Mikrochim.
Acta 127, 281-286 (1997)
Determination of Some Trace Elements in High-Purity Aluminium,
Zinc and Commercial Steel by AAS After Preconcentration on
Amberlite XAD-1180 Resin
Serife Tokallo~lu, Senol Kartal, and Latif Eiqi*
Department of Chemistry,Erciyes University,TR-38039 Kayseri, Turkey
Abstract. The determination of trace metals, e.g. Bi,
Cd, Pb, in high-purity aluminium, zinc and commercial
steel by flame or graphite furnace atomic absorption
spectrometry following their preconcentrations as iodo
complexes on XAD-1180 resin by means of a short
column system is described. The recoveries are quan-
titative (>~ 95%). The relative standard deviations
varies between 6% and 10%. The relative errors are
less than 8% in a concentration range of 1 x 10 -3 - 4 x
10-5%. Detection limits for flame AAS and GFAAS
were in the ranges of 0.002-0.110 pg/ml and 0.0003-
0.004 pg/ml or in the ranges of 0.08-4.40 pg/g and
0.012-0.16 pg/g with respect to the solid samples,
respectively.
Key words: AAS,preconcentration,XAD-1180,tracesof bismuth,
cadmium and lead, high-purityaluminiumand zinc, steel.
Trace impurities and doped elements strongly influ-
ence the chemical and physical properties of high-
purity metals, alloys and catalyzers [1]. The determi-
nation of impurities in these samples is essential to
control their qualities and to investigate the potential
influence and synergistic action of the impurities.
With most of the instrumental methods, their reliable
direct determinations are not possible because of
strong interferences caused by the sample matrix and
because of the low concentration level of analytes. It
is useful, therefore, to employ preconcentration and
separation methods combined to instrumental meth-
ods such as spectrophotometry, AAS, AES, etc. For
such work, short chromatographic columns have
* To whom correspondenceshould be addressed
Mikrochimica Acta
9 Springer-Verlag1997
Printed in Austria
recently become popular and the use of sorption
resins, particularly Amberlite XAD resins, as packing
materials has substantially increased [2-5]. An
advantage of XAD resins is that only relatively small
volumes of eluent, such as 2 ml, need to be used for
stripping the column quantitatively. This feature
provides a high analytical preconcentration factor
for large volume samples. Furthermore, XAD resins
consisting of hydrophobic polystyrenedivinylbenzene
polymers can adsorb neutral complexes formed
between metal ions and inorganic ligands as well as
metal chelate complexes [2-9]. The possibility to
adsorb complexes with inorganic ligands on the resins
with a high adsorption capacity is advantageous as
consequently no free inorganic ligands are retained.
Very little works have been done to apply the
retention of inorganic complexes onto XAD resin for
the isolation of trace elements on an XAD resin
column. Recently, we have made an attempt to use
such a combination for the preconcentration of Bi, Cd,
Cu and Pb in zinc matrices with the aid of a mixture
of iodo and thiocyanato complexes [8, 9]. In this
work, the retention of trace metal ions as iodo
complexes on a column filled with XAD-1180 resin
was investigated for the reliable determination of the
important analytes in selected metal samples such as
high purity aluminium, zinc and commercial steel.
Experimental
Apparatus
A Hitachi atomicabsorption spectrometer(ModelZ-8000) with an
air/acetylene flame and Zeeman background correction was used
for the determinationof the metal ions in all solutions.The sample
282 ~. Tokaho~lu et al.

Table 1. The operation conditions for flame AAS

Parameters Cadmium Lead

Lamp current/mA 7.5 7.5

Wavelength/nm 228.8 283.3
sample
Spectral slit width/nm 1.3 1.3
solution
Air flow rate/1 rain -1 9.5 9.5
Acetylene flow rate/1 rain -1 2.3 2.5
Burner height/a.v. 7.5 7.5

disc
Table 2. The operation conditions for GFAAS

Parameters Cadmium Bismuth

Lamp current/mA 7.5 12.5

Wavelength/nm 228.8 223.1
Slit width 1.3 0.2
Sample volume/gl 10 10 21--- to vacuum
Carrier gas (200 ml/min) Ar Ar
Temperature programme/time
Dry 1 80 to 100~ 80 to 100~ s
Dry 2 100~ s 100 to 120~ s
Ash 1 250 to 300~ 250 to 300~ s
Ash 2 300~ s 300~ s
Atomizationa 1500 ~C/6 s 2000 ~C/10 s Fig. 1. Preconcentration system with a short glass column
Clean 1800~ s 2400~ s

a Gas interrupt mode use.

solutions were introduced into the nebulizer of the flame atomic
absorption spectrometer (flame AAS) with the injection technique
[10]. For graphite furnace atomic absorption spectrometry
(GFAAS), a Hitachi Model 180-704 graphite tube atomizer was
used. Injection volumes were 100 gl for flame AAS and 10 gl for
GFAAS. The optimum operating conditions for flame AAS and
GFAAS were shown in Tables 1 and 2, respectively.
Calibration in flame AAS and GFAAS were performed with
synthetic standard solutions and by standard addition method,
respectively.
Chemicals
All chemicals used were of analytical-reagent grade. Water,
redistilled in a quartz apparatus, was used throughout. As the
work stock solutions, 1000 gg/ml, of Bi, Cd, Co, Cr, Cu, Fe, Mn,
Ni, Pb, and Zn were prepared by dissolving the respective nitrate
salts in 1% (w/w) HNO3. Working solutions were prepared by
appropriate dilution prior to use.
In the digestion of alurninium, zinc and steel, hydrochloric acid
37% (suprapur, Merck) and nitric acid 65% (suprapur, Merck)
were used. Sodium iodide (suprapur) was used to prepare a 0.1 M
NaI solution. Acetone used for elution was of extra pure quality
and purchased from Merck, Darmstadt.
Resin and Column Preparation
Amberlite XAD-1180 resin (particle size, 0.3-0.9 mm; Rohm and
Haas Co.) was ground and sieved to 0.1-0.2 mm. It was washed
succesively with methanol, water, 1 M HNO3 in acetone, water, 1
M NaOH and water.
Short glass columns with an inner diameter of 10 mm and a
length of I00 mm, provided with porous frits, were filled up to a
height of about 25 mm with a suspension of 400 mg Amberlite
XAD-1180 resin in water (Fig. 1). Before use, the resin was
preconditioned with a high-purity solution of 0.3 M HC1 and 0.1 M
NaI. After completing each experiment, the column was rinsed
with water and stored for the next experiment.
Procedures
Test working. The test solutions used contained 1-10 gg of metal
ions such as Bi, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn. They were
prepared in a 25 ml volume of 0.3 M HC1 and 0.1 M NaI. The
solutions were passed through the resin column at a rate of 8-9
ml/min. The column was then washed with a solution of 0.3 M HC1
and 0.1 M NaI with high purity with respect to the analytes and the
retained metal ion-complexes were eluted with 8 ml of acetone at a
1-3 ml/min rate. The effluent was collected in a 25 ml beaker and
evaporated to dryness. Subsequently, it was cooled and with 1 M
HC1 the volume was brought carefully to 2 or 10 ml in an
appropriate volumetric flask. The metal ions in the final
concentrate were determined with flame AAS.
Analysis of Aluminium and Zinc
Samples of aluminium (50-400 rag) and zinc (40-50 rag) present
as metal turnings were separately weighed in a glass beaker of 200
ml and dissolved by slowly adding a minimum amount of
concentrated HC1. The solutions were evaporated to near dryness
on a hot plate. The residues were dissolved and diluted to 50 ml
with a solution of 0.3 M HC1 and 0.1 M NaI. This solution was
passed through the column and the analytes were determined as
described above.
Trace Elements in High-Purity Aluminium, Zinc and Commercial Steel by AAS
Analysis of Steel
100-300 mg amounts of steel samples were accurately weighed in
a 400 ml glass beaker and treated with 10-15 ml of concentrated
HC1. The beaker was covered and gently heated to dissolve the
sample. Then 5-10 ml of concentrated HNO3 was added and
heating was continued. The solution was evaporated to near
dryness to expel the nitrous oxides. The residue was dissolved and
diluted to 300 ml with a solution of 0.3 M HC1 and 0.1 M NaI. This
solution was passed through the column and the concentration of
Bi and Cd in the final analyte solution were determined by
GFAAS.
Results and Discussion
Effect of the Reagent Concentration and Sample
Volume on the Recovery
Previously, we have shown that for Bi, Cd, Cu and Pb
a quantitative recovery from a solution of 0.1 M
H2SO4, 0.4 M NaI and 0 . 0 5 M K S C N could be
achieved with the XAD-1180 resin column [8]. In this
study, the influences of the HC1 and HNO3 concentra-
tions on the recoveries of Bi, Cd, Co, Cr, Cu, Fe, Mn,
Ni, Pb and Zn from the acid solutions which contained
0.1 M NaI but no KSCN were investigated in detail. It
was found that Bi, Cd, Cu and Pb were quantitatively
recovered with 0.05-2.0 M HC1 (Fig. 2). When
working with HNO3, quantitative recoveries for Pb
and Cd were obtained within an acid concentration
range of 0.01-1.5 M (Fig. 3). As seen from Fig. 3, the
recovery for Cu and Bi decreased from 90% to 65%
80
70"
j . L
60
50
o o% ~ ~is
HCI, M
283
when the HNO3 concentration increased from 0.01 M
to 2.0 M. Over the range of 0.05-2.00 M of both two
acids the recoveries for other examined metals were
found to be 50-75% for Zn, 10-20% for Ni and Fe,
~<5% for Co, Mn and Cr (Figs. 2 and 3).
According to these results and to the data given in a
previous study [8], the addition of potassium thiocya-
nate brought only an advantage for Bi, Cd, Cu and Pb
when working in nitric acid and sulfuric acids.
However, with a mixture of 0.3 M HC1 and 0.1 M
NaI quantitative recoveries for these four analytes
could be realized. Consequently, the contamination
due to the number of reagents and their relatively
large amounts in our previous work [8] could be
considerably decreased.
To obtain knowledge about the reason for the
insufficient recoveries for bismuth and copper in the
case of HNO3, the preconcentration procedure was
repeated with a test solution containing a fixed
amount of analyte and either 0.1 M NaI, 0.3 M HC1
or 0.3 M HNO3. The recoveries from the solution
prepared with 0.1 M NaI were found to be ~>95% for
Cu, Cd and Pb and 78% for Bi. On the other hand, the
recoveries were found to, be ~< 10% for Cd, Cu, and
Pb, and ~ 35% for Bi with HC1; and for all four
analytes under 5% with HNO3. In this case, the
addition of HNO3 decreases the recoveries as com-
pared to a 0.1 M NaI solution, which can be explained
with a partial oxidation of iodide in the HNO3 solu-
j
Fig. 2. Influence of the HC1
concentration on the recoveries
for Bi (A), Cd (O), Cu (IN), Pb
(11) and Zn (&) from a solution
containing 0.1 M NaI (Recoveries
for Co, Cr, Fe, Mn and Ni
< 20%)
284 $. Tokaho~lu et al.

100-

90- "1~, "\

"0. \',
9...,.. '\

80

...... "O-~ ...... \

O
r
e~
7O

60 Fig. 3. Influence of the HNO3

concentration on the recoveries
for Bi (A), Cd (O), Cu ( D , Pb
(m) and Zn ( A ) from a solution
50 containing 0.1 M NaI (Recov-
' 0'.5 i 115 eries for Co, Cr, Fe, Mn and
HNO3,M Ni < 20%)

tion. In contrast, the addition of 0.3 M HC1 improved
the recovery for bismuth as compared the one for a
solution containing 0.1 M NaI. The improvement
might be due to a synergistic effect that is very well
known in solvent extraction.
Studies were also carried out with solutions of large
volumes with the aim to enrich these analytes from
solutions with very low concentrations by a high
preconcentration factor. Accordingly, 1-10 lag of
metal ions could be recovered from the solutions by
increasing the sample volume with respect to the
and 1000 lag/ml Fe. The retention of lead was also
quantitative to up to 5000 lag/ml A1. It could not be
recovered, however, from Fe(III) solutions. Bi, Cd and
Pb were quantitatively recovered from up to 1000 lag/
ml Zn. The concentrations of A1, Zn and Fe, which
passed into the effluent when test solutions with the
Table 3. Dependence of Bi, Cd and Pb recoveries on the concen-
tration of A13+ as nitrate salt
A13+, gg/ml Recovery, % (n= 3)

present method. The results showed that quantitative Test solution Effluent Bi Cd Pb
recoveries for Bi and Cd could be obtained from 400
0 0 98 96 96
ml volumes and in the case of Pb from 100 ml 500 20 98 100 96
samples. The recovery for Cu, however, decreases 1000 60 100 99 95
considerably after the volume exceeds 25 ml. Based 5000 130 98 101 96
10000 180 99 98 87
on a final sample volume of 2 ml, the highest pre- 20000 220 97 102 82
concentration factors found were 200 for Cd and Bi,
50 for Pb and 12.5 for Cu. Table 4. Dependence of Bi, Cd and Pb recoveries on the concen-
tration of Zn 2+ as nitrate salt

Matrix Effects on Recovery Zn 2+, gg/ml Recovery, % (n= 3)

A series of experiments were performed to assess the Test solution Effluent Bi Cd Pb

analytical application to real metal samples, such as 0 0 98 96 96
zinc, aluminium and steel samples. For these studies 5o0 85 96 100 84
different amounts of matrix ions were added to fixed 1000 160 102 105 73
2000 250 70 80 30
amounts of analytes and afterwards they were 3000 270 23 48 15
determined by the combined procedure. The results 5000 300 21 18 10
are given in Tables 3-5. The retention of Cd and Bi 10000 516 10 45 45
20000 818 45 45 45
was found to be quantitative to up fo 20000 lag/ml A1
Trace Elements in High-Purity Aluminium, Zinc and Commercial Steel by AAS 285

Table 5. Dependence of Bi, Cd and Pb recoveries on the concen- Table 6. Determination of B• Cd and Pb in high-purity aluminium,
tration of F e 3+ as nitrate salt zinc and commercial steel (n = 7)
Fe3+, gg/ml Recovery, % (n= 3) Samples Analyte Reference value, % *Thisprocedure, %

Test solution Effluent Bi Cd Pb Aluminium Bi - d(9.84 4- 0.99) x 10 -6

(R0) aCd (3.75-4-0.42)x 10-5 (3.91- 0.32) x 10-5
0 0 98 96 96 aPb (1.90-t-0.11)x 10-4 (2.05-4-0.14) • 10 -4
500 10 96 100 84 Zinc bBi (2.2 • 0.2) x 10-4 d(2.08• 0.21) x 10-4
1000 40 102 98 73 (Zn-1) cCd 2 • 10 -4 (1.84• • 10 -4
2000 60 70 80 30 CPb 1.4 x 10-3 (1.40 • 0.13) x 10-3
3000 70 23 48 15 Steel Bi - d(3.42 4- 0.36) x 10-5
5000 100 21 18 10 Cd - d(2.02• 0.19) • 10 -6
10000 206 10 45 45
20000 212 45 45 45 * Mean-t-SD, a See ref. 15, b See ref. 8, ~ Certified value,
a GFAAS.

m a x i m u m tolerable concentrations given above were
used, were found to be 130 gg/ml, 160 gg/ml and 40
gg/ml, respectively.
Also, the matrix effects of aluminium, zinc and iron
in the direct determination of Bi, Cd, Cu and Pb with
flame AAS without preconcentration were tested for
variable matrix ion concentrations in 1 M HC1.
Aluminium, zinc and iron did not interfere below
concentrations of up to 3000 gg/ml for the analytes
(with except of Bi, up to 1000 pg/ml for iron).
Consequently, the concentrations of the remaining A1,
Zn and Fe in the effluents as indicated above had no
interferences in the determination of Bi, Cd, Cu and
Pb with flame AAS. Therefore, in flame AAS
calibrations were performed with synthetic standard
solutions. However, it is known that the residuals of
the A1, Zn and Fe matrices interfered in the deter-
mination of Bi, Cd and Pb with GFAAS [11-13].
These effects of the remaining A1, Zn and Fe in the
effluents were investigated. It was found that Bi, Cd
and Pb signals detected with GFAAS vary from 5 to
20% when the matrix concentration reaches 200 gg/
ml A1 or Zn, and 100 gg/ml Fe. Accordingly, calibra-
tion by standard addition was performed in the case of
GFAAS.
Analytical Performance
The analytical performance of the procedure was
illustrated by the results from flame atomic absorption
spectrometric measurements. The relative standard
deviations, (s/2, n = 7), in the case of 0.2 gg/ml Bi,
0.02 ~tg/ml Cd and 0.2 gg/ml Pb were found to be 3,
1.5 and 2%, respectively. The recoveries for Bi, Cd
and Pb from test solutions prepared in 0.3 M HC1 and
0.1 M NaI and in the presence of an interferent up to
the tolerable concentrations determined were better
than 95%, which confirms the accuracy of the proce-
dure. The accuracy was also investigated by the ana-
lyses of standard reference samples (Table 6). The
detection limits (3~, n = 20) for Bi, Cd and Pb in the
blank solutions by flame AAS were found to be 0.110,
0.002 and 0.016 gg/ml, respectively [14]. The detec-
tion limits for the GFAAS measurements in the blank
solutions were 0.004 gg/ml for Bi, 0.0003 gg/ml for
Cd and 0.002 gg/ml for Pb. In the case of real samples
(50 mg), these would be in the ranges of 0.08-4.4 pg/
g for flame AAS and 0.012-0.16 gg/g for GFAAS.
The detection limits will decrease at increasing sampl-
ing amounts.
Analysis of Aluminium, Zinc and Steel
The combined analysis method was applied to the
analysis of high-purity aluminium, zinc and commer-
cial steel samples as described. The aluminium (R0)
and zinc (Zn-1) were taken from "Alusuisse pure alu-
minium standard series" (Switzerland) and "Metallic
pure zinc series of Zinc et All• (Belgium), res-
pectively. The concentrations of Bi, Cd and Pb in
aluminium, however, have not yet been certified. For
this reason, the results found with preconcentration of
the trace elements on activated carbon and graphite
furnace atomic absorption spectrometry (GFAAS) and
presented in a previous paper [15] were used as com-
parative values in the aluminium analysis. The con-
centration of the analytes in Zn-1 (with except of Bi)
are certified. For comparison the Bi concentration
determined as described in [8] is given in Table 6. The
commercial steel sample was taken from a steel
factory in Ere~li (Turkey). The analysis results for
the aluminium, zinc and steel samples are given
in Table 6. From a statistical analysis for the
comparison of two samples, it was found that the
286 Trace Elements in High-Purity Aluminium, Zinc and Commercial Steel by AAS
results for Cd in A1-R0 and Bi, Pb in Zn-1 were
within the 95% confidence level and for Pb in A1-R0
and Cd in Zn-1 they were within the 99% confidence
level. The analytical concentration error in the
range of l x 1 0 - 3 - 4 x 10.5 % was less than 8%
and the RSDs were below 10%. The correctness of
the determinations of Bi in aluminium and steel,
and Cd in steel was verified by a determination of
the recovery of spikes from their solutions prepared
for analysis. The recoveries were always higher
than 95%, which confirms the accuracy of the
results.
Conclusion
In conclusion, the results in this paper imply that iodo
complexes of Bi, Cd and Pb metal ions in 0.3 M HC1
are retained by Amberlite XAD-1180 resin. A1, Co;
Cr, Fe, Mn, Ni and Zn ions are not retained by this
collector and accordingly can be considered as
potential matrices. Therefore, this analytical proce-
dure was applied for precise and accurate determina-
tions of Bi, Cd and Pb in A1, Zn and Fe matrices and it
may be expected that the procedure can be applied
also in the case of Co, Cr, Mn and Ni samples.
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Received February Z 1996. Revision July 18, 1996.