Anal Bioanal Chem (2008) 391:11351137
DOI 10.1007/s00216-008-1975-2
TECHNICAL NOTE
Feasibility of using solid sampling graphite furnace atomic
absorption spectrometry for preparation of spiked filter
papers with Cu and Zn as standards for direct solid analysis
Cassiana S. Nomura & Danielle P. Intima &
Pedro V. Oliveira & Iolanda A. Ruffini &
Francisco J. Krug
Received: 31 October 2007 / Revised: 6 February 2008 / Accepted: 11 February 2008 / Published online: 12 March 2008
# Springer-Verlag 2008
Abstract An approach was developed for the preparation
of cryogenic ground spiked filter papers with Cu and Zn for
use as synthetic calibrating standards for direct solid micro-
analysis. Solid sampling graphite furnace atomic absorption
spectrometry was used to evaluate the microhomogeneity and
to check the applicability of the synthetic calibrating standards
for the direct determination of Cu and Zn in vegetable certified
reference materials. The found concentrations presented no
statistical differences at the 95% confidence level. The
homogeneity factors ranged from 2.7 to 4.2 for Cu and from
6.4 to 11.5 for Zn.
Keywords Solid sampling . Graphite furnace .
Calibrating standard . Microhomogeneity
Introduction
Many atomic spectrometric techniques have been proposed
for qualitative and quantitative determinations of elements
by direct solid analysis. However, the main obstacle of
C. S. Nomura (*)
Centro de Cincias Naturais e Humanas,
Universidade Federal do ABC,
09210170 Santo Andr, SP, Brazil
e-mail: cassiana.nomura@ufabc.edu.br
D. P. Intima : P. V. Oliveira
Departamento de Qumica Fundamental,
Instituto de Qumica, Universidade de So Paulo,
05513-970 So Paulo, SP, Brazil
I. A. Ruffini : F. J. Krug
Centro de Energia Nuclear na Agricultura,
Universidade de So Paulo,
13400-970 Piracicaba, SP, Brazil
adopting this type of method is the instrument calibration
and sample microhomogeneity [1, 2].
The spectrometer calibration against standard aqueous
solutions has been successfully employed for the direct solid
analysis by solid sampling graphite furnace atomic absorption
spectrometry (SS-GF-AAS) [13]. On the other hand,
calibrations using certified reference material (CRM) were
necessary for a lot of applications [35]. For laser ablation
inductively coupled mass spectrometry (LA-ICP-MS) and
laser-induced breakdown spectrometry (LIBS), solid stan-
dards are imperative in the majority of applications [68].
Unfortunately, practical use of CRMs presents some diffi-
culties or restrictions: certified materials with matrix compo-
sitions equivalent to that of the sample may not be available;
most commercially CRMs are recommended only for masses
size higher than 100500 mg [9]; and it is not trivial to find
CRMs containing different concentrations of one specific
analyte. For these reasons many strategies have been
proposed to calibrate equipment, such as standard addition
and the use of synthetic calibrating standard [2, 1013].
The objective of this work was to prepare cryogenic
ground spiked filter papers with Cu and Zn for direct solid
microanalysis. SS-GF-AAS was used to evaluate the
microhomogeneity and to check the applicability of the
synthetic calibrating standards for the direct determination
of the elements in vegetable certified reference materials.
Experimental
Materials
A ZEEnit 60 atomic absorption spectrometer (Analytik
Jena AG, Jena, Germany) equipped with a manual solid
1136 Anal Bioanal Chem (2008) 391:11351137

0.06
sampling accessory was used. The spectrometer was
0.05
a b
operated with hollow cathode lamps for Cu (1=324.8 nm,
0.05

Absorbance / sample mass (s mg-1 )

4.0 mA, and 0.8-nm slit) and for Zn (1=307.6 nm, 4.0 mA.
0.04

Integrated Absorbance (s)

and 0.8-nm slit). An alternative wavelength was used for 0.04
Zn, and a three-field-mode Zeeman-effect background
0.03
corrector was used for Cu. The magnetic field strength 0.03
was 0.8 T for both elements. The heating program used was
the same as previously described [14]. The ground filter 0.02
0.02
papers and CRMs were directly weighed on to the boat-
type platform using a microbalance, Auto Balance AD-4 0.01
0.01
(Perkin-Elmer, Norwalk, USA) with a precision of
0.001 mg. A Spex 6750 cryogenic mill (Spex, Metychen, 0.00 0.00
0 5 10 15 20 25 30 35 40 45 5 10 15 20 25 30 35 40 45
NJ, USA) was used to grind the filter papers. A flame
Zn (ng) Zn (mg kg-1 )
atomic absorption spectrometer, AA5-FL (Analytik Jena
Fig. 2 Analytical calibration curves for Zn: a increasing sample mass
AG), was used for Cu and Zn determinations in the of one calibrating standard, and b four calibrating standards contain-
digested filter papers, performed in a Microwave 3000 ing different concentration of Zn
(Anton Paar, Graz, Austria).
analysis. The homogeneity factor (He) [15] was determined
Procedure by SS-GF-AAS using masses around 200 g for Cu and
1,000 g for Zn. The calibration curves were made using
High-purity water provided by a Milli-Q water purification different approaches: one was based on increasing masses
system (Millipore, Bedford, MA, USA) was used throughout. (100 to 1,400 g) of one calibrating standard (4.88
Whatman 513 (mass around 1.2 g) filter papers were spiked 0.22 mg kg1 Cu and 36.10.1 mg kg1 Zn); another was
with 1 mL reference solutions containing 5, 10, 20, and based on weighing similar masses (ca. 150 g for Cu and ca.
40 mg L1 of Cu and Zn, prepared by dilutions of the 1,000 g for Zn) of the calibrating standards. A 10-L
1,000 mg L1 stock solutions (Titrisol, Merck). The papers aliquot of 500 mg L1 Pd(NO3)2 (Suprapur, Merck) was used
were dried in a stove (Fanen, So Paulo) at 30 C for 24 h as chemical modifier for Zn. The vegetable CRMs (apple
and ground (5 min of precooling, 2 min of grinding, and leaves SRM 1515, rice flour NIES 10a, bush branches GBW
1 min of coolingrepeated five times for each filter paper). 07603, spinach SRM 1570a, peach leaves SRM 1547,
Masses (ca. 200 mg) of ground filter papers were digested
with 2 mL conc. HNO3 + 1 mL of conc. H2O2 + 3 mL H2O
in a closed vessel microwave oven using the following Table 1 Analysis of certified reference materials after spectrometer
heating program (temperature/C; ramp/min; hold/min): calibration using synthetic calibrating standards
(140, 5, 1), (180, 8, 2), and (220, 4, 10). The accuracy of CRM Certified value Type 1a Type 2b
this procedure was checked by SRM 1515 (apple leaves)
Cu (mg kg1)
NIES 10a 3.50.3 3.80.1 3.50.1
0.14 a 3.0 b SRM 1515 5.640.24 6.220.06 5.820.50
GBW 07603 6.60.8 6.71.1 6.31.1
SRM 1570a 12.20.6 13.11.2 12.31.1
Absorbance / sample mass (s mg-1 )

0.12
2.5
SRM 1547 3.70.4 3.80.2 3.50.2
Integrated Absorbance (s)

0.10 IAEA 359 5.670.17 6.200.70 6.260.57

2.0
NBS 1567a 2.10.2 2.00.1 2.00.1
0.08
Zn (mg kg1)
1.5
0.06
NIES 10a 25.20.8 26.01.5 25.43.7
SRM 1515 12.50.3 15.21.4 14.91.3
1.0
0.04 GBW 07603 554 493 483
SRM 1570a 823 773 762
0.02 0.5
SRM 1547 17.90.4 20.11.0 19.70.9
IAEA 359 38.60.8 38.62.1 37.82.2
0.00 0.0 NBS 1567a 11.60.4 13.20.3 12.90
0.0 0.5 1.0 1.5 2.0 0 5 10 15 20 25 30 35
Cu (ng) Cu (mg kg-1 ) a
Calibration type 1 (using increasing sample mass of one calibrating
Fig. 1 Analytical calibration curves for Cu: a increasing sample mass standard)
b
of one calibrating standard, and b four calibrating standards contain- Calibration type 2 (using four calibrating standards containing
ing different concentration of Cu different concentration of Cu and Zn)
Anal Bioanal Chem (2008) 391:11351137
cabbage IAEA 359, and wheat flour NBS 1567a) were used
to check the accuracy of the proposed methods.
Results and discussion
The concentrations of Cu and Zn in each calibrating standard
by FAAS were (Cu/Zn in mg kg1): (4.880.22/9.722.20; sampling techniques, such as LA-ICP-MS and LIBS. We
9.620.24/12.42.4; 18.10.6/20.42.0 ;and 33.30.3/ would like to stress that this investigation will be done in
36.15.3). The analysis of SRM 1515 showed good agreement
with the recommended concentration at the 95% confidence
level (certified value/found value in mg kg1): (5.640.24/
5.840.14) for Cu and (12.50.3 and 12.01.5) for Zn.
All calibrating standards were homogenous for Cu (He =
2.74.2) indicating acceptable homogeneity for microanalysis.
For Zn, He values were slightly higher: 9.722.20 mg kg1
(He =10.6) and 12.42.4 mg kg1 (He =11.5).
The analytical calibration curves derived by increasing
mass of one calibrating standard are shown in Fig. 1a (y=
0.072890.00126x, R2 =0.98800.0049) for Cu and Fig. 2a
(y=0.001360.00002x, R2 =0.98370.0022) for Zn. The
analytical calibration curves using four calibrating standards
containing different concentration of Cu and Zn are shown,
respectively, in Fig. 1b (y=0.077910.00259x, R2 =0.9984
0.1019) and Fig. 2b (y=0.001390.00005x, R2 =0.9978
0.0013). The residual standard deviations of the calibration
lines are 1.7% for Cu and 1.5% for Zn for calibrations using
increasing mass of one calibrating standard and lower than
3.5% for both analytes when all standards are used. The ratios
between slopes of calibration curves are approximately 1 for
Cu (0.07289/0.07791 = 0.94) and Zn (0.00136/0.00139 =
0.98), ensuring the adequacy of using both calibrating
procedures for SS-GF-AAS.
Analytical curves derived using aqueous solutions showed
the same behavior of those obtained using solid calibrating
standards (y=0.080110.00273x, R2 =0.99590.0110) for
Cu and (y=0.001340.00003x, R2 =0.99740.0016) for
Zn. In this specific case, the determinations of Cu and Zn
by SS-GF-AAS could be done against aqueous calibrations.
The CRMs results using calibration with increasing mass
of one standard (type 1) and using four standards (type 2) are
shown in Table 1. All found values are in agreement with
the certified concentration at the 95% confidence level.
1137
Conclusion
This is an initial investigation of the production of synthetic
calibrating standards for direct solid sampling microanaly-
sis (He <10). SS-GF-AAS was shown to be a good tool for
the material production. The results found in this work
suggest this material could be employed in others solid
the near future.
Acknowledgments The authors are grateful to Fundao de Amparo
Pesquisa do Estado de So Paulo (FAPESP) for finacial support and
for a fellowship to CSN; to Conselho Nacional de Desenvolvimento
Cientfico e Tecnolgico (CNPq) for financial support and research-
ship to PVO and FJK; and to Coordenao de Aperfeioamento de
Pessoal de Nvel Superior (CAPES) for a fellowship to DPI.
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