Cd, Cr, Mn, Pb and Zn.

Acknowledgements
Thanks are due to the National Found Scientific Research of the Ministry of Education, Science and Technology of Bulgaria for financial
support of this work under registration N X-544.

1656

I . Boe ski et al. r Spectrochimica Acta Part B: Atomic Spectroscopy 55 (2000) 16431657

Table 9
Conventional detection limits ng mly1 . and the same detection limits with respect to the dissolved solid in g gy1 .
CL, conv.
ng mly1 .

CL,conv.
g gy1 .

Sample
No

Best analysis
lines, pm

1.
2.
3.
4.

Ba II 455 403

7.0
7.0
7.0
7.0

0.35
0.35
0.35
0.35

1.
2.
3.
4.

Cd II 214 438

30.0
31.0
35.0
23.0

1.50
1.55
1.75
1.15

1.
2.
3.
4.

Cr II 267 716

10.5
10.5
11.3
9.6

0.53
0.53
0.57
0.48

1.
2.
3.
4.

Mn II 257 610

1.7
2.3
2.8
1.7

0.09
0.10
0.14
0.09

1.
2.
3.
4.

Pb II 220 353

75.0
75.0
83. 0
68. 0

3.75
3.78
4.15
3.40

1.
2.
3.
4.

Zn II 202 548

19.0
19.0
21.0
17.5

0.95
0.95
1.10
0.88

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