SPECTROCHIMICA

ACTA
PART B

ELSEVIER Spectrochimica Acta Part B 51 (1996) 1837-1847

Flow injection for the determination of Se(IV) and Se(VI) by

hydride generation atomic absorption spectrometry with microwave
oven on-line prereduction of Se(VI) to Se(IV) 1
J.L. Burguera*, P. Carrero, M. Burguera, C. Rondon, M.R. Brunetto, M. Gallignani
IVAIQUIM (Venezuelan Andean Institute for Chemical Research), Faculty of Sciences, University of Los Andes, P.O. Box 542,
5101-A Merida, Venezuela
Received 26 July 1995; accepted 8 March 1996

Abstract

An on-line flow injection system has been developed for the selective determination of Se(IV) and Se(VI) in citric fruit juices
and geothermal waters by hydride generation atomic absorption spectrometry with microwave-aided heating prereduction of
Se(VI) to Se(IV). The samples and the prereductant solutions (4 tool 1-1 HCI for Se(IV) and 12 tool 1-1 HC1 for Se(VI)) which
circulated in a closed-flow circuit were injected by means of a time-based injector. This mixture was displaced by a carrier
solution of 1% v/v of hydrochloric acid through a PTFE coil located inside the focused microwave oven and mixed downstream
with a borohydride solution to generate the hydride. The linear ranges were 0-120 and 0-100 ~g 1-1 of Se(IV) and Se(VI),
respectively. The detection limits were 1.0 ttg 1-1 for Se(IV) and 1.5/~g 1-l for Se(VI). The precision (about 2.0-2.5% RSD) and
recoveries (96-98% for Se(IV) and 94-98% for Se(VI)) were good. Total selenium values were also obtained by electrothermal
atomic absorption spectrometry which agreed with the content of both selenium species. The sample throughput was about 50
measurements per hour. The main advantage of the method is that the selective determination of Se(IV) and Se(VI) in citric fruit
juices and geothermal waters is performed in a closed system with a minimum sample manipulation, exposure to the environ-
ment, minimum sample waste and operator attention.

Keywords: Citric fruit juices; Geothermal waters; Hydride generation; On-line flow injection; Se(IV); Se(VI)

1. I n t r o d u c t i o n Nutrition Board of the US National Research Council

Selenium has received much attention as an essen-
tial and also as a very toxic element [1]. Thus, food
and water must be monitored for trace amounts of this
element. An estimated safe and adequate daily dietary
intake has been established as 1 0 - 2 0 0 ~g day -1,
depending on age [2]. Specifically, the Food and
* Corresponding author.
1This paper was published in the Special Issue of Spectrochimica
Acta, Part B, devoted to Flow Analysis.
[3] has recommended a dietary selenium allowance of
0.87 #g kg -1 or, with rounding, 55 and 70 #g day-1 for
the reference North American adult female and male,
respectively. Although selenium levels in ground and
surface waters are generally low (less than 10/zg 1-1),
high concentrations of this element may occur in asso-
ciation with geological features or due to the corrosion
of household plumbing by soft, acidic water [4]. The
concentration of selenium in fruits is also low, usually
below the 100 ttg 1-1 levels [5]. However, the levels of
selenium in individual foods of plant origin are highly

0584-8547/96/$15.00 Copyright 1996 Elsevier Science B.V. All rights reserved

PII S0584-8547(96)01521-2
1838 J.L. Burguera et al./Spectrochimica Acta Part B 51 (1996) 1837-1847
variable, depending on the soil conditions under
which such foods are grown.
In toxicology it has long been known that great
differences in toxic properties occur among the var-
ious species of an element, because they follow dif-
ferent metabolic pathways. In particular, selenium
absorption, retention and distribution within the
body, and the amounts, forms and routes of excretion
vary with the chemical forms and amounts of the ele-
ment ingested [6]. Although precise feeding compar-
isons of the relative toxicity or nutritional activities of
the different selenium compounds have not yet been
made, it is known that selenite is more toxic than
selenate [7]. Thus, the study of the selenium species
in waters, food and biological fluids would provide a
better understanding of the requirements of this ele-
ment in the living system.
Most methods for selenium determination analyze
total selenium [8]. However, relatively few analytical
methods have been applied for the selective determi-
nation of the different selenium species present in
various matrixes. Chromatographic techniques
coupled with different detector systems have been
extensively used for the separation and determination
of all selenium species. This approach minimizes
interferences from the matrix. However, errors may
arise from a lack of efficiency in the separation, e.g.
due to incomplete retention on the column, decompo-
sition of the species, incomplete recovery of the eluate
or peak overlap [9]. There are few electrochemical
methods that can be applied for selenium speciation
in biological fluids, or electrochemical methods that
can be applied for selenium speciation in biological
fluids and environmental samples [8,10,11]. However,
the complete mineralization or conversion of Se(VI)
to Se(IV) (the electroactive form) makes sample pre-
paration more complex and increases the risk of
sample contamination and of losses of selenium.
Spectrofluorimetric methods have been also used for
the determination of the different inorganic species of
selenium [8,10]. Although very sensitive, an initial
acid digestion step is required for this technique and
the analytical figures of merit may be markedly influ-
enced by extractants, temperature and the hydrogen
ion concentration.
The detection of methyl selenide species is carried
out after gas chromatographic (GC) separation on the
basis of their different retention times with a wide
variety of detection methods such as: electrothermal
atomic absorption spectrometry (ETAAS) [12] and
microwave-induced helium plasma detection
(MWPO) [13].
The most commonly applied technique for inorganic
selenium species determination is based on hydride
generation (HG) with atomic spectrometry (AS)
detection [10]. In all of these techniques, Se(IV) is
determined directly after derivatization process,
whereas Se(VI) is determined by difference after
reduction of the solution with HC1, and the organic
selenium content is also determined by difference
after destroying organic compounds by oxidation.
These techniques are highly sensitive and yield detec-
tion limits in the ng 1-1 and are not subject to major
interferences or high background noise levels [14].
The severe and systematic imprecisions reported for
this technique are almost due to the use of improper
sample decomposition [8]. The tolerance limits for
other hydride-forming elements in the determination
of selenium could be improved by one or two orders
of magnitude by using a flow injection (FI) instead of
a batch system and optimizing the analytical condi-
tions systematically [15]. According to the literature
on total selenium determination in biological and
environmental materials, the combination of FI tech-
niques with HG-AAS is an accepted method [16-21].
To our knowledge, only one paper has described an FI
closed system with thermal heating at 140C for the
determination of Se(IV) and Se(VI) by HG-AAS with
on-line prereduction of Se(VI) to Se(IV) [22]. No
losses of selenium occur and the method has been
successfully applied to the speciation of both
inorganic species in sea water.
This paper proposes inorganic selenium speciation
in lemon juice and geothermal waters using an auto-
mated time-based FI-HG-AAS system with on-line
prereduction of Se(VI) using microwave (MW)
heating.
2. Experimental
2.1. Apparatus
Atomic absorption measurements were made with a
Varian-Techtron model AA-1475 spectrometer
equipped with an air-acetylene burner head, a
 J.L. Burguera et al./Spectrochimica Acta Part B 51 (1996) 1837-1847
7.0 m A conventional selenium hollow cathode lamp,
and a deuterium-arc background corrector was used
for this study. The flame was obtained with a flow
rates of 181 min -1 for air and 2.01 min -1 for acetylene.
The wavelength used was 196.0 nm with a spectral
bandpass of 1.0 nm. An open-ended quartz tube, 6 cm
long, 6 m m inner diameter and 8 cm tubing inlet, was
used for hydride atomization. The atomizer was
located about 5 m m above the burner slot in the opti-
cal path, and aligned with the help of the adjusting
mechanisms of the instrument. The system also
included an Ismatec IPC eight-channel peristaltic
pump and 0.8 m m i.d. Acidflex tubing, unless other-
wise stated. Details of the construction and function-
ing of the time-based injector (TBI) were previously
described [23,24]. This injector was operated by a
programmable Gralab model 900 electronic timer. A
Prolabo MW Microdigest oven model 301 was used.
Thi:; oven has a timing cycle and a variable heating
cyc: e based on power setting up to 200 W (frequency
i 1
NaBH4 I ~
3 ml min-l[_:_ J
_2/
1 3
I
L. . . . . . . . . . . . . . . . ..I
Twae-based
rejecter
NaBH. i [i
Pump
Fig. 1. Schematic diagram of the FI-MO-HG-AASmanifolds. R l-R4: tubing lengths 150, 140, 40 and 50 cm, respectively.Different flow rates
were achieved by varying the pump tube sizes. 1-6 indicate sets of tubing V 1-V6, respectively.Here the TBS injector is in the filling operation,
thus the set of tubing 1 (VI, V3 and Vs) is opened (-C)-), while the set of tubing 2 (V2, V4 and V6) is dosed (-e-). For further details and
operating procedure, see text.
1839
of 2450 MHz), controlled by means of a Prolabo
Maxidigest TX 32 programmer. The gas phase separa-
tor (GPS) was the same as previously described [25].
An ice trap (Fig. 1) was used to reduce the tempera-
ture of the hot effluent and therefore to help to control
flow disturbances. The ETAAS verification measure-
ments were performed using a Perkin-Elmer model
2100 atomic absorption spectrometer with an HGA-
700 furnace and an AS-90 furnace autosampler. Pyro-
litic coated graphite tubes were used with pyrolytic
graphite platforms.
2.2. Reagents
All reagents were of analytical-reagent grade (from
Sigma Chemicals or Merck) and distilled deionized
water was used.
Stock standard solutions (1000 m g l -~ of the
analyte) were prepared by dissolving 0.5531 g of
Na2SeO4 (for Se(IV)) or 0.6104 g of Na2SO4 (for
Time~
Spectrcrne~r
Atom~r
~~'~~- N2
[:co
ch~rnbet Gas phase
~eio~rator
Microw;lveo v e ~
1840 J.L. Burguera et al./Spectrochimica Acta Part B 51 (1996) 1837-1847

Se(VI)) in water and diluting to 250 ml in each case.
Working standard solutions were prepared daily and
diluted with water prior to analysis.
A 0.5% (w/v) sodium tetrahydroborate (NaBH4)
solution was prepared daily by dissolving 5.0 g of
NaBH4 in 0.5% (w/v) NaOH and diluting quantita-
tively to 1 1 with the same solution. This stabilized
solution can be stored for at least a week without
changes in the reductant activity.
2.3. Sample preparation
Juice samples were obtained by squeezing the fruit,
and after filtration through a filter paper (Whatman
No. 1), these were kept under refrigeration until
their analyses. Geothermal waters [26] were collected
under an anaerobic environment, as previously
described [27]. Spiked samples were homogenized
in an ultrasonic bath for 5 min.
2. 4. Determination procedure
Samples and all reagents were fed through their
respective lines at room temperature, as indicated in
Fig. 1. For the present work, the TBI has two sets of
tubing (set 1: V1, V3 and Vs; set 2: V2, V4 and V6) ,
which are used for regulating the introduction and
mixing of sample and prereductant solution, and to
carry this mixture downstream through the FI system.
The duration and function of each sequence of the FI-
MW oven program are as follows. In sequence 1
(filling operation), the tubing set 1 was opened long
enough to allow the carrier solution to fill the tubing
up to the GPS. At the same time, the tubing set 2 was
closed; in this way, the sample and prereductant solu-
tion could be recirculated at will without waste and
cross-contamination. The duration of this sequence
was 30 s. In sequence 2 (injection operation) as the
solenoid valve of the TBI is switched to the alternate
position (injection cycle), the tubing set 2 was opened
and the tubing set 1 was closed to allow the mixing of
sample and reductant solutions in R1, while the
carrier/washing solution recirculated. The duration
of this sequence was 10 s. In sequence 3 (measure-
ment operation) the synchronous activation of the
solenoid to its initial position (as in sequence 1) and
turning on the MW oven ensures the appropriate heat-
ing conditions for the prereduction of Se(VI) to
Se(IV), while the sample/prereductant solution passes
through the coiled FFFE tubing (R2) located inside the

0.60
i
0.48

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e /" ,

0.24 - 1 /// ."

0.00 i t i I I I I

0.05 0.095 0.163 0.253 0.385 0.50 0.77 0.95 1.87

B o r o h y d r i d e c o n c e n t r a t i o n ( % W / V )

Fig. 2. Effectof sodiumborohydrideon the absorbancefroman aqueousstandardsolutioncontaining10 #g i-1 of Se(IV)and Se(VI).Curves 1

and 2 are absorbancesignals obtainedfor Se(IV)and Se(VI),respectively.Experimentalconditionsas specifiedin Table 1.
 .LL. Burguera et aL / Spectrochimica Acta Part B 51 (1996) 1837-1847 1841

MW oven. An additional continuous stream of NaBH4
solution, introduced after the MW oven, ensures a
stable baseline and thus eliminates the problem of
varying blank levels. The separation of the gas-liquid
phase is completed in the GPS and the resulting vapor
is carded with a nitrogen flow into the quartz atomi-
zation cell. The results presented here are the means
of five determinations.
3. Results and discussion
3.1. Optimization of operating conditions
The reagent concentrations and injected volumes,
carrier flow rates and transfer line length were opti-
mized using the one-factor-at-a-time method.
from Se(IV) and Se(VI) solutions was found to be
0.5% (w/v) using 2 and 12 mol 1-1 hydrochloric acid
concentrations, respectively. At this NaBH4 concen-
tration, the selenium absorption signals were well
defined and the lagging edges of the peaks had
returned to the base line well within the 5 s integration
period. At NaBH4 concentrations below 0.75% (w/v)
the lagging edges showed significant and prolonged
tailing. Concentrations of the reductant higher than
0.75% (w/v) led to a decrease in sensitivity and caused
extremely sharp but non-reproducible signals, prob-
ably because the generation of hydrogen and its trans-
fer to the atomization cell exceeds the rate of
formation of hydrogen selenide considerably [28]. A
concentration of 0.5% (w/v) was then used in further
studies, which is in agreement with the optimal con-
centration also found by Cobo et al. [22].

3.2. Effect of NaBH4 concentration 3.3. Effect of reagents and sample volume

To determine the optimum NaBH4 concentration, The system exhibit strong dependence on the total
different concentrations in the range 0.05-1.85% volume of solution in which the analyte is present.
(w/v) were tested. Fig. 2 shows that the optimum con- Fig. 3 shows the average peak heights from both
centration of NaBH4 for producing hydrogen selenide selenium species as a function of the sample and

1.00 -

0.80 -

II 0.80 -
t~ / 2
eo,,,. /.-
/.

m
,Q
< 0.40 -
/ 1

.1+"
1
4
0.20

I I I I I I I
0.00
0.2 0.3 0.4 0.5 0.6 0.7 0.8 1 1.25 1.5
V o l u m e (ml)

Fig. 3. Effectof sample and prereductantsolutionvolumes.Curves 1 and 2: absorbancesignals obtainedfrom 5 ng of Se(IV),respectively;

curves3 and 4: absorbancesignalsfroma solutioncontaining10 t*gI-1 of Se(VI)and Se(VI),respectively.Experimentalconditionsas specified
in Table 1.
1842 J.L. Burguera et al./Spectrochimica Acta Part B 51 (1996) 1837-1847

prereductant solutions variable volumes, for a fixed
amount (5 ng) of selenium situated in the linear part
of the calibration curve (curves 1 and 2) and variable
amounts of Se from a solution of 10/~g 1-1 of Se(IV)
and Se(VI) (curves 3 and 4). The minimum volume
that can be used is determined by the ability of the
system to provide thorough mixing of the sample
solution with the prereductant solution of hydro-
chloric acid, and this depends on the length of tubing
located inside the oven (see below). The peaks tend to
broaden and decrease with increasing solutions
volumes, indicating a delayed release of the hydride
from the solution. It is clear that the loss of sensitivity
may be due to inadequate and inhomogeneous mixing
of the sample with the hydrochloric acid and NaBH4
solution, and to partial dissolution of the gaseous
hydride in the solution on its way to the atomization
cell. Although the precision of the measurements
remains satisfactory throughout the whole volume
range (RSD < 5%), as the injected volumes decreased
the signals obtained were less reproducible; for exam-
ple, for the injections of 0.25, 0.50 and 1.50 ml, the
RSDs were 4.0, 2.0 and 1.0%, respectively. The injec-
tion of different volumes of a 10/~g 1-1 of Se(IV) and
Se(V) solution shows that no advantageous effect was
observed by changing the amounts of analyte and
prereductant when the injected volumes were over
0.50 ml; above this volume steady signals were
observed. Therefore, the choice of appropriate
injected volumes was determined by the sensitivity
and precision required for the determinations. As the
injection of 0.50 ml volumes yield satisfactory results,
this was chosen for further studies.
3.4. Influence of tubing lengths
Previously, it was shown [29,30] that for selenium
hydride the type of connection between the reaction
cross and the GLS affects the completeness of strip-
ping of the hydride. The completeness of stripping
increases with increasing length of the stripping
device. As the main scope of the present work was
to determine selectively both selenium species with
the aid of MW heating, experiments were carried out
with knotted reaction coils (Re in Fig. 1) of different
lengths located inside the MW oven cavity. Fig. 4
shows that the length of R2 influenced the hydride
generation rate and the release of analyte from the
sample solution. These effects were more pronounced
in the case of Se(VI), probably because longer

0.70

0.56

$ 0.42
g=

.o'7,
J
o
.o /
< 0.20 i

0.14
I
.-'
/

0.00 J I i i i I i I I

20 40 80 1 O0 120 140 160 180 200 220 240

Tubing length (cm)
Fig. 4. Effectof the tubinglengthinsidethe MWo v e n (R2)on the absorbanceobtainedfroma solutioncontaining10 #g 1-1of Se(IV)(curve1)
and of Se(VI)(curve2). Experimentalconditionsas specifiedin Table 1.
 J.L. Burguera et al./Spectrochimica Acta Part B 51 (1996) 1837-1847
residence times of the sample solution are required to
allow an appropriate thermal treatment of the sample
for the quantitative reduction of Se(VI) to Se(IV). On
the other hand, the peak height absorbances were
largely independent of the length of the reaction coil
used after the oven (R3) and the confluence point with
the tetrahydroborate solution (R4), suggesting a rela-
tive little overall dispersion in our system. However,
they were as short as possible (R 3 ---40 cm and R4 -- 50
cm) to avoid a very slight but steady drop in sensi-
tivity due to dispersion. Previous results have shown
that under these conditions the hydride formation and
the completeness of the stripping processes are suffi-
cient before the reaction mixture reaches the gas-
liquid phase separation unit.
3.5. Effect of nitrogen flow rate
In addition to transporting the hydrogen selenide to
the atomization cell, the carrier gas also expels any air
present in the system and avoids the oxidation of
H2Se, hence allowing precise measurements to be
made in the ultraviolet region. In this study, the carrier
gas flow rate was varied in the range 50-300
ml min-1. Fig. 5 shows dependence of the absorption
0.70 -
0.64
8 0.58
C
< 0.52
/ :
0.46
0.40 I I
50 70 90
Fig. 5. Effectof nitrogencarriergas on the absorbancesignals obtainedfor Se(IV)(curve 1) and Se(VI)(curve2). Experimentalconditionsas
specifiedin Table 1.
1843
signal from 5 ng of Se(IV) and Se(VI) on nitrogen
flow during the determination step. Tailing of the
peak shape and the noise levels increased slightly
with decreasing flow rate, probably due to the fact
that a too low flow rate may be inadequate for the
efficient transfer of the hydride into the quartz cell
and removal of the decomposition products from the
atomizer. A flow rate above 125 ml min -1 failed to
give a further increase in the absorption signal. In
this case a too high carrier gas flow decreased the
absorbance of the analyte due to a shorter residence
time of the analyte atoms in the atomizer [28]. There-
fore, an analytical flow rate of 125 ml min -1 was
chosen for all further work.
3.6. Effect of MW power setting and of hydrochloric
acid concentration
Hydrochloric acid concentrations > 4 mol 1-~ have
little influence on the sensitivity obtained for Se(IV)
provided that the MW oven power settings exceeds
20% of its full capacity (Fig. 6), whereas the same
effect was observed for Se(VI), but when the HC1
concentrations are < 7 mol 1-1, and the MW oven
power settings are below 70% of its full capacity
i l I J A I
100 140 170 220 250 300
N i t r o g e n Flow (ml r a i n - l )
1844 J.L. Burguera et aL/Spectrochimica Acta Part B 51 (1996) 1837-1847

0.70 -

12
~, - o - -

f . 1 -~
0.58 -
.f"

j- J
j" / 10
0.42 j"
J A"7. j"
.,,.,
t

GO
-8
< 0.28 o~ , -

J t...~ -'~'7" . . .
..t-" , -~

f ..-
joJ" ....
0.14 ~- " /

4
0.00 :
0 20 40 60 80 1 O0
Microwave-oven p o w e r setting ( % )

Fig. 6. Effect of the MW oven power setting on the absorbance obtained from a solution of 10 /zg 1 - 1 of Se(IV) at hydrochloric acid
concentrations of 2, 4, 6, 8, 10 and 12 mol l-1 (curves 1-6, respectively). Other experimental conditions as specified in Table 1.

0.70

o /
0.80
,/ .
t
5/ .. 4
.; //
/ ,/ t
J
/ / /
0.50 / p
c
=,
,Q /, / t 2
v / / ,s
Q
/1 / t
< 0.40 1
/

/ - _ :- 2 2 ~
0.30

0.20 I t I ! : ~ t
0 10 20 30 40 50 60 70 80 90
Microwave-oven power setting (%)

Fig. 7. Effect of MW oven power setting on the absorbance obtained from a solution of 10 #g 1-1 of Se(VI) at hydrochloric acid concentrations
of 2, 4, 6, 8, 10 and 12 tool 1-1 (curves 1-6, respectively). Other experimental conditions as specified in Table 1.
 J.L. Burguera et al./Spectrochimica Acta Part B 51 (1996) 1837-1847 1845

0.30

200
0.25

j
8 0.20 / / / 120
11 / /
/' /
o
o
.Q
< 0.15
J ./
/ ""/ / " 80

0.10 - ./ /:
J- -" ~" 40

0.05 J I I I I '

40 50 60 70 80 90 100
Microwave-oven power setting (%)

Fig. 8. Effect of MW oven power setting and Se(VI) concentration on the absorbance obtained from a solution of 10/zg 1-: of Se(1V) and 4
mol 1-t HCI. Numbers indicate Se(VI) concentration in ~tg l -a, respectively. Other experimental conditions as specified in Table 1.

(Fig. 7). Acidic concentrations < 4 mol 1-1 gave lower and 10/zg 1-1 in Se(IV) was studied. As can be seen
sensitivity and poor reproducibility in the determina- in Fig. 8, the on-line selective determination of Se(IV)
tion of Se(IV), regardless of the MW oven power in the presence of Se(VI) is possible at MW oven
settings, owing to incomplete and varying reduction power settings below 60% of its full capacity. As
of the NaBH4. The RSD of the signals obtained from the reduction of Se(VI) is strongly temperature
Se(IV) and Se(VI) by the use of 4-12 mol 1-z HCI dependent [10], an increase in the oven power
were always within the range 0.5-2.5%, whereas increased the temperature and the reduction process.
the RSD for 3, 2 and 1 mol 1-1 HCI concentrations On the other hand, the selective determination of
were 3.8, 4.9 and 5.9, respectively. It also was
found that the signal from Se(VI) increased with
HCI concentration and with oven heating. This obser- Table 1
Optimum operating MW-FI-HG conditions
vation could be due to the fact that the reduction of
Se(VI) to Se(IV) occurred spontaneously, even at Component Parameter Value
room temperature, at HC1 concentrations > 9 mol 1-1
MW Power select control for Se(IV) 40%
and appeared to go rapidly to completion as the tem- Power select control for Se(VI) 95%
perature increased. Hence, 4 and 12 mol 1-1 HC1 were Prereduction coil (R2) length 170 cm
used for the determinations of Se(IV) and Se(VI), HG [HCI] for Se(IV) 4 mol 1-1
respectively. [HC1] for Se(VI) 12 mol 1-1
[Carrier solution] of HC1 1% v/v
[NaBH4] 0.5% w/v
3. 7. Effect of M W oven setting and of Se(Vl) Nitrogen flow rate 125 ml min -~
concentration FI Sample and prereductant 3 ml min -~
solutions flow rate
The effect of variable concentrations of Se(VI) and Carrier solution flow rate 2 ml min -~
Additional stream of NaBH4 2 ml min -I
of MW oven power settings on the absorbance solution flow rate
obtained from solutions that were 4.0 mol 1-1 HC1
1846 J.L. Burguera et al./SpectrochimicaActa PartB 51 (1996) 1837-1847

Table 2 0.70 #g 1-1 detection limit, 2 - 2 5 0 #g 1-1 linear range

Figures of merit for Se(IV) and Se(VI) obtained in a solution where and precision of 2.5-3% (SD) for both species deter-
both species were present mined in sea water [22]. The accuracy of the pro-
Parameter Species cedure was investigated by determining both
selenium species in Se(IV)- and Se(VI)-spiked
Se(lV) Se(VI)
lemon juice and geothermal water samples. The
Regression line (A = mC + b) a A = 0.0050 A = 0.0040 results are shown in Table 3. The fact that only
Se + 0.0003 Se + 0.001 Se(IV) is quantitatively recovered from samples
Linear range (~g 1-1) 0-120 0-100
Correlation coefficient (r 2) 0.9992 0.9996 spiked with both selenium species indicate that, by
Precision (%)b 2.0 2.5 following the previously given procedure their
Detection limit (/zg 1-1)c 1.0 1.5 speciation in the samples under study is possible.
The accuracy of the proposed procedure was further
aA and C indicate the absorbance and analyte concentration in
#g l -l, respectively. investigated by determining the total selenium content
b RSDs from 10 replicate measurementsperformed with 10/~g 1-1 in lemon juice and geothermal water samples by
solutions of each selenium species. ETAAS, following the procedure described by
c Detection limits based on three times the standard deviation of Burguera et al. [31]. In this work, the total selenium
the blank signal. Experimental conditions as specified in Table 1.
contents found for lemon juice (7.42 + 0.1 #g 1-1) and
geothermal water (10.7 ___ 0.1/.tg 1-1) samples were in
Se(IV) was found to depend on the concentration of good agreement with those obtained for both samples
Se(VI) (Fig. 8). This selectivity was possible only by ETAAS (7.55 0.2 and 10.8 0.2 #g 1-I for
when the weights of the two selenium species do lemon juice and thermal water samples, respectively),
not exceed 1:4 (Se(IV):Se(VI)). with a confidence level of 98%, which is an indication
of satisfactory accuracy of the proposed method and
3.8. Figures of merit of the proposed method that in these samples the selenium is found in its
inorganic forms.
The linear range for each analyte, the detection
limits and reproducibility of the measurements using 3.9. Analysis of real samples
the on-line MW aided prereduction of Se(VI) were
determined under the optimum conditions given in In the samples under study, selenium is present as a
Table 1. The results are shown in Table 2. The con- mixture of Se(IV) and Se(VI), with a predominant
centration of Se(VI) was calculated as the difference presence of Se(IV). The relative contents of Se(IV)
between total selenium and Se(IV). These levels are in are 70, 71, 100 and 68% in geothermal water and
good agreement with previously published values of lemon, mandarin and orange juices, respectively. In
this work the total selenium contents are found to be
lower than those previously reported by Arruda et al.
Table 3 (34.6-42.7 #g 1-t in orange juice) [5].
Recovery studiesa
Sample Spiked amount / Found / Recovery / %
(/.Lg 1-I) (~g 1-1) 4. Conclusions
Se(IV) Se(VI) Se(IV) Se(VI) Se(IV) Se(VI)
The present work clearly shows that it is relatively
Lemon juice 5 10 10.2 12.0 98 98 simple to obtain quick and accurate results for Se(IV)
10 5 15.3 7.0 100 96
Geothermal 5 10 12.3 13.0 96 97 and Se(VI) at low concentrations in citric fruit juices
water and geothermal waters by using M W thermal aided
10 5 15.2 8.0 99 94 on-line prereduction. The on-line system and reduc-
a The endogenous Se(IV) and Se(VI) contents were of 5.3 and tion steps reduces sample handling and makes com-
2.0 #g l-I (in lemon juice) and 7.5 and 3.3 #g 1-1 (in geothermal plete automation of the inorganic selenium species
water), respectively.Experimentalconditions as specifiedin Table 1. determination possible. MW heating has several
 J.L. Burguera et al./Spectrochimica Acta Part B 51 (1996) 1837-1847
advantages, particularly in that it allows strict control
over the heating power as well as over the time the
heating is applied.
Acknowledgements
The authors acknowledge the financial support
given by the CDCHT, (Consejo de Desarrollo Cienti-
rico, Humanistico y Technologico) of Los Andes
University, M~rida, Venezuela.
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