Analytica Chimica Acta 470 (2002) 195204

Determination of trace elements in biological materials using

tetramethylammonium hydroxide for sample preparation
Patrcia Martins a , Dirce Pozebon a, , Valderi L. Dressler b , Gisele A. Kemieciki a
a

Instituto de Qumica, Universidade Federal do Rio Grande do Sul, Av. Bento Gonalves, 9.500-91.501-970 Porto Alegre, RS, Brazil
b Depto. de Qumica, Universidade Federal de Santa Maria, 97.105-900 Camobi, Santa Maria, RS, Brazil
Received 28 May 2002; received in revised form 15 July 2002; accepted 1 August 2002

Abstract
A method to prepare milk powder, bovine liver and bovine muscle samples for analysis by electrothermal atomic absorption
spectrometry (ETAAS) is proposed. Samples are mixed with a small amount of tetramethylammonium hydroxide (TMAH)
and a stable and homogeneous slurry is produced in ca. 2 h with heating at 6070 C. After such sample preparation and
dilution with water, trace elements are determined in certified reference materials. Pyrolysis and atomisation temperatures
are optimised for each element, and several modifiers are investigated. External calibration is used for every analyte. Limits
of detection (LODs), precision and accuracy are reported for Cd, Pb, Ni, Cr, Cu and Ag and compared with those obtained
after conventional acid digestion. The main advantages of the proposed method are the simplicity of sample preparation and
the longer lifetime of the graphite tube.
2002 Elsevier Science B.V. All rights reserved.
Keywords: Tetramethylammonium hydroxide; Electrothermal atomic absorption spectrometry; Biological samples; Cd; Pb; Ni; Cr; Cu; Ag

1. Introduction
Biological sample analysis by electrothermal
atomic absorption spectrometry (ETAAS) is usually
performed in an acidic solution of the sample. Sample
dissolution by nitric acid and hydrogen peroxide is
preferred, since the background signal is not significantly increased. In this procedure, to avoid contamination and to increase the sample throughput rate,
digestion in closed vessels and microwave heating are
usually recommended [1]. As an alternative to the acid
digestion of biological materials, a tertiary amine and
ethylenediaminetetraacetic acid (EDTA) were used to
prepare powdered and skimmed milk samples [2] and
Corresponding author. Fax: +55-51-33167304.
E-mail address: dircepoz@iq.ufrgs.br (D. Pozebon).

plants [3] for analysis. The analytes were determined

using inductively coupled plasma mass spectrometry
(ICP-MS) and inductively coupled plasma atomic
emission spectrometry (ICP-AES). The quaternary
ammonium species tetramethylammonium hydroxide
(TMAH), was used for milk samples preparation, with
good results obtained by ICP-MS only for Cu and I,
owing to memory effects, spectral interference and
the insolubility of the analyte in the alkaline medium
[4]. However, it was observed that Mn, Sn, Cu and
Fe extraction from bovine liver were efficient [5].
The direct introduction of TMAH solutions into the
plasma is not recommended in order to avoid build-up
of deposits on the spectrometer interface and also
because of the plasma loading [6]. Consequently, conventional nebulisation of samples containing TMAH
for introduction into the plasma is difficult, even

0003-2670/02/$ see front matter 2002 Elsevier Science B.V. All rights reserved.
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P. Martins et al. / Analytica Chimica Acta 470 (2002) 195204

for ICP-AES. In these techniques, alternative procedures for sample introduction must be used, as for
instance, electrothermal vaporisation (ETV) or spray
chamber freezing [6,7]. It is reported that TMAH is
also applicable to human hair sample preparation for
the determination of Al, Zn, Cu, As, Cd, Ni and Pb
by ETAAS, after reagent addition and heating [8,9].
TMAH has also been used for aquatic plants, lobster hepatopancreas, dogfish muscle and dogfish liver
solubilisation with determination of Cu, Cd, Pb, Ni,
Mn and Cr by ETAAS [10]. This work demonstrated
that aquatic plant solubilisation was not complete just
simply by use of TMAH, it was also necessary to
sonicate the slurry sample. By using TMAH and sonication, precise and accurate results were obtained in
the analysis of animal and vegetal tissues. The need
of sonication for analyte extraction from vegetal tissues has already been demonstrated in previous work
[6] regarding the determination of several elements in
biological samples prepared with TMAH. In this case,
the analytes were determined by ETVICP-MS [6].
In other work, TMAH has been used for in situ wet
digestion of serum together with K2 Cr2 O7 as a modifier in order to eliminate carbon build-up in ETAAS
for Al determination [11]. TMAH proved to be very
efficient for the elimination of carbonaceous residue
formation and accumulation in the graphite tube when
Al is determined in serum by ETAAS. TMAH has
also found application in sample preparation for elemental speciation since the mild reaction conditions
preserve the speciation integrity of the sample [12].
Solid and slurry sampling procedures that avoid
complete sample digestion have generated considerable interest. The solid samples, as slurries or as
concentrated extracts, may reduce the risks of contamination and the time required for sample preparation.
Owing to the lower dilution involved, it is expected
that the limits of detection (LODs) may be improved
as well. In the preparation of the slurry, acid can be
used for a partial extraction of the analyte, ammonia
(0.35% (m/v) in water) and thixotropic agents, such
as Triton X-100, glycerol or xylene, are usually added
and an ultrasonic probe, connected to the autosampler arm, may be used to stabilise and homogenise
the slurry [1316]. In many cases, simple aqueous
standards may be used as calibrants.
As previously mentioned, an alternative approach
for sample preparation of biological tissues is the use

of TMAH, which may produce a stable slurry or in

some cases an apparently homogeneous solution [6].
Samples treated with TMAH may be suitable for analysis by ETAAS [8,13,18], since this technique does
not require totally dissolved or decomposed samples.
Slurries, if stable, can be analysed, since the organic
matter can be volatilised during the pyrolysis step of
the furnace temperature program.
The main purpose of the present work was to investigate the effect of experimental conditions on the
determination of trace elements in biological samples (bovine muscle, bovine liver and milk powder)
by ETAAS following sample preparation with a small
amount of TMAH. The proposed method is compared
with a more conventional acid dissolution, both using
external calibration.

2. Experimental
2.1. Instrumentation
Integrated absorbance signals were measured using
an atomic absorption spectrometer AAS5-ZEISS, now
AnalytikjenaAG (Jena, Germany) equipped with a
deuterium arc lamp background corrector and hollow
cathode lamps. Pyrolytic graphite coated tubes (AnalytikjenaAG, No. 334481: 026.25) containing a totally
pyrolytic graphite platform were used. The manufacturers recommended operational conditions were employed, except for the graphite furnace program, which
was optimised. Argon, 99.996%, from White Martins
(So Paulo, SP, Brazil) was used as a sheath gas. For
the sample acid digestion, a microwave oven (Prolabo,
model 7195) was used, following a program recommended by the manufacturer for similar samples.
2.2. Materials and solutions
All chemicals used were of analytical reagent grade,
unless otherwise specified. The water was de-ionised
in a Milli-Q system (Millipore Corp., Bedford, MA).
Its resistivity was 18.2 M cm. The nitric acid (65%)
from Carlo Erba (Milan, Italy) was further purified by
sub-boiling distillation in a quartz still (Hans Krner,
Rosenheim, Germany). Suprapur hydrogen peroxide
30% from Merck (Darmstadt, Germany) was used for
the sample acid digestion. The calibration solutions

P. Martins et al. / Analytica Chimica Acta 470 (2002) 195204

197

Table 1
Concentrations of the final solutions of the modifiers and their amounts employed
Modifier

Concentration (%)

Rh
Pd
Ir
Mg(NO3 )2
NH4 H2 PO4
Pd + Mg(NO3 )2
Pd + NH4 H2 PO4

0.1
0.2
0.12
0.1
0.3
0.1 + 0.05
0.1 + 0.15

Analyte/modifier (g)
Cr

Cd

Pb

Ni

Cu

Ag

15

10

10
20
20

5
10
10

20

10

10

were prepared from 1000 g ml1 stock solutions

from Merck by dilution with 2% (v/v) nitric acid. A
25% (m/v) TMAH methanolic solution from Riedel
de Han (Seelze, Germany) was used to prepare
the samples. Modifier solutions prepared from a 1%
(m/v) Pd stock solution (Perkin-Elmer), ammonium
dihydrogenphosphate (Merck) in 2% (v/v) nitric acid,
magnesium nitrate (Merck, Suprapur ) in water, iridium chloride (Aldrich) in a 1 + 1 mixture of nitric and
hydrochloric acids and 1.5% (m/v) rhodium solution
(SigmaAldrich) were used. The stock solutions of
the modifiers were diluted with water to the concentrations shown in Table 1. The amounts of the modifiers employed for each analyte are also shown in
Table 1.
The following certified reference materials were
analysed: NBS 1577a (bovine liver) from the National Bureau of Standards and Technology, now National Institute of Standard and TechnologyNIST

(Gaithersburg, MD); NIST 1549 (non-fat milk powder); and NIST 8414 (bovine muscle powder). For
the sample aliquot placed in an acid-decontaminated
15 ml polypropylene flask, a volume of TMAH as
specified in Table 2 was added. Subsequently, the
mixture was heated in a water bath (6070 C) for
60 min and let to stand for 30 min, being from time
to time manually agitated. Then the volume was
made up to 10 ml with water. If necessary, during
analyte measurements the sample solutions were
still diluted with water. This subsequent dilution employed (named as dilution factor (DF)) is also given
in Table 2.
For the acid digestion in the microwave oven ca.
0.250 g of each certified sample was used. To the sample aliquot placed in the flask of the microwave oven
2.5 ml of the HNO3 and 0.5 ml of H2 O2 were added.
The final volumes of the acid digested sample solutions were made up to 25 ml with water.

Table 2
Amount of sample, TMAH and dilution of the slurries (from an initial volume of 10 ml)
Analyte

Certified samples
NIST

Cr
Cd
Pb
Ni
Cu
Ag

1549a

NIST 1577ab

NIST 8414c

Mass (mg)

TMAH (ml)

DF

Mass (mg)

TMAH (ml)

DF

Mass (mg)

TMAH (ml)

DF

0.2532
0.2500
1.0000
1.0000
0.2502
1.0000

0.125
0.125
0.250
0.250
0.125
0.250

2
2
2
4
4
2

0.2550
0.1550
0.2550
0.1550
0.1550
0.1162

0.125
0.375
0.375
0.375
0.375
0.250

4
8
2
2
225
2.5

0.2500
0.2606
0.1162
0.2606
0.2606
0.1007

0.250
0.250
0.250
0.250
0.250
0.100

3
2
2.5

2
2

DF: dilution factor.

a Non-fat milk powder.
b Bovine liver.
c Bovine muscle powder.

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P. Martins et al. / Analytica Chimica Acta 470 (2002) 195204

The volume of calibration solution, or sample

solution, delivered to the graphite furnace was
10 l, while the volume of the modifier solutions
was 520 l. The sample solutions were pipetted
and delivered into the graphite tube separately to
avoid precipitate formation in the capillary tip of the
autosampler pipettor. If no acid was present in the
solution of the modifier, as in the case of Mg(NO3 )2
and NH4 H2 PO4 , all of them could be pipetted and
delivered to the graphite tube together.

3. Results and discussion

3.1. Method development
It is known that TMAH is an efficient reagent to solubilise tissues samples, mainly animal tissue [719].
A methanolic solution of the reagent must be used
as it is most appropriate for animal tissues containing
fats [10]. TMAH reaction with animal tissue is perceptible through foam formation, viscosity and odour
resembling an esterification reaction and soap formation. Although the solution or slurries formed with
the addition of TMAH are viscous, they are sufficient
stable for using a standard autosampler to pipette them
into the graphite tube, and ultrasonic mixing is not
necessary. Even so the sample solution containing
TMAH and any acidic solution must be pipetted separately in order to avoid precipitation in the capillary tip
of the autosampler pipettor, possibly due to a reaction
with proteins in the TMAH medium and HNO3 . Due
to this fact the washing solution of the autosampler
should also not be acidified. However, the formation
of a precipitate is not easy to see, because the sample
solution is viscous and usually dark.
A potential problem with a solution containing
large amounts of proteins and dissolved solids, and
with slurry and solid sampling, is the interference
from matrix components requiring a high pyrolysis
temperature and chemical modifiers to stabilise the
analyte and remove the bulk of the concomitants prior
to atomisation. The most serious interference is related to the build-up of a carbonaceous residue within
the graphite tube, which severely have an effect on
repeatability and sensitivity. It also may interfere with
the background correction and even hinders the analyte determination because of the partial attenuation

of the light beam. Besides, some of the analyte may be

retained inside the carbonaceous residue and occasionally released. Therefore, in some ETAAS applications
the periodic removal of this residue is still considered
necessary in order to maintain the required analytical
performance [11]. However, in some cases, it is possible to decrease these residues by using sufficiently
high pyrolysis temperatures and chemical modifiers.
It is well established that the higher the pyrolysis temperature and/or the longer the sample is exposed to that
temperature, less carbonaceous residue remains on the
platform. However, simply changing the temperature
may not be enough to avoid the carbon build-up effect
and to remove the matrix residues from the graphite
tube. Matrix modifiers may change the characteristics
of the matrix and thus facilitate its degradation and
elimination [11], and sample dilution decreases the
sample amount introduced into the graphite tube.
In this work as high a pyrolysis temperature as possible was sought, using different modifiers reported
in [17,18,20] and by the ETAAS instrument manufacturers. Considering the three samples studied in this
work, bovine liver, bovine muscle and non-fat milk
powder, it has been verified that it was more difficult
to remove the milk powder matrix from the graphite
tube. Initially the pyrolysis and atomisation temperatures were studied for each analyte using the non-fat
milk powder sample solution. In order to guarantee
correct drying of the sample aliquot solution introduced into the graphite tube before the pyrolysis step,
a program with three drying steps was optimised. A
clean-out step at 2600 C for 3 s was used as the final
step of the ETAAS program. A higher clean-out temperature was avoided in order to extend the graphite
tube lifetime. The final program optimised for the analysis of the three studied samples is shown in Table 3.
Regarding the effect of the chemical modifiers,
Fig. 1 demonstrates that Pd is very efficient for
all analytes. For Cd, the addition of Mg(NO3 )2 or
NH4 H2 PO4 , besides Pd addition, does not extend the
possibility of using higher pyrolysis temperatures nor
significantly increases the signal of the analyte. The
signal suppression that was caused by the sample matrix is still pronounced. In Fig. 1 it is also possible to
observe that Pd, in comparison to Rh and Ir, is the
best modifier for Pb, in contrast to the results reported
in other work that demonstrated the advantages of
using Ir [6]. However, it must be clear that another

P. Martins et al. / Analytica Chimica Acta 470 (2002) 195204

199

Table 3
Temperature program of the graphite furnace
Step

Temperature ( C)

Heating rate, ( C s1 )

Hold (s)

Argon flow rate (ml min1 )

Dry
Dry
Dry
Pyrolysisa
Atomisationb
Cleaning

90
130
300
6001500
15002300
2600

10
6
10
30
FPc
2

15
15
20
35
6
3

250
250
250
250
0d
250

The temperatures for pyrolysis of various elements: Pb, 800 C; Cd, 600 C; Cr, 1300 C; Cu, 1300 C; Ni, 1500 C; Ag, 1000 C.
The temperatures for atomisation of various elements: Pb, 2000 C; Cd, 1650 C; Cr, 2300 C; Cu, 2000 C; Ni, 2300 C; Ag, 1500.
c FP: full power.
d Reading in this step.
a

technique was employed in that work (ETVICP-MS)

in which a smaller amount of modifier is used that
acts as the analyte vapour carrier and also as a modifier. Divergent behaviour could be expected for other
analytes when these two techniques are compared.
According to Fig. 1, with Pd addition it is also possible to use higher pyrolysis temperatures for Cu,
Ni and Ag. The positive effect of Pd on the Ag and
Cu signals in the presence of TMAH has already
been demonstrated [6,11]. Concerning the use of the
modifier for Ni, Tsalev et al. [18] reports the use of
Mg(NO3 )2 + Pd as shown in Fig. 1; the analyte signal
in fact increases in the presence of this modifier mixture. Considering the results obtained related to the
pyrolysis temperatures, the following modifiers were
adopted: Pd + NH4 H2 PO4 for Cd, Pd for Ag, Cu and
Pb, and Mg(NO3 )2 + Pd for Ni. Regarding Cr, the
addition of Mg(NO3 )2 increases the analyte signal
up to 1300 C, decreasing after that, and at higher
pyrolysis temperatures the analyte signal is greater
in the absence of the modifier. However, it was verified that there was a significant memory effect in the
absence of Mg(NO3 )2 , perhaps due to the formation
of chromium carbides. So, this modifier was used for
further Cr measurements.
In this study, a very high and variable background
was observed for all analytes when low pyrolysis
temperatures were used (around 300600 C), this
problem being more pronounced for Cd, as a pyrolysis temperature >600 C is critical for this element
(Fig. 1). A comparable background behaviour was
also observed by Almeida and Lima [11] during the
determination of Al in serum samples by ETAAS
using K2 Cr2 O7 as the modifier. However, in this case

a high pyrolysis temperature could be used and in

this condition the TMAH promoted an in situ protein decomposition thus preventing the formation of
carbonaceous residues inside the graphite tube.
The Cd pyrolysis temperature curves shown in
Fig. 1 demonstrate that the signal of this element
decreases considerably in the presence of the sample matrix. The upper Cd curves were obtained in
the absence of the sample whereas the lower ones
were obtained for the spiked non-fat milk powder,
but in both conditions the Cd concentrations are very
similar. Consequently, the initial sample solutions
were still diluted (see Table 2) in order to obtain
quantitative recoveries. The dilutions were gradually
varied until accurate results were obtained. It should
be pointed out that in this work as small an amount of
TMAH and sample as possible were used, in order to
obtain low blank signals and achieve sample dilution
to improve the limits of detection (LODs) and to apply the method for the determination of low analyte
concentrations. In this way, external calibration could
be used rather than the analyte addition technique,
which was avoided because it is time consuming and
the calibration graph needs to be strictly linear in
order to obtain accurate results.
As the calibration solutions cannot be prepared in
TMAH solutions, taking into account that some analyte precipitation occurs in the alkaline medium, matrix matching with TMAH was also used to verify
the influence of the reagent on the analyte signals. In
this procedure, the same amount of TMAH as present
in the sample preparation was added to the analytical solutions by the autosampler directly into the
graphite tube. However, the presence of TMAH has no

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P. Martins et al. / Analytica Chimica Acta 470 (2002) 195204

P. Martins et al. / Analytica Chimica Acta 470 (2002) 195204

influence on the blank-corrected signals of the analytes

present in the calibration solutions. Another study [10]
reports the use of TMAH for biological sample preparation and analyte determination by ETAAS using
the same magnitude of dilution used here, excepted
the amount of TMAH. In the present work, smaller
amounts of TMAH were used which were optimised
in order to prevent high blanks as mentioned earlier,
besides avoiding the corrosion of the graphite tube
that was observed to be more pronounced when the
concentration of the alkaline reagent was higher. In
addition, if the sample solution is too concentrated
and viscous, it is more difficult to deliver it into the

201

graphite tube. Due to these facts and the matrix effects

earlier mentioned the initial sample solutions were
diluted with water (Table 2) for the determination of
all analytes. For a different reason, a higher dilution
of the bovine muscle sample solution was necessary
for Cu determination as the concentration of this analyte is high in this sample.
3.2. Durability of the graphite tube
In Fig. 2 the graphite tube lifetime is compared
using both an acidic solution and a TMAH sample
solution containing Cu. This figure demonstrates

Fig. 2. Lifetime of the graphite tube for Cu determination in non-fat milk powder sample prepared with TMAH [A] and acid digested
[B]. Each point is the average of 20 measurements.

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P. Martins et al. / Analytica Chimica Acta 470 (2002) 195204

Table 4
Analysis of certified samples using TMAH for sample preparation
Samples (g g1 )

Analyte
NIST 1549a
Certified
0.019
0.0005

0.7
0.026
<0.0003

Pb
Cd
Ni
Cu
Cr
Ag

Found
0.003
0.0002
0.1
0.0007

nd
nd
nd
0.65 0.05
0.025 0.002
nd

NBS 1577ab
Certified
0.34
0.27

193
0.088
0.06d

NIST 8414c

Found
0.08
0.04

0.43
0.32
nd
201
0.065
0.041

10
0.12

Certified
0.04
0.03

0.38
0.013
0.05
2.36
0.071

9
0.013
0.009

Found
0.24
0.011
0.04
0.06
0.038

0.46
0.020
0.073
2.39
0.12
0.031

0.02
0.006
0.014
0.03
0.028
0.019

The uncertainties are the standard deviations for five replicates; nd: not detected.
a Non-fat milk powder.
b Bovine liver.
c Bovine muscle powder.
d Informed.

that the tube lifetime is superior when the sample is

prepared with TMAH, using the concentrations shown
in Table 2, as the graphite tube performance starts to
get worse around 400 firings when the acid digested
sample solution is analysed. For TMAH the performance is good even for 800 firings. It is important to
remark that the final acid concentration for digested biological samples solutions containing very low heavy
metals concentrations is typically ca. 10% HNO3 , using a closed vessel. On the other hand much smaller
amounts of TMAH are sufficient to solubilise the sample, so the final concentration of the alkaline reagent
is low, which decreases deterioration of the graphite
tube.

3.3. Analytical results

The concentrations of the analytes measured in the
reference materials using TMAH for sample preparation are shown in Table 4, where it is possible to see
that the agreement with the certified values is good.
Regarding Cr, a memory effect for this analyte has
been observed in the samples treated with TMAH. In
order to minimise this effect a blank (a solution of
TMAH in the same concentration as in the sample)
was run between each run of the sample solutions.
In Table 5, the respective limits of detection (LODs, 3
S.D.) of the analytes are shown, using sample preparation with TMAH or acid digestion. By comparing the

Table 5
Comparison of the limits of detection
Samples (g g1 )

Analyte
NIST 1549a

Pb
Cd
Ni
Cu
Cr
Ag
a

NIST 8414c

TMAH dissolution

Acid digestion

TMAH dissolution

Acid digestion

TMAH dissolution

Acid digestion

0.069
0.008
0.051
0.029
0.015
0.053

0.11
0.004
0.16
0.029
0.052
0.011

0.070
0.012
0.22
0.029
0.026
0.015

0.11
0.008
0.16
0.029
0.052
0.021

0.12
0.012
0.048
0.029
0.052
0.010

0.11
0.012
0.16
0.029
0.052
0.014

Non-fat milk powder.

Bovine liver.
c Bovine muscle powder.
b

NBS 1577ab

P. Martins et al. / Analytica Chimica Acta 470 (2002) 195204

LOD values presented in Table 5 it can be observed

that they are almost of the same order of magnitude,
which may differ in relation to the characteristics of
the sample and dilutions involved. The R.S.D.s for 10
consecutive measurements were also similar for both
procedures, being <10% for the TMAH solution or
the acid solution when 25 pg of Pb, Ag, Cu and Cd,
40 pg of Cr and 50 pg of Ni were introduced into the
graphite tube.
Real samples analysis were also investigated using
the proposed method. It was observed that ca. 150 l of
TMAH was sufficient to solubilise 0.25 g of in natura
bovine muscle and bovine liver samples. By making
up the volume of the mixture to 14 ml quantitative
recoveries were obtained for all spiked analytes. For
real milk powder sample analysis, the same amount
of TMAH and final dilutions as presented in Table 2
were necessary.
Silva et al. [10] obtained higher LODs for Cu and
Ni in certified biological reference materials (aquatic
plants, lobster hepatopancreas, dogfish muscle and
dogfish liver) than those obtained in the present work,
when using TMAH and ETAAS. The higher LOD
values may be attributed to the blank signals as they
use much higher concentration of TMAH (a reagent
that cannot easily be obtained in high purity) [7].
However, in the work of Silva et al. [10] the blank
signals were not decisive since the analytes concentrations in their analysed samples are typically higher
than they are in the analysed samples in the present
work (non-fat milk powder, bovine liver and bovine
muscle). Therefore, for lower analyte concentration
determination the amount of THAH to be used should
be optimised.

4. Conclusions
The proposed sample preparation procedure compares well with the more conventional nitric acid
dissolution for the determination of Cr, Ni, Ag, Pb
and Cd in non-fat milk powder, bovine liver and
bovine muscle by ETAAS. Sample preparation with
TMAH is very simple and relatively fast requiring
only small amounts of reagent and glassware. Besides, the lifetime of the graphite tube is long, as
TMAH in the concentration used does not erode the
graphite tube, which is not usually possible when

203

acidic solution samples are analysed. Thus, it is possible to verify that more than 800 firings with the
same graphite tube can be achieved. This result is
in accordance with previously reported work [11]
concerning the use of TMAH that comments on the
possibility of using the same graphite tube for more
than 900 runs for Al determination in serum samples. This can decrease analysis costs significantly in
ETAAS. However, the Cr, Ni, Ag, Pb and Cd LODs
in ETAAS determination may not be considerably
improved in relation to the acid digestion procedures on account of the matrix effects and impurities
TMAH.

Acknowledgements
We thank Fundao de Amparo Pesquisa do Estado do Rio Grande do Sul (FAPERGS) for financial
support.
References
[1] S. Wu, X. Feng, A. Wittmeier, J. Anal. Atom. Spectrom. 12
(1997) 797.
[2] J.A. Nbrega, Y. Glinas, A. Krushevska, R.M. Barnes, J.
Anal. Atom. Spectrom. 12 (1997) 1243.
[3] J.A. Nbrega, Y. Glinas, A. Krushevska, R.M. Barnes, J.
Anal. Atom. Spectrom. 12 (1997) 1239.
[4] S. Strup, A. Stachini, S. Caroli, P. Falconieri, J. Anal. Atom.
Spectrom. 5 (1990) 1581.
[5] J.L.M. De Boer, F.J.M. Maessen, Spectrochim. Acta B 38
(1983) 739.
[6] D. Pozebon, V.L. Dressler, A.J. Curtius, J. Anal. Atom.
Spectrom. 13 (1998) 1101.
[7] T. Cho, I. Akabane, Y. Murakami, in: K.E. Jarvis, A.L.
Gray, J.G. Williams, I. Jarvis (Eds.), Plasma Source Mass
Spectrometry, Royal Society of Chemistry, Special Publication No. 85, London, 1989, pp. 94119.
[8] B.J. Stevens, Atom. Spectrosc. 5 (1983) 176.
[9] A.S. Ribeiro, A.J. Curtius, D. Pozebon, Microchem. J. 64
(2000) 105.
[10] R.G.L. Silva, S.N. Willie, R.E. Sturgeon, R.E. Santelli, S.M.
Sella, Analyst 124 (1999) 1843.
[11] A.A. Almeida, J.L.F.C. Lima, J. Anal. Atom. Spectrom. 15
(2000) 1019.
[12] S.N. Willie, D.C. Grgoire, R.E. Sturgeon, Analyst 122 (1997)
751.
[13] L. Ebdon, M. Foulkes, K. Sutton, J. Anal. Atom. Spectrom.
12 (1997) 213.
[14] F. Vanhaecke, S. Boonen, L. Moens, R. Dams, J. Anal. Atom.
Spectrom. 10 (1995) 81.

204

P. Martins et al. / Analytica Chimica Acta 470 (2002) 195204

[15] D.C. Grgoire, N.J. Miller-Ihli, R.E. Sturgeon, J. Anal. Atom.

Spectrom. 9 (1994) 65.
[16] S.A. Darke, J.F. Tyson, Microchem. J. 50 (1994) 310.
[17] D.L. Tsalev, V.I. Slaveykova, R.B. Georgieva, Anal. Lett. 29
(1996) 71.

[18] D.L. Tsalev, V.I. Slaveykova, P.B. Mandjukov, Spectrochim.

Acta Rev. 13 (1990) 225.
[19] D. Pozebon, V.L. Dressler, A.J. Curtius, Talanta 51 (2000)
903.
[20] A.B. Volinski, J. Anal. Chem. 50 (1) (1995) 2.