Food Chemistry 122 (2010) 188–194

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Food Chemistry
journal homepage: www.elsevier.com/locate/foodchem

Total content of As, Sb, Se, Te and Bi in Spanish vegetables, cereals and pulses
and estimation of the contribution of these foods to the Mediterranean daily
intake of trace elements
M.N. Matos-Reyes a, M.L. Cervera a,*, R.C. Campos b, M. de la Guardia a
a
Department of Analytical Chemistry, University of Valencia, 50 Dr. Moliner Street, 46100 Burjassot, Valencia, Spain
b
Department of Chemistry, Pontifícia Universidade Católica do Rio de Janeiro, Rua Marquês de São Vicente, 225, 22453-900, Rio de Janeiro, RJ, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: As, Sb, Se, Te and Bi were quantified in vegetables, pulses and cereals, in order to increase the available
Received 15 December 2008 information on the presence of these elements in the Mediterranean daily intake. Samples were dry
Received in revised form 24 November 2009 ashed and the ashes dissolved with diluted HCl. Hydride generation atomic fluorescence spectrometry
Accepted 20 February 2010
was used for quantification. Limits of detection (LOD) ranged from 0.2 to 1.7 ng g1 and the accuracy
was assessed by the analysis of three certified reference materials, Rice Flour (NIST 1568a), Tomato
Leaves (NIST 1573) and Cabbage (IAEA 359). Good concordance between results found and certified val-
Keywords:
ues were always observed. As, Sb, Se, Te and Bi levels varied in samples analysed from values under the
HG-AFS
Dry ashing
LOD till 1001, 47, 270, 104 and 48 ng g1, respectively.
Arsenic Ó 2010 Elsevier Ltd. All rights reserved.
Antimony
Selenium
Tellurium
Bismuth
Pulses
Cereals
Vegetables
Daily intake

1. Introduction food composition data are important to both, consumers and

Foods together with water provide the major proportion of the
total daily intake of trace elements by humans. Vegetables, cereals
and pulses are some of the most common foods in human diet
around the world. Besides soil and water, foods can be also con-
taminated with trace metals by the introduction of mechanized
farming, the increasing use of chemicals, sprays, preservatives,
food processing and package. In order to get the minimum adverse
impact, it is important to measure and continuously monitor the
levels of trace elements in various kind of foods. Trace element
Abbreviations: ETAAS, electrothermal atomic absorption spectrometry; HG-AAS,
hydride generation atomic absorption spectrometry; FI-HG-AAS, flow injection
hydride generation atomic absorption spectrometry; FI-HG-GF-AAS, flow injection
hydride generation graphite furnace atomic absorption spectrometry; HG-AFS,
hydride generation atomic fluorescence spectrometry; ICP-MS, inductively coupled
plasma mass spectrometry; Q-ICP-MS, quadrupole inductively coupled plasma
mass spectrometry; ICP-OES, inductively coupled plasma optical emission
spectrometry.
* Corresponding author. Fax: +34 96 3544838.
E-mail address: M.luisa.cervera@uv.es (M.L. Cervera).
health professionals, and in recent years food labeling legislation
has highlighted this requirement. By the way, trace element deter-
mination in complex matrices, such as food, often requires exten-
sive sample preparation and/or extraction treatments prior to
their determination by instrumental techniques.
Table 1 summarizes the main sample digestion methods pro-
posed in the literature for the determination of As, Sb, Se, Te and
Bi in vegetables, cereals and pulses classified according to the
different analytical techniques used. It can be seen that the use
of microwave assisted digestion is the most commonly used
method. Although this digestion procedure is not complete, resi-
dues of organic matter and acids seems to not be problematic for
measurements made by high atomisation temperature tech-
niques such as electrothermal atomic absorption spectrometry
(ETAAS) (Cho & Suh, 1999; de Gregori, Pinochet, Fuentes, & Po-
tin-Gautier, 2001; Gawalko, Nowicki, Babb, Tkachuck, & Wu,
1997; Tsukada & Hasegawa, 2002), inductively coupled plasma
optical emission spectrometry (ICP-OES) (Cocchi, Vescovi, Petrini,
& Petrini, 2006; d’llio, Alessandrelli, Cresti, Forte, & Caroli, 2002;
Dursun, Musa-Ozcan, Kasik, & Ozturk, 2006) and inductively

0308-8146/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.foodchem.2010.02.052
 M.N. Matos-Reyes et al. / Food Chemistry 122 (2010) 188–194 189

Table 1
Methods and sample treatments proposed for the determination of As, Sb, Se, Te and Bi in vegetables, cereals and pulses.

Element Sample Sample treatment Method Ref.

As Asparagus Digestion: HNO3 + K2SO4 ETAAS Xue and Fu (2000)
As, Se Rice flour Microwave acid digestion ETAAS Cho and Suh (1999)
As, Se Rice Dry ashing ETAAS Rivero-Hughet et al. (2006)
Sb Cabbage Microwave digestion: HNO3 + HClO4 + HF ETAAS Tsukada and Hasegawa (2002)
Sb Alfalfa Microwave digestion: HNO3 + H2SO4 + H2O2 ETAAS de Gregori et al. (2001)
Se Garlic, onion Wet digestion ETAAS Izgi et al. (2006)
Se Garlic Microwave digestion ETAAS Wysocka, Bulska, and Wrobel (2003)
Vegetables Digestion: HNO3 + Triton X-100 Regina-Rosa, de Moraes, Gomes-Neto, Araujo-
Nobrega, and Araujo Nogueira (2002)
Se Wheat, rice-flour, rice- Microwave digestion in closed vessels with HNO3, ETAAS Gawalko et al. (1997)
bran, wheat products microwave digestion in focused open-vessel with
H2O2 + HNO3
Te Garlic Preconcentration by co-precipitation HG-AAS Kaplan et al. (2005)
As Several vegetables Dry ashing FI-HG-AAS Muñoz et al. (2002)
Se Cereals Microwave digestion: HNO3 + H2O2 FI-HG-GF- Ajtony et al. (2005)
AAS
Sb Alfalfa Microwave digestion: HNO3 + H2SO4 + H2O2 or HG-AFAS de Gregori et al. (2001)
HNO3 + H2O2
As Vegetables Dry ashing HG-AFS Diaz et al. (2004)
As Corn, wheat, rice flour Wet digestion: HNO3 + HClO4 HG-AFS Jiang, 1999
and wheat flour
As, Se Rice, cereal foods Microwave digestion: HNO3 + H2O2 ICP-MS d’llio et al. (2002)
Sb Cabbage Microwave closed vessel digestion: HNO3 + HClO4 + HF Q-ICP-MS Cubadda et al. (2002)
Sb, Se, Onion Microwave digestion: HNO3 ICP-MS Gundersen et al. (2000)
Te,
Bi, Se Garlic Microwave digestion ICP-MS Wysocka et al. (2003)
As, Se Onion, lettuce Acid digestion: HNO3 precipitation ICP-OES Atanassova, Stefanova, and Russeva (1998)
Se Rice Acid-assisted microwave: HNO3 + H2O2 ICP-OES d’llio et al. (2002)
As, Se, Edible mushrooms Microwave digestion: HNO3 ICP-OES Dursun et al. (2006)
Bi
Bi Cereal, cereal flour Wet digestion and dry ashing ICP-OES Izgi et al. (2006)
As, Se Edible mushroom Microwave digestion: HNO3 ICP-OES Cocchi et al. (2006)

coupled plasma mass spectrometry (ICP-MS) (Cubadda, Raggi,
Testoni, & Zanasi, 2002; d’llio, Alessandrelli, Cresti, Forte, & Car-
oli, 2002; Gundersen, Bechmann, Behrens, & Sturup, 2000). How-
ever, when it is necessary to generate covalent hydrides for
atomic absorption spectrometry (AAS) or atomic fluorescence
spectrometry (AFS), the residues of organic matter and acids
could interfere with the hydride generation, being necessary
the use of high dilution factors, which sometimes make impossi-
ble the quantitative determination of ultra trace levels of toxic
elements. Nevertheless, dry ashing completely destroys the or-
ganic matter providing a preconcentration of samples and get
clean blanks and thus, limits of detection (LOD) values attainable
are very low. However, it is necessary to ensure that, there are
no losses of elements to be determined during the ashing process
and to do it, the use of ashing aids is mandatory (Rivero-Huguet,
Huertas, Francini, Vila, & Darre, 2006; Muñoz et al., 2002; Diaz
et al., 2004).
Concerning the elements studied, it must be noticed that, ar-
senic is a common element present in food and thus, the level of
human exposure is considered part of the health protection pro-
grams because its toxicity. In general, vegetables, pulses and cere-
als are important pathways for the As uptake in the food chain.
Matrices of plant do not tend to accumulate arsenic in high levels
but it has been reported that rice can cumulate inorganic arsenic,
the most toxic As species (d’Amato, Forte, & Caroli, 2004; Matos-
Reyes, Cervera, Campos, & de la Guardia, 2007; Sanz, Muños-Oliva,
& Camara, 2005). The increase of studies focused on the analytical
chemistry of Sb and its compounds can partly be attributed to the
recognition of its possible harmful effect. In general, only fairly
limited information is available about the effects of Sb on human
health. So far, Sb has not been identified as an essential element
for humans. Selenium is a trace element of a great importance,
since it is essential for humans and animals at low concentration
and also it is an antioxidant present in essential enzymes (Dumont,
Vanhaecke, & Cornelis, 2006). However, its excessive intake often
results in the manifestation of toxic syndromes. Its levels in agri-
cultural soils primarily influence the presence of selenium in the
human food chain. Excessive Se intake in human diet results in
dermatitis, dizziness, brittle nails, gastric disturbances, hair loss,
and a garlic odor on the breath. Tellurium is regarded as rare,
non-essential element, usually occurring at low concentration lev-
els, and it is known its toxicity for humans (Cava-Montesinos, Cer-
vera, Pastor, & de la Guardia, 2003a, 2003b). Bismuth is not an
essential element for plants and animals (Tokman & Akman,
2004). With the extensive use of Bi in different areas of life, it
has been distributed in the environment and the chance of expo-
sure of this element to organisms has also increased (Das, Chakr-
aborty, Cervera, & de la Guardia, 2006).
Regarding methodologies and data available in the scientific lit-
erature about the content of the studied elements in vegetables,
cereals and pulses it must be noticed that there are many studies
on As and Se but only few ones on Sb, four studies on Bi determi-
nation in cereals (Izgi, Gucer, & Jacimovic, 2006), edible mush-
rooms (Dursun et al., 2006), cauliflower and vegetables (Lagunas-
Solar, Pina, Flocchini, Solis, & Mireles, 2005) and several studies
on Te in garlic (Kaplan, Cerutti, Salonia, Gasquez, & Martínez,
2005; Khoo & Ye, 2002), and onion (Gundersen et al., 2000) being
thus required the development of methodologies to do this kind
of determination in an accurate way.
On considering the dietary intake of the aforementioned ele-
ments it has been reported that the daily intake of arsenic from
foods consumed by habitant in the south-east of Spain was
221 lg day1 (Delgado-Andrade, Navarro, Lopez, & Lopez, 2003).
In another study, the daily dietary intake of arsenic found for the
Spanish population from Valencia was 245 lg day1 (Devesa
et al., 2001). It is important to take into account that both studies
were based on diets in which the mainly food was fish and in min-
or degree vegetables, pulses and cereals. Very little is known about
190 M.N. Matos-Reyes et al. / Food Chemistry 122 (2010) 188–194

the dietary intake of Sb. The dietary exposure to antimony for an
average secondary school student was estimated to be
0.036 lg kg1day1 (http://www.cfs.gov.hk., 2007). The intake of
Se for human varied between 10 and 70 lg day1, depending on
the age and sex, and can be toxic if the intake overcomes
5 mg kg1 day1 in adults and 0.1 mg kg1 day1 in children (Ruk-
gauer, Klein, & Kruse-Jarres, 1997). The dietary intake of Te and Bi
from foods has been estimated around 100 lg day1 (Seiler & Sigel,
1994) and between 5 and 20 lg day1, for Te and Bi, respectively
(Slikkerveer & de Wolff, 1989). As it could be observed additional
data are necessaries to have a good information about the human
intake. So, this work has been focussed on the determination of As,
Sb, Se, Te and Bi in vegetables, pulses and cereals that represent an
important part of the Mediterranean diet using fully validated
methodologies, based on sample dry ashing followed by HG-AFS
determination.
2. Experimental
2.1. Instrumentation
A continuous flow hydride generation atomic fluorescence
spectrometer model PSA Millennium Excalibur 10055 from PS Ana-
lytical (Kent, UK) was used to do the determinations. Boosted dis-
charge hollow cathode lamps of As, Sb, Se, Te and Bi, all of them
from Photron (Victoria, Australia), were used as excitation sources.
Table 2 summarizes the experimental conditions employed for the
determination of the aforementioned elements in food samples.
Other equipments used included a Cryodos lyophilizer (Telstar,
Barcelona, Spain), a PL 5125 sand bath (Raypa Scharlau, Barcelona,
Spain), and a Heraeus K1253 muffle furnace equipped with a Euro-
therm Control 902 controller (Madrid, Spain).
(Deventer, Holland) were used. A reducing solution containing
50% (w/v) KI from Merck plus 10% (w/v) ascorbic acid from Scharlau
Chemie (Barcelona, Spain) was employed to reduce As(V) and Sb(V)
to the III – oxidation state, while KBr Scharlau was employed to
reduce Se(VI) and Te(VI) to their IV- oxidation state. The ashing
aid agent used was a mixture of 20% (w/v) Mg(NO3)6H2O and 2%
(w/v) MgO. Both reagents were from Scharlau. Sodium tetrahydro-
borate, Fluka, dissolved in 0.1 mol L1 NaOH, was used to generate
the corresponding hydrides, previously to the AFS measurements,
this solution was prepared daily and filtered before use. Argon
C-45 (purity >99.995%) was employed as carrier gas and synthetic
air was used to dry the formed hydride. Both gases were supplied
by Carburos Metálicos (Barcelona, Spain).
2.3. Certified reference material and samples
The certified reference materials NIST 1573 (Tomato leaves) and
NIST 1568a (Rice Flour) were obtained from the National Institute
of Standards and Technology, and IAEA-359 Cabbage from Interna-
tional Atomic Energy Agency. Vegetable, pulse and cereal samples
were purchased at the local market of Valencia city.
2.4. General procedures
2.4.1. Sample preparation
Vegetable samples were carefully washed; the edible parts
were cut and crushed, and finally frozen at 20 °C. Afterwards,
they were freeze–dried for a minimum of 48 h at a chamber pres-
sure of 0.05 mbar. The dried samples were crumbled and pulver-
ized with a mill. The resulting fine powder was stored in
polyethylene bottles and kept in desiccator until analysis. Pulses
and cereal samples were crushed and stored in the same way.

2.4.2. Dry ashing mineralization for total element determination

2.2. Reagents, solutions and samples
Approximately 1 g of sample was accurately weighed and trea-
ted with 2.5 mL of an ashing aid suspension containing 20% (w/v)
All reagents used were of analytical grade and all solutions were
Mg(NO3)26H2O plus 2% (w/v) MgO, and 5 mL of 50% (v/v) HNO3.
prepared in ultrapure water with a minimum resistivity of
The mixture was evaporated to dryness in a sand bath and miner-
18.0 MX cm obtained from a Milli-Q Millipore system (Bedford,
alized in a muffle furnace at 450 °C with a gradual increase in tem-
MA, USA). A 1000 mg L1 As(III) stock solution was prepared by dis-
perature (Matos-Reyes et al., 2007). The white ashes were wetted
solving As2O3 from Riedel de Häen (Hannover, Germany) in a 20%
with 1 mL of water and dissolved with 9 mL of 10% (v/v) HCl. For
KOH solution Panreac (Barcelona, Spain), neutralized with 20% (v/v)
As and Sb determination, 3 mL of this solution were transferred
H2SO4 and diluted with 1% (v/v) H2SO4. The 1000 mg L1 Sb(III)
to a 50 mL polyethylene tube, as well as 8.75 mL of concentrated
stock solution was prepared from C4H4KO7Sb1/2H2O Fluka (Buchs,
HCl and 600 lL of the 50% (w/v) KI plus 10% (w/v) ascorbic acid
Switzerland). The 1000 mg L1 Se(IV) and Bi(III) standard solutions
reducing solution. The volume was made up to 30 mL with ultra-
were both supplied by Merck (Darmstadt, Germany). The stock
pure water. For the Se, Te and Bi determinations, 5 mL of the sam-
solution of Te(IV) was prepared by dissolving the appropriate
ple solution were transferred to a 50 mL polyethylene tube, as well
amount of Na2TeO3 Merck (Darmstadt, Germany) in ultrapure
as 16.7 mL of concentrated HCl and 0.5 g of KBr. This solution was
water. For the dissolution of residues obtained after dry ashing of
diluted to 50 mL with ultrapure water and was warm during
samples 37% (w/w) HCl Merck and 65% (w/w) HNO3 J.T. Baker
30 min at 70–75 °C. The experimental HG-AFS measurement con-
ditions are shown in Table 2.
Table 2
Experimental conditions employed for As, Sb, Se, Te and Bi determination by HG-AFS. 3. Results and discussion
Parameter As Sb Bi Se Te
3.1. Improvement of the hydride generation conditions for As, Sb, Bi, Se
Wavelength (nm) 197.3 217.6 223.1 196.0 214.3
Primary current (mA) 27.5 17.5 12.0 20.0 15.0 and Te determination
Boost current (mA) 35 15 10.1 25.1 17.6
Delay time (s) 10 15 15 15 15 HG-AFS is a highly sensitive technique, but there are many
Analysis time (s) 30 30 30 30 30 experimental parameters that must be controlled in order to
Memory time (s) 30 30 30 30 30
HCl (mol L1) 3.5 3.5 4 4 4
achieve the best performance. The effect of HCl and NaBH4 concen-
NaBH4 % (w/v) 0.7 0.7 1.2 1.2 1.2 trations were checked carefully together with the influence of the
Ar flow rate (mL min1) 300 300 300 300 300 reaction coil length and the discrete volume of sample injected
Air flow rate (L min1) 2.5 2.5 2.5 2.5 2.5 aiming to verify the adequacy of the conditions used in previous
Carrier flow rate (mL min1) 9 9 9 9 9
studies (Cava-Montesinos et al., 2003a, 2003b). In relation to the
NaBH4 flow rate (mL min1) 4.5 4.5 4.5 4.5 4.5
influence of HCl and NaBH4 concentrations no performance
 M.N. Matos-Reyes et al. / Food Chemistry 122 (2010) 188–194
improvement was observed by changing the previous conditions
(Cava-Montesinos et al., 2003a, 2003b). The same was true for
the reaction coil length, thus, a 17.5 cm reaction coil recommended
by the instrument manufacturer was used. In order to minimize
the sample consumption and to measure the five elements in a
same sample solution, the fluorescence signals obtained by contin-
uous aspiration of the sample at a flow rate of 9 mL min1 were
compared with those obtained by the injection of a discrete sample
volume. The discrete injection of 2 mL provided fluorescence sig-
nals for As, Sb and Bi of the same order than those found by contin-
uous aspiration. In the case of Se and Te it was selected a volume of
3 mL to avoid sensitivity losses.
3.2. Accuracy studies
Two samples of vegetables and cereals were spiked before the
dry ashing mineralization with lL volumes of standard solutions
of each element at a final concentration level of 100 ng g1 of As,
Sb, Se, Te and Bi. Average recovery percentages (three replicate)
are shown in Table 3. Results obtained for the five elements under
study gave recoveries ranging from 90 to 100%, thus, it is possible
to conclude that no analyte loss and no contamination were oc-
curred during the whole procedure.
The accuracy of the method was also assessed by analyzing three
certificate reference materials 1568a Rice Flour and 1573 Tomato
Leaves from NIST and IAEA-359 Cabbage. For NIST 1568a the certi-
fied values were 0.29 ± 0.03 and 0.38 ± 0.04 lg g1 for As and Se,
respectively. After the analysis by the proposed procedures
(n = 5), concentrations of 0.27 ± 0.01 and 0.37 ± 0.01 for As and Se,
respectively, were obtained. The certified As value for NIST 1573
was 0.27 ± 0.05 lg g1 and it was found 0.26 ± 0.01 lg g1 follow-
ing the developed procedure. For IAEA-359 Cabbage the referred
values were 0.10 and 0.13 lg g1 for As and Se, respectively and
concentrations of 0.099 ± 0.001 and 0.130 ± 0.012 lg g1 for As
and Se, respectively, were found by the present method. Thus, in
all the cases a good agreement between certified and obtained val-
ues were observed, indicating the reliability of the proposed proce-
dure for the determination of As and Se in vegetable and cereal
samples. Unfortunately there is no available certified material of
this type for Sb, Te and Bi. The t-test was applied at the 99% confi-
dence level for the comparison between certified and obtained
results and no significant difference was found between both data
population.
3.3. Analytical of figures of merit
Limits of detection (LOD) were calculated by dividing three
times the standard deviation of the fluorescence signal of 10 re-
agent blanks by the slope of the calibration line, in the best exper-
imental conditions for each studied element. The limit of detection
was also established for the samples taking into account the sam-
ple mass and dilution factor involved in the methodology. Limit of
Table 3
Analytical figures of merit.
Element R2 LOD (ng g1) LOQ (ng g1)
As 0.9996 0.5 1.7
Sb 0.9997 0.2 0.7
Se 0.9999 0.7 2.3
Te 0.9999 1.7 5.7
Bi 0.9997 1.4 4.7
Note: Recovery percentages values obtained in the analysis of samples spiked before the dry ashing step with 100 ng g1 of As, Sb, Se, Te and Bi (values reported are the
average of three separate assays plus minus the corresponding standard deviation).
191
quantification (LOQ) and the precision of the method (RSD) were
also calculated. LOQ and RSD ranged from 0.7–5.7 ng g1 and
7.0–8.7%, respectively (see Table 3).
3.4. Analysis of vegetable, pulse and cereal samples by HG-AFS
Table 4 shows the total content of As, Sb, Se, Te and Bi in veg-
etables. The levels of the aforementioned elements expressed in
ng g1 dry weight show a wide variation, and no common ten-
dency related to the type of sample was observed. For As, the
highest levels were found in mushroom, endive and carrot, while
for Sb the highest levels were found in chard, spinach and parsley
samples. Aubergine, artichoke, cauliflower, and lettuce showed
the highest levels for Se. The levels of Te were lower than those
of the other elements in all the samples, but mushroom showed
an appreciable concentration (104 ng g1). The highest content
for Bi was found in zucchini and artichoke samples. In the case
of pulses, concentrations were lower than for vegetables (see
Table 4). Arsenic (13–61 ng g1) and selenium (15–270 ng g1)
concentrations were, as in the case of vegetables, the highest
ones. Antimony, tellurium and bismuth are at levels in general
lower than in vegetables. In cereal samples, As and Se are at con-
centration levels higher than those found for the other trace ele-
ments considered (see Table 4). The highest As levels were found
in wheat bran, rice semolina, rye flour and rice. The As levels
found in rice probably could be attributed to the quality of water
used for cultivation. The difference between the As contents
found in wheat semolina (86 ± 4 ng g1) and wheat flour (<LOD)
is probably due to the ingredients used in the elaboration of
wheat semolina. For Bi, all levels were below the LOD in cereals,
while Sb and Te levels were in all cases below 2.9 ng g1 and
20 ng g1, respectively.
Table 5 shows the average content of As, Sb, Se, Te and Bi in
the three types of foods considered in the present work compared
with those reported previously in the literature. As it can be seen,
this information was still incomplete and in all the cases, data are
missing for one or more elements. Regarding As and Se, results of
the same order have been found for rice (As, Se), carrot (As),
onion (Se) and garlic (Se). However big differences can be appre-
ciated between results reported previously and those found in the
present study for the rest of foods considered. It is different for Sb
and Bi. Results found through this study were of the same level
than results reported for onion and mushroom in the literature
(Gundersen et al., 2000). In the case of Te, results found for garlic
and onion agree well with those reported by Kaplan and Gunder-
sen. Sb, Te and Bi have been poorly studied in foods of vegetable
origin and it is difficult to compare data found in the present
study with data reported before (Dursun et al., 2006; Gundersen
et al., 2000; Kaplan et al., 2005; Khoo & Ye, 2002). So, it can be
concluded that the present work provides detailed information
on the total contents of As, Sb, Se, Te and Bi in many matrices
not evaluated before.
RSD (%) Recovery (%)
Vegetables Pulses Cereals
7.7 99.5 ± 0.1 96.3 ± 0.3 97.2 ± 0.8
8.4 93.4 ± 0.2 90.1 ± 0.1 91.4 ± 0.3
7.0 96.2 ± 0.4 95.4 ± 0.6 97.0 ± 0.6
8.7 98.4 ± 0.7 97.6 ± 0.7 98.2 ± 0.3
7.4 94.4 ± 0.5 96.7 ± 0.5 96.2 ± 0.4
192 M.N. Matos-Reyes et al. / Food Chemistry 122 (2010) 188–194

Table 4
As, Sb, Se, Te and Bi contents (ng g1) in vegetable, pulses and cereal samples obtained by HG-AFS and referred to dry weight (±s, n = 3).

Classification Sample As Sb Se Te Bi
Flour Artichoke 45 ± 5 3±1 77 ± 4 <LOD 15 ± 1
Cauliflower 163 ± 9 4±1 115 ± 5 <LOD 3.4 ± 0.4
Bulb Garlic 83 ± 3 16 ± 1 41 ± 4 <LOD 2.4 ± 0.3
Onion 39 ± 5 2.4 ± 0.4 10 ± 1 <LOD 5±1
Fruit Zucchini 38 ± 3 2.0 ± 0.2 10 ± 3 0.9 ± 0.1 48 ± 5
Aubergine 84 ± 3 2.3 ± 0.1 86 ± 5 <LOD <LOD
Tomato 20 ± 3 16 ± 2 47 ± 2 <LOD 6.9 ± 0.4
Green pepper 65 ± 7 <LOD <LOD 10 ± 1 <LOD
Red pepper 74 ± 4 <LOD 31 ± 4 11 ± 2 <LOD
Leaves and green shoots Chard 131 ± 4 47 ± 3 21 ± 1 1.15 ± 0.04 10 ± 3
Spinach 57 ± 6 44 ± 5 22 ± 2 0.92 ± 0.08 8.6 ± 0.2
Parsley 53 ± 9 58 ± 3 32 ± 3 <LOD <LOD
Broccoli 43 ± 1 3 ± 0.4 <LOD <LOD <LOD
Lettuce 48 ± 6 1.6 ± 0.3 79 ± 1 <LOD <LOD
Endive 605 ± 12 0.05 ± 0.01 <LOD 0.9 ± 0.1 <LOD
Root Carrot 241 ± 3 0.35 ± 0.03 59 ± 2 56 ± 4 <LOD
Whole plant Mushroom 1001 ± 21 0.17 ± 0.01 <LOD 104 ± 9 <LOD
Pulses String bean 30 ± 6 3±1 15 ± 4 <LOD 15 ± 4
Blank bean 13 ± 2 0.27 ± 0.06 204 ± 4 <LOD <LOD
Read bean 14 ± 3 0.76 ± 0.08 109 ± 4 <LOD <LOD
Castellana lentil 29 ± 1 1.3 ± 0.1 <LOD <LOD <LOD
Chickpea 61 ± 2 1.5 ± 0.1 270 ± 4 <LOD <LOD
Cereals Wheat semolina 86 ± 4 <LOD 50 ± 6 <LOD <LOD
Wheat flour <LOD 0.34 ± 0.05 50 ± 3 <LOD <LOD
Corn flour <LOD 0.5 ± 0.1 109 ± 2 <LOD <LOD
Rice 105 ± 4 0.43 ± 0.04 67 ± 2 0.91 ± 0.15 <LOD
Rice semolina 145 ± 5 0.42 ± 0.06 67 ± 5 1.41 ± 0.08 <LOD
Wheat bran 175 ± 5 2.9 ± 0.3 <LOD 12.7 ± 0.5 <LOD
Rye flakes 4±1 2.9 ± 0.1 <LOD 1.3 ± 0.2 <LOD
Rye flour 154 ± 5 <LOD <LOD 20 ± 2 <LOD

Table 5
Reported and obtained contents of As, Sb, Se, Te and Bi in vegetables, pulses and cereals.

Sample As Sb Se Te Bi Ref
Garlic 0.015a Izgi et al. (2006)
54.4–65.0b Kaplan et al. (2005)
6.75a Khoo and Ye (2002)
83 ± 3b 16 ± 1b 41 ± 4b <1.7b 2.4 ± 0.3b P.S.
Onion 1.43 ± 0.83b 59.5 ± 18.7b 2.06 ± 1.00b 0.12 ± 0.068b Gundersen et al. (2000)
0.024a Izgi et al. (2006)
16b Amokrane and Benamar (2002)
39 ± 5b 2.4 ± 0.4b 10 ± 1b <1.7b 5±1 P.S.
Cauliflower 120–250a Somer and Unal (2004)
163 ± 9b 4 ± 1b 115 ± 5b <1.7b 3.4 ± 0.4b P.S.
Carrot 0.59 ± 0.11a Arancibia, Lopez, Zuñiga, and Segura (2006)
241 ± 3b 0.35 ± 0.03b 59 ± 2b 56 ± 4b <1.4b P.S.
Mushroom 23.4a 4.43a Cocchi et al. (2006)
0.12–44a <0.014–1.3a 0.04–33.2a Randa and Kucera (2004)
0.5–116.7a 0.0–31.6a 0–5.9a Dursun et al. (2006)
1001 ± 21b 0.17 ± 0.01a <0.7b 104 ± 9b <1.4b P.S.
Lentil 208 ± 88b Kumar and Krishnaswamy (1997)
29 ± 1b 1.3 ± 0.01b <0.7b <1.7b <1.4b P.S.
Rice 0.01–0.61a Rivero-Hughet et al. (2006)
0.3–0.4a Heinemann, Fagundes, Pinto, Penteado, and Lanfer-Marquez (2003)
99 ± 43b Kumar and Krishnaswamy (1997)
105 ± 4b 0.43 ± 0.04b 67 ± 2b 0.91 ± 0.15b <1.4b P.S.
Wheat flour 0.045 ± 0.003b Alamin, Bejey, Kucera, and Mizera (2006)
<0.5b 0.34 ± 0.05b 50 ± 3b <1.7b <1.4b P.S.

P.S.: Present Study.

a
lg g1.
b
ng g1.

3.5. Estimation of daily dietary intake of total As, Sb, Se, Te and Bi
Taking into account the concentration of As, Sb, Se, Te and in
the studied matrices (see Table 4), their contribution to the mean
daily element intake in the Valencia diet (considering only the
aforementioned samples) was calculated by multiplying the aver-
age concentration of each element in each type of food by its mean
consumption in Valencia per person day1 (Llobet, Falco, Casas,
Teixido, & Domingo, 2003). For those cases for which the element
concentration was below the limit of detection (LOD), calculations
 M.N. Matos-Reyes et al. / Food Chemistry 122 (2010) 188–194
Table 6
Contribution of vegetables, pulses and cereals to the mean daily As, Sb, Se, Te and Bi intakes by the population of Valencia (Spain) established from concentration levels found in
this study.
Food Daily Mean As Daily As Mean Sb Daily Sb
consumption (ng g1) intake (ng g1) intake
(g/person) (lg person1) (lg person1)
Vegetables 189.12 164.12 31.04 13.32 2.52
Pulses 14.61 29.4 0.43 1.37 0.02
Cereals 179.9 111.5 20.06 1.25 0.22
were performed assuming a value equal to a half of the detection
limit (Llobet et al., 2003). Obtained results, associated to the three
groups of foods studied are summarized in Table 6. For comparison
purposes it must be noticed that dietary arsenic intakes estimated
from various countries range from less than 10 lg day1 to
200 lg day1 (http://www.inchem.org/documents, 2008). These
values are reflective of different dietary habits and also provide
important variations in assumptions used to calculate them. The
Joint FAO/WHO Expert Committee on Food Additives established
0.002 mg kg1 as a provisional maximum tolerable daily intake
for ingested arsenic (World Health Organisation, 1981). On consid-
ering Sb, the Food and Nutrition Board of the US National Research
Council recommends a range of 50–200 lg day1, 10–40 for in-
fants and 20–120 for children under 6 years, which are coherent
with data found in this work (http://www.cfs.gov.hk, 2007). So,
it can be concluded that the considered foods contribute to the
daily intake of As, Sb, Se, Te and Bi in a reasonable reduced
proportion.
4. Conclusions
Dry ashing followed by hydride generation atomic fluorescence
spectrometry provided an adequate methodology for the determi-
nation of As, Sb, Se, Te and Bi in vegetables, pulses and cereals. The
analysis of certified reference materials assured the accuracy of the
procedures and the limits of detection were adequate in most
cases. Good recoveries were obtained which evidence no analyte
loss and no contamination during the whole procedure.
Data found for the studied elements indicate that foods con-
sumed in Valencia contain levels of trace elements under the limits
tolerated by the law and that the contribution of the foods evalu-
ated to the daily intake of As, Sb, Se, Te and Bi remain under the
standards recommended by international organisms.
Acknowledgements
The authors gratefully acknowledge the support of the Pro-
gramme Alban, the European Union Programme of High Level
Scholarships for Latin America, scholarship No. E05D049710BR,
CNPq, Brazilian science funding agency and the Ministerio de Edu-
cación y Ciencia Project AGL2007-64567.
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