The Science of the Total Environment 234 Ž1999.

197]201

Cadmium and lead in infant cereals }

electrothermal-atomic absorption spectroscopic
determination

´U , A.M. Frigola
M. Roca de Togores, R. Farre
Nutrition and Food Chemistry, Faculty of Pharmacy, Uni¨ ersity of Valencia, A¨ da. Vicent Andres ´ s r n, 46100
´ Estelles
Burjassot, Spain

Received 26 February 1999; accepted 6 May 1999

Abstract

Because infant cereals are an important component of the infant diet from the fourth month of life onwards and
therefore contribute to the dietetic intake of metals by infants, cadmium and lead were measured in samples of
cereals commercially available in Spain. For this purpose an electrothermal atomic absorption ŽET-AAS. method for
determining cadmium and lead in these products was studied. The ET-AAS instrumental conditions and tempera-
turertime furnace program were selected. The analytical parameters of the method Žlinearity, detection and
quantification limits and precision. show its usefulness in measuring cadmium and lead in infant cereal products. The
method was applied to eight different types of infant cereals from four different manufacturers, in all 29 different
infant cereal products commercially available in Spain. The cadmium and lead contents of milk-free infant cereals
range from 6.6 to 35.8 ngrg and from 36.1 to 305.6 ngrg, respectively, while the ranges corresponding to milk-added
infant cereals are 2.9]40.0 ngrg for cadmium and 53.5]598.3 ngrg for lead. The cadmium and lead contents of
cereal products of the same type from different manufacturers is responsible for the large confidence intervals and
made it impossible to detect significant differences among the different products. Given the values found for lead
and the correlation between chronic exposure to low lead doses and neuropsychological damage in early childhood,
efforts should be made to reduce lead contamination. Q 1999 Elsevier Science B.V. All rights reserved.

Keywords: Cadmium; Lead; Contents; Infant cereals

U
Corresponding author. Tel.: q34-9-6386-4950; fax: q34-9-6386-4954.
E-mail address: rosaura.farre@uv.es ŽR. Farré.

0048-9697r99r$ - see front matter Q 1999 Elsevier Science B.V. All rights reserved.
PII: S 0 0 4 8 - 9 6 9 7 Ž 9 9 . 0 0 2 6 0 - 0
198 M. Roca de Togores et al. r The Science of the Total En¨ ironment 234 (1999) 197]201
1. Introduction
Cadmium and lead are significant environmen-
tal pollutants. Anthropogenic activities such as
agriculture, industry and urban life increase the
cadmium and lead content of soils and waters,
thereby contributing to the contamination of raw
materials ŽPuchades et al., 1989; Schumacher et
al., 1991; Baxter et al., 1992.. The cadmium and
lead contents in food can also increase signifi-
cantly through manufacturing processes and
through contact with the materials used in the
packaging ŽCabrera et al., 1995..
The main route of exposure to cadmium and
lead is via diet. Age affects the absorption of
heavy metals from foods, especially in the case of
lead, with children up to 4 years of age showing a
higher Ž40]50%. lead absorption from the diet
than adults Ž5%. ŽBranca and Costa, 1986; Fox,
1987.. For this reason infants and young children
are highly susceptible to lead intoxications and
constitute a high-risk group ŽBranca and Costa,
1986; Puchades et al., 1989.. This is a matter for
concern because the neurotoxic effects of lead
involve cognitive functions that can be com-
promised even with relatively low lead intakes
ŽCabeza and Dıaz,´ 1996.. Children exposed to
lead in the first 2 years of life are especially
vulnerable to its neurotoxicity effects and run the
risk of enduring developmental handicaps ŽShan-
non, 1998..
Electrothermal atomic absorption spectroscopy
is the technique most often applied to determine
cadmium and lead in foods either after a dry or
wet destruction of the organic matter ŽSkurikhin,
1993; Tahvonen and Kumpulainen, 1996. or with-
out destruction by direct determination in slurries
ŽJeng et al., 1994..
The aim of our study was to measure cadmium
and lead in samples of different infant cereals
commercially available in Spain, because they are
an important component of the infant diet from
the fourth month of life onwards and therefore
contribute to the dietetic intake of these metals
by infants. For this purpose an electrothermal
atomic absorption spectroscopic method ŽET-
AAS. for determining cadmium and lead in these
products was studied.
2. Materials and methods
2.1. Samples
Eight different types of infant cereals from four
different manufacturers, in all 29 different
products, were selected, concentrating on the
types and brands most widely sold in Spain. The
samples of these products to be analyzed were
provided by the manufacturers in their commer-
cial packaged form.
2.2. Apparatus
The following instruments were used in the
mineralization of the sample: a Eurotherm fur-
nace fitted with a Eurotherm temperature pro-
grammer, a Select Regisplac with thermostat
heating plate.
A Perkin-Elmer atomic absorption spectrome-
try model 1100 fitted with graphite furnace
ŽHGA-400. and a deuterium background correc-
tor. Perkin-Elmer cadmium and lead electrode-
less discharge lamps and an EDL system 2-power
supply were also used.
Non-pyrolitic graphite tubes ŽPerkin Elmer
070699. and 99.9998% argon were used.
To avoid possible contamination, all glassware
was soaked in nitric acid Ž ds 1.40 grml. for 10
min and rinsed with deionized water before use.
2.3. Reagents
All the reagents were of analytical reagent
grade. Deionized water Millipore Milli-Q system
was used throughout.
Nitric acid: 65% Žsp. gr. 1.40 Merck.. Cadmium
and lead standard solutions Ž1000 mgrml, Titrisol
Merck.. Standard working solutions Ž2]40 ngrml
for cadmium and 40]400 ngrml for lead. were
prepared from the stock solution immediately be-
fore use. Blanks consisting of 400 ml HNO3 at
65% completed with water to 10 ml were also
prepared.
2.4. Analytical procedure
2.4.1. Dry organic matter destruction
The organic matter of 10 g of sample was
 M. Roca de Togores et al. r The Science of the Total En¨ ironment 234 (1999) 197]201 199

destroyed by ashing in a temperature-pro- Cd: 110r5r10, 500r5r15, 2000Ur2r5, 2600r

grammed furnace. The temperature was in-
creased slowly, at a rate of 508Crh to obtain a
final temperature of 4508C. This temperature was
maintained for 24]48 h. In order to complete the
digestion, the residue was soaked with concen-
trated nitric acid Žsp. gr. 1.4. Ž1 ml.. Between 48
and 72 h were needed to completely destroy the
organic matter of the sample. White ashes indi-
cated that the process was complete and was then
dissolved by adding Ž400 ml. concentrated nitric
acid and the volume made up to 10 ml with water.
The solution was frozen until used for determina-
tion.
Pyrex vessels used in dry matter digestion were
soaked in nitric acid Ž ds 1.40 grml. for 10 min,
rinsed with deionized water and subjected to fur-
nace temperature program before use. Blanks
ŽPyrex vessels containing 1 ml HNO3 . were car-
ried out during the organic matter destruction to
assess the absence of contamination.
2.4.2. ET-AAS determination
Instrumental conditions: l Žnm. 228.8 and 283.3
for Cd and Pb, respectively; injected volume Ž20
ml.; reading time Ž7 s.. Measuring was done in the
peak height mode.
Temperature Ž8C.rtime Žs. furnace programs:
1r1; and
Pb: 130r5r10, 500r5r15, 2300Ur2r5, 2600r
1r1 ŽU mini-flow..
Uncoated graphite tubes were used through-
out. Argon of 99.9998% purity was used as the
purging gas through the graphite tube.
The validity of the method for determining
cadmium and lead in infant cereals has been
thoroughly tested. No matrix interferences were
encountered. The analytical parameters Žlinearity,
detection and quantification limits, instrumental
and method precision and accuracy. of the method
are given in Table 1.
The precision depends basically upon the re-
producibility of the digestion procedure, dilution
of the sample and injection to the furnace. The
values obtained were acceptable, taking into ac-
count the low levels of the cadmium and lead of
the analysed infant cereal products, and also the
fact that the injection was carried out manually
because an automatic injector was not available.
In order to estimate how many samples of each
product had to be analyzed to obtain representa-
tive values, the following equation was applied:
n G Ž t ny 1 sny1r« . 2 , where n s number of sam-
ples; t ny 1 s Student’s t; sny1 s standard devia-
tion and « maximum accepted error Ž5%. at a

Table 1
Analytical parameters: linearity, detection and quantification limits, precision and accuracy a

Parameters Cadmium Lead

Linearity Žngrml. 2]40 40]400

y s 8.83= 10y3 x q 0.088 y s 2.53= 10y4 x q 0.015
r s 0.996 r s 0.999
Detection Žngrg. 0.33 14.9
Quantification limits Žngrg. 0.68 30.3
Precision ŽR.S.D.%.
Instrumental 4.5 14
Method 7.4 16
Accuracy Ž n.b
Recovery assays Ž%. 100.1]105.0 95.1]107.6
a
n s number of samples. The lowest value of the range of linearity correspond to the lowest content that was possible to
differentiate from the blank at a given sensitivity. LDs x q 3sny 1; LQ s x q 10sny1 , where x and sny1 were the mean value and
standard deviation of six blanks.
b
Infant cereals were analysed nine times at the unspiked level and and nine additional analyses were carried out on the spiked
samples. Results are the confidence intervals at a 95% confidence level.
200 M. Roca de Togores et al. r The Science of the Total En¨ ironment 234 (1999) 197]201

confidence level of 95%. According to this for-
mula, four samples were needed.
Therefore aliquots of four different packages
of the same product were taken and analyzed.
3. Results and discussion
The cadmium and lead contents of the ana-
lyzed infant cereals are reported in Tables 2 and
3, respectively.
Taking into account the possible cadmium and
lead contamination due to raw materials and pro-
cessing methods, one-way variance analysis was
applied to the cadmium and lead contents of the
analyzed infant cereals in order to detect statisti-
cally significant differences between:
v milk-free and milk-added products;
v different types of milk-free products; and
v different types of milk-added products
to detect significant differences among different
types of products. Therefore, statistically signifi-
cant differences were detected only between the
different types of milk-free infant cereals } i.e.
the lead content of cream of rice differed signifi-
cantly from the others at 95 and 99% probability
levels.
The cadmium and lead contents of milk-free
infant cereals ranges from 6.6 to 35.8 ngrg and
from 36.1 to 305.6 ngrg, respectively. The ranges
corresponding to milk-added infant cereals are
2.9]40 ngrg for cadmium and 53.5]598.3 ngrg
for lead. The cadmium and lead contents are in
the ranges mentioned by Jedrzejczak and Szteke
Ž1991. in the same type of products in Poland,
that is - 2]70 ngrg and - 20]400 ngrg, respec-
tively. In general, the lead contents in our study
are higher than the mean Ž32.8 ngrg. reported by
Dabeka and McKenzie Ž1988. for dry infant cere-
als in Canada, while the cadmium content agrees
with the mean Ž33.6 ngrg. given by these authors.

The high variability in the cadmium and lead

contents of infant cereals of the same type from 4. Conclusions
different manufacturers is responsible for the
large confidence intervals and made it impossible The fact that the lead and cadmium contents in

Table 2 Table 3
Cadmium and lead Žngrg. contents of milk-free infant cereals a Cadmium and lead Žngrg. contents of milk-added infant
cereals a
Product Manufacturer Cadmium Lead
Žngrg. Žngrg. Product Manufacturer Cadmium Lead
Žngrg. Žngrg.
Gluten-free cereals A 7.8" 1.4 50.4" 5.3
B 7.3" 0.4 84.3" 22.1 Gluten-free cereals A 8.4" 1.2 299.4" 76.8
C 35.8" 0.8 71.3" 16.0 B 2.9" 0.4 274.0" 66.8
D 7.7" 2.6 36.1" 6.9 C 5.7" 0.2 68.1" 11.2
Cereals A 14.8" 0.6 64.6" 3.3 D 5.2" 1.3 54.6" 20.1
B 14.4" 0.8 88.3 " 14.3 Cereals A 9.8" 3.9 318.0" 71.9
C 24.2" 0.8 53.3" 7.4 B 14.6" 0.8 312.2 " 73.6
D 3.8" 0.4 53.5" 8.6 C 10.5" 2.7 418.1" 87.4
Rice cream A 9.8" 1.5 221.9" 14.7 Cereals with honey A 40.0" 1.5 598.3" 13.5
B 9.4" 0.7 280.2" 48.4 B 6.8" 0.5 90.7" 3.1
C 17.9" 0.6 249.9" 7.5 D 31.3" 0.6 53.5" 8.6
D 8.0" 0.5 305.6" 18.3 Cereals with fruits A 4.0" 0.4 54.7" 7.7
Cereals with honey A 23.9" 1.3 212.9" 13.3 B 6.7" 0.8 60.6" 11.4
B 9.1" 0.7 59.3" 7.7 C 24.2" 1.1 509.8" 78.7
D 6.6" 0.3 55.2" 4.4 D 5.2" 1.4 295.9" 37.9
a a
Number of analyzed samples from each manufacturer s 4. Number of analyzed samples from each manufacturer s 4.
A]D indicate different manufacturers. xs Mean value of all A]D indicate different manufacturers. xs Mean value of all
samples of the same type. samples of the same type.
 M. Roca de Togores et al. r The Science of the Total En¨ ironment 234 (1999) 197]201
the analyzed samples are higher than the detec-
tion and quantification limits of the method
together with the values obtained for precision
and recoveries indicates that the described ET-
AAS method with prior dry ashing of the sample
is useful for measuring these metals in infant
cereals.
Given the values found for lead in the infant
cereals and the correlation between chronic expo-
sure to low lead doses and neuropsychological
impairment in the early childhood reported by
different authors, it is important that efforts be
made to reduce lead contamination through con-
trol of raw materials and manufacturing processes.
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