Analytica Chimica Acta 445 (2001) 269275

Determination of residual carbon by inductively-coupled

plasma optical emission spectrometry with axial and
radial view configurations
Sandro T. Gouveia a , Fernando V. Silva b,c , Letcia M. Costa b ,
Ana Rita A. Nogueira c , Joaquim A. Nbrega b,
a Universidade Federal do Cear, Fortaleza, CE, Brazil
b Departamento de Qumica, Universidade Federal de So Carlos, P.O. Box 676, 13560-970 So Carlos, SP, Brazil
c Embrapa Pecuria Sudeste, So Carlos, SP, Brazil

Received 8 February 2001; received in revised form 3 July 2001; accepted 3 July 2001

Abstract
In this work it was evaluated the performance of inductively-coupled plasma optical emission spectrometers (ICP-OESs)
with axial and radial view configurations for residual carbon content (RCC) determination. The effects of carbon compound
source (urea, l-cysteine, and glucose), sample medium, and internal standards on RCC determination were systematically
evaluated. All measurements were carried out with two ICP spectrometers using the carbon atomic emission lines: 247.857
and 193.025 nm. The results obtained using axial and radial configurations showed that both the carbon source and the
sample medium did not affect significantly the emission intensities. The sample medium only caused drastic influence
when H2 SO4 was employed probably due to transport interference that can be corrected employing Y as internal standard.
The sensitivity attained using axial view ICP-OES was 20-fold better than that reached using radial view ICP-OES based
on the slopes of the analytical curves at the most sensitive wavelength (193.025 nm). Using radial and axial ICP-OESs,
high concentrations of Fe (>100 mg l1 ) interfered at 247.857 nm wavelength. An addition-recovery experiment was made
by adding urea to an acid-digested sample and all recoveries were in the 100 5% range for axial and radial measure-
ments. At this wavelength, R.S.D. <2.0% (n = 10) and detection limits of 33 and 34 g ml1 C, were measured for
ICP-OESs with radial and axial configurations, respectively. Biological samples were acid-digested using a closed-vessel
microwave-assisted procedure and RCC was determined using both ICP-OES configurations. 2001 Elsevier Science
B.V. All rights reserved.
Keywords: Residual carbon content; Microwave-assisted digestion; Inductively-coupled plasma optical emission spectrometry; Radial and
axial configurations

1. Introduction

Frequently instrumental techniques require com-

plete sample decomposition before measurements.
Corresponding author. Fax: +55-162608350. Usually acid wet digestion is implemented combin-
E-mail address: djan@zaz.com.br (J.A. Nobrega). ing oxidant agents and heating for destroying the

0003-2670/01/$ see front matter 2001 Elsevier ScienceB.V. All rights reserved.
PII: S 0 0 0 3 - 2 6 7 0 ( 0 1 ) 0 1 2 5 5 - 7
270 S.T. Gouveia et al. / Analytica Chimica Acta 445 (2001) 269275

organic fraction of the sample [1]. However, due to assess the digestion efficiency of microwave-assisted
the high stability of some organic compounds present digestion procedures.
in samples or formed during decomposition, incom-
plete oxidation is generally observed. Spectroanalyt-
ical techniques may not be critically affected by the 2. Experimental
residual carbon content (RCC) [2,3]. On the other
hand, the application of electroanalytical techniques 2.1. Instrumentation
can be severely limited [46]. Therefore, RCC is an
important parameter to be controlled depending on Axial and radial view simultaneous ICP-OESs
the instrumental technique used. Additionally, RCC (Vista AX and RL, Varian, Mulgrave, Australia)
measurement is an important parameter to evaluate equipped with CCD detectors were used in this study.
the efficacy of sample decomposition procedures. The spectrometers provided wavelength coverage
Different approaches were proposed for RCC de- from 167 to 785 nm with the optical system purged
termination [68]. Elemental analysis or spectropho- with argon and the Echelle polychromator ther-
tometric titration of the organic matter with chromic mostated at 34 C. In the axial arrangement the cool
acid can be used for this purpose [6]. In this latter plasma tail was removed from the optical path using
procedure, controlled reaction conditions and experi- an end-on gas to purge the plasmaspectrometer in-
enced analysts are required to reach suitable accuracy. terface. An argon snout purge system was employed
Inductively-coupled plasma optical emission spec- in the radial configuration to produce an argon purged
trometry (ICP-OES) was also applied for RCC deter- environment between the pre-optical system and the
mination [7,8]. The RCC presents in natural waters plasma in order to allow readings below 190 nm
was determined by Emteryd et al. [7] using a flow wavelength. The operational parameters established
injection system coupled to an ICP-OES spectrome- for RCC determination in each configuration are
ter [7]. The measurements were made at 193.091 nm listed in Table 1. All measurements were carried out
wavelength and solutions prepared from citric acid using liquid argon to decrease signal blank caused by
or potassium hydrogen phthalate were used for cali- plasma gas contamination [8].
bration. The obtained results were in agreement with The RCC was monitored at C I 193.025 and
those determined by elemental analysis. Krushevska 247.457 nm wavelengths. The same instrumental con-
et al. [8] also used the C emission line 193.091 nm to ditions and nebulizer system (V-groove) were used in
perform RCC determination in milk sample digests. both ICP-OES spectrometers to facilitate the compari-
Recoveries of aliphatic and aromatic compounds were son of performance of axial and radial configurations.
evaluated in different sample media. Recovery val-
ues around 100% were achieved using Sc as internal Table 1
standard. The authors also mentioned memory effects Instrumental parameters for RCC determination using axial and
radial ICP-OESs
in the spray-chamber when measuring aromatic com-
pounds. Long washout times were required to reduce Instrumental parameter Axial and radial
this effect. Power (kW) 1.0
Considering the emerging of solid state detectors Plasma gas flow (l min1 ) 15.0
and changes of the optical system in ICP-OESs, the Auxiliary gas flow (l min1 ) 1.5
Observation heighta 9
present work investigated the determination of RCC in
Nebulizer gas flow (l min1 ) 0.90
acid-digested biological samples using ICP-OESs with Spray chamber SturmanMasters
axial and radial view configurations. The main exper- Nebulizer V-groove
imental parameters and figures of merit were system- Sample flow rate (ml min1 ) 0.80
atically evaluated and further correlated with the em- Analytical wavelengths (nm)
ployed configuration. The axial and radial ICP-OESs CI 193.025
developed procedures were compared to TOC an- CI 247.857
alyzer in order to assess the accuracy of obtained Y II 371.022
results. The developed procedures were also applied to a Only for radial view configuration.
 S.T. Gouveia et al. / Analytica Chimica Acta 445 (2001) 269275 271

The acid digestions were performed in a microwave-
oven (ETHOS 1600, Milestone, Sorisole, Italy)
equipped with 10 perfluoralkoxy Teflon (PFA)
closed vessels with calibrated resealing pressure relief
mechanism (maximum operating pressure 110 atm).
The vessels were put on a rotating turntable inside the
microwave oven cavity. Before using, the PFA vessels
were acid cleaned and rinsed with deionized water.
The heating programs used for acid digestions are de-
scribed further on. A sub-boiling apparatus (subPUR,
Milestone) was also used to distill the concentrated
nitric acid. The total carbon determination used to
evaluate the accuracy of the proposed procedure was
carried out in a total carbon analyzer (TOC 5000
Shimadzu, Japan).
2.2. Reagents and solutions
All solutions were prepared using analytical grade
reagents and Milli-Q distilled and deionized wa-
ter (Millipore, Bedford, MA, USA). Sub-boiled dis-
tilled nitric acid and hydrogen peroxide (Mallinck-
rodt, Mexico) have also been used to perform the
microwave-assisted digestions.
Stock solutions containing 5.0% m/v C in aque-
ous medium were prepared from glucose (C6 H12 O6 ,
Merck, Germany), urea (CH4 N2 O, Reagen, Brazil)
and l-cysteine (C3 H7 NSO2 , Sigma, USA). Test
solutions containing 0.05 and 0.25% m/v C were
prepared in HNO3 (1.4 mol l1 ), HNO3 + H2 O2
(1.4 mol l1 + 0.30% v/v) and H2 SO4 (1.8 mol l1 )
media and used to evaluate the influence of carbon
source and sample medium in C emission intensities.
Evaluation of Fe interference was carried out using
solutions containing 0.05% m/v C plus 10, 100 and
500 mg l1 Fe, respectively. Carbon addition-recovery
experiments were performed using 0.05% m/v C refer-
ence solutions and additions of 0.10% m/v C as urea,
glucose, l-cysteine and citric acid. Addition of carbon
to an acid-digested sample was also performed.
For RCC determination the analytical curve used
(0.05, 0.10 and 0.25% m/v C) was prepared in
1.4 mol l1 HNO3 using urea stock solution. Yt-
trium as internal standard was added to all reference
solutions and samples in a final concentration of
1.0 mg l1 .
2.3. Samples
Standard reference materials NIST-1577b Bovine
liver, NIST-8435 Whole milk powder, NIST-1515 Ap-
ple leaves, and NIST-1570a Spinach leaves (National
Institute of Standards and Technology, Gaithersburg,
MD, USA) were digested and RCC was determined
using TOC analyzer in order to check the accu-
racy of the proposed procedures. Lyophilized bovine
liver and soybeans samples were microwave-assisted
acid-digested using different heating programs. The
RCC in all diluted digests was determined using
ICP-OESs with axial and radial view configurations.
2.4. Sample preparation
The microwave-assisted digestions were carried out
using 250 mg of sample and an oxidant mixture con-
taining 2 ml of HNO3 plus 1 ml of H2 O2 . According
to the procedure recommended by Krushevska et al.
the digests were transferred to 10 ml glass beakers and

Table 2
Microwave-assisted digestion programs employed to decompose lyophilized bovine liver and soybeans samples
Step Microwave digestion programsa

1 2 3 4 5 6

Time Power Time Power Time Power Time Power Time Power Time Power
(min) (W) (min) (W) (min) (W) (min) (W) (min) (W) (min) (W)
1 1 250 1 250 1 250 1 250 1 250 1 250
2 1 0 1 0 1 0 1 0 1 0 1 0
3 3 250 3 250 3 250 3 250 3 250 3 250
4 5 400 10 400 5 400 5 400 5 400 5 400
5 5 600 5 800 2.5 600 7.5 600 7.5 800
a A sixth step consisting of 5 min of ventilation without any applied power was implemented in all tested programs.
272 S.T. Gouveia et al. / Analytica Chimica Acta 445 (2001) 269275

evaporated gently at 120 C to remove the volatile car- Table 4

bon compounds [8]. After, the digests were quantita-
tively transferred to 10 ml volumetric flasks and the
volume was made up with H2 O. It was used the mi-
crowave digestion program 1 described in Table 2.
The time and power parameters in the last step
of the microwave heating program 1 were systemat-
ically modified to evaluate its effect on the digestion
of lyophilized bovine liver and soybeans samples. All
evaluated programs are presented in Table 2. The di-
gestion efficiency was evaluated by determining the
RCC in the digests.
2.5. Total carbon analyzer
The accuracy was evaluated comparing the obtained
results with those established using a total carbon an-
alyzer (TOC). In the comparative method, the residual
carbon presents in the sample digests was thermally
converted into CO2 and detected by an infrared sen-
sor. The analytical curve was obtained using reference
solutions containing 1.0, 5.0, 11 and 17 mg l1 C pre-
pared using potassium hydrogen phthalate (C8 H5 O4 K,
Nacalai Tesque, Japan) in aqueous medium. The sam-
ple digests were diluted according to the analytical
curve concentration range.
3. Results and discussions
3.1. Carbon source and sample medium evaluation
The influence of carbon source on C emission
intensities was evaluated using reference solutions
Ratio of carbon emission intensities in axial and radial view con-
figurations ICP-OESs
(nm) Ratio (axial/radial)
Glucose Urea l-Cystein
193.025 18 16 18
247.857 22 20 23
prepared from different organic compounds. Glucose,
urea and l-cysteine were used to prepare reference
solutions in the 0.502.0% m/v C concentration range.
This concentration range showed a non-linear behav-
ior in axial configuration at the 193.025 nm wave-
length. Probably, the elevated carbon concentration
caused self-absorption effects at the most sensitive
wavelength. Thus, measurements were repeated using
solutions containing from 0.05 up to 0.25% m/v C.
The parameters of the analytical curves obtained by
ICP-OES axial and radial view configurations for
each evaluated carbon source are shown in Table 3.
The sensitivity of the measurements was not affected
by carbon source in both studied configurations. The
relative standard deviations of the slopes for curves
obtained using glucose, urea and l-cysteine reference
solutions were around 10 and 3% for axial and radial
view configurations, respectively. We can conclude
that any tested compound could be used for calibra-
tion owing to the low differences observed, however,
it should be mentioned that aromatic compounds can
generate memory effects and therefore aliphatic com-
pounds are recommended for preparation of standard
solutions [8]. All further measurements were car-
ried out using urea. Table 4 shows that axial view
improved sensitivities for all C sources.

Table 3
Analytical curves parameters obtained for glucose, urea and l-cysteine reference solutions established by ICP-OESs with axial and radial
view configurations
Reference solution (nm) Slope Linear coefficient Linear correlation coefficient

Axial Radial Axial Radial Axial Radial

Glucose 193.025 115 6.48 23928 481 0.9993 1.0000
247.857 8.24 0.37 774 39.7 0.9995 0.9999
Urea 193.025 95.9 6.12 24058 554 0.9948 1.0000
247.857 6.86 0.35 950 44.4 0.9946 1.0000
l-Cystein 193.025 115 6.31 25911 469 0.9990 1.0000
247.857 8.30 0.36 782 36.9 0.9996 1.0000
 S.T. Gouveia et al. / Analytica Chimica Acta 445 (2001) 269275 273

The sample medium can influence the analytical sig- Table 6

nal either by physical effects, such as changes in neb-
ulization efficiency, or by chemical processes, such as
alteration of excitation mechanisms in the plasma. The
carbon emission intensities were evaluated in different
media (HNO3 , HNO3 /H2 O2 and H2 SO4 ). All results
were compared to those obtained using reference so-
lutions prepared in aqueous medium. In axial and ra-
dial view configurations, deviations minor than 10%
were observed when HNO3 or HNO3 /H2 O2 medium
was used. Sulfuric acid medium caused a pronounced
decrease in C emission intensities with both config-
urations. This could be related to the higher viscos-
ity of this solution that affects the efficiency of sam-
ple transport to the plasma. This undesired effect of
H2 SO4 can be corrected employing Y as internal stan-
dard. The analytical curve for RCC determination was
prepared in 1.4 mol l1 HNO3 taking into account the
final acid concentration of diluted digests.
3.2. Iron interference
The measurements of carbon at 247.857 nm emis-
sion line for RCC determination can be spectrally
interfered by Fe II 247.857 nm. This Fe ionic line
is two-fold more intense than the C atomic line at
this same wavelength. Based on this effect, the in-
fluence of Fe on carbon measurements at 193.025
and 247.857 nm wavelengths in both configurations
was evaluated. For axial configuration, at 247.857 nm
wavelength, iron caused positive interferences
(Table 5). At 193.025 nm emission line, the signal
variation was lower than 10%. The same behavior
was observed for radial configuration, however, at
observation height of 14 mm the Fe interference on
LOD and BEC for axial and radial view configurations
(nm) Axial Radial
BEC LOD BEC LOD
(mg l1 ) (mg l1 ) (mg l1 ) (mg l1 )
193.025 149 34.0 126 33.0
247.857 251 19.0 90.5 33.0
247.857 nm wavelength was slightly more pronounced
than that observed at 9 mm.
3.3. Limits of detection and memory effects
The limits of detection (LOD) at 193.025 and
247.857 nm wavelengths were determined consider-
ing the background equivalent concentration (BEC)
[9] and the results for both configurations are pre-
sented in Table 6. The background repeatability was
similar in both plasma views, but the measurements at
247 nm in radial view configuration presented higher
R.S.D. due to the low sensitivity at this wavelength.
Despite the highest intensities obtained using axial
configuration, the highest background equivalent con-
centration also increased and affected negatively the
LOD. Therefore, the LODs were similar using axial
and radial configurations. It should be pointed out that
the detection limits with both arrangements could be
slightly deteriorated by C contamination of the plasma
gas despite of the use of liquid argon.
The occurrence of memory effects was investigated
by continuous monitoring of the emission signals of
glucose, urea and l-cysteine solutions intercalated
with blank solution aspiration. For all carbon sources
the C emission intensities decreased quickly after

Table 5
Effect of Fe on C recoverya
Iron (mg l1 ) Recovery (%)

Axial Radial

193.025 nm 247.857 nm 193.025 nm 247.857 nm

9 mma 17 mma 9 mma 17 mma

10 97.2 99.2 98.5 100 104 105

100 97.6 117 99.5 101 112 123
500 103 178 104 103 145 167
a Observation heights.
274 S.T. Gouveia et al. / Analytica Chimica Acta 445 (2001) 269275

Table 7
RCC determined using ICP-OESs with axial and radial view configurations and TOC analyzer in biological sample digestsa
Sample RCC (wt.%)

Axial Radial TOC

NIST-1577b bovine liver 9.82 0.53 10.6 0.01 10.2 0.3

NIST-8435 whole milk powder 14.5 2.0 16.6 1.1 15.3 1.0
NIST-1515 apple leaves 7.79 0.14 8.70 0.10 7.23 0.12
NIST-1570a spinach leaves 8.42 0.32 8.98 0.12 6.89 0.15
a Standard deviation based on sample in quadruplicate (n = 4).

Table 8
Effect of microwave-assisted heating program on RCC in acid digests of lyophilized bovine liver and soybeansa
Microwave program RCC (wt.%)

Lyophilized bovine liver Soybean

Axial Radial Axial Radial

1 10.5 0.8 9.04 0.49 12.3 0.6 10.7 0.6

2 11.0 0.4 10.8 0.5 13.2 1.0 14.1 0.8
3 6.64 0.34 5.55 0.16 8.24 0.58 6.68 0.50
4 9.56 0.75 9.15 0.94 10.5 0.6 10.9 0.6
5 6.20 0.75 5.32 0.79 7.71 1.02 7.27 0.87
6 3.52 0.48 3.35 0.28 5.91 1.6 3.99 0.84
a Standard deviation based on sample in quadruplicate measurements (n = 4).

stopping their nebulization. Thus, the SturmanMasters
chamber was effective for avoiding memory effects.
3.4. Carbon recovery
Additions of 0.05% m/v C to reference solutions
generated recovery values around 100 5% for all
tested carbon compounds in both ICP-OESs config-
urations. Similar results were obtained when C was
added to a lyophilized bovine liver digest, indicating
the absence of matrix effects.
3.5. Residual carbon content determination
The RCCs for biological samples digested using
the microwave digestion programs showed in Table 2
were determined by ICP-OESs with axial and radial
view configurations and TOC analyzer. All measure-
ments with ICP-OESs were carried-out at 193.025 nm.
Table 7 summarizes the obtained results. According
to a paired t-test all results are in agreement at 95 or
99% confidence levels.
The results obtained for lyophilized bovine liver and
soybeans samples digested using different microwave
heating programs are shown in Table 8.
It can be seen that when nominal power was in-
creased from 400 to 800 W in the last step (programs
2 and 3), the RCC decreased 45% in both samples. On
the other hand, when the heating time was increased
from 2.5 to 5 min (programs 1 and 4), the same pro-
nounced effect was not observed. Increasing the heat-
ing time from 2.5 to 7.5 min (programs 4 and 5), the
RCC decreased 38 and 26% for lyophilized bovine
liver and soybeans samples, respectively. These re-
sults indicate a more pronounced effect of nominal
power than heating time on the efficiency of decom-
position. Lower RCCs were reached using simultane-
ously higher nominal power and longer heating time.
4. Conclusions
The developed procedures were suitable for RCC
determination in biological sample acid digests. When
 S.T. Gouveia et al. / Analytica Chimica Acta 445 (2001) 269275
compared to RCC determination using TOC analyzer,
axial and radial ICP-OESs procedures reduced the
analysis time and decreased sample manipulation.
Additionally, the ICP-OES multi-elemental charac-
teristics enable the simultaneous monitoring of other
analytes. Both configurations evaluated presented re-
sults in agreement with those obtained using TOC
analyzer. However, the determination carried out with
axial view configuration presented higher sensitiv-
ity and similar deviations compared to the radial
one. Considering the procedures tested to perform
microwave-assisted acid digestions, it was observed
a more pronounced effect of applied power on the
efficiency of organic compounds decomposition.
Acknowledgements
The authors are grateful to Fundao de Amparo
Pesquisa do Estado de So Paulo by the financial
support (98/10814-3) and by the fellowship provided
275
to F.V.S. (00/00997-4). A.R.A.N., J.A.N. and L.M.C.
are grateful to CNPq by researchships and fellowship
provided. S.T.G. is grateful to CAPES-PICDT by fel-
lowship provided.
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