Sensors and Actuators B 118 (2006) 192–197

Leaching of aluminium from cooking pans and food containers

Marta I.S. Verı́ssimo, João A.B.P. Oliveira, M. Teresa S.R. Gomes ∗
Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal
Available online 23 May 2006

Abstract
Aluminium is not an essential element to humans, and is considered to be a toxic metal ion. Since Al pans are the most commonly used cooking
utensils in rural places an acoustic wave sensor was developed to quantify the amount of metal leaching when cooking some recipes. Sensitive
layer of the sensor consists of a membrane with a specific ionophore for the aluminium, in a PVC/plasticizer matrix.
Red cabbage samples cooked with different acidic additives (lemon juice, wine vinegar and cider apple vinegar) showed that low pH values
increased leaching of aluminium. Red cabbage cooked with lemon juice at pH 2.6 showed 5.1 mg Al/100 g red cabbage. Tomato sauce cooked with
and without sugar, showed 2.7 ± 0.2 and 4.9 ± 0.2 mg Al/100 g tomato sauce, respectively. The same samples, stored in aluminium containers in
a refrigerator for 48 h, showed 2.8 ± 0.2 and 5.0 ± 0.2 mg Al/100 g tomato sauce, respectively.
Results obtained with the new piezoelectric aluminium sensor are not statistically significant different (α = 0.05), both in terms of accuracy and
precision, from the ones obtained by UV–vis methodology.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Bulk acoustic wave sensor; Cookware; Aluminium; Aluminium containers; Food contamination

1. Introduction Although the kidney appears to be able to excrete the alu-

Aluminium is quite ubiquous in nature but its bioavailabil-
ity is very low. On account of low absorption across the human
gastrointestinal tract, aluminium was earlier not considered to
have any adverse effect on human health. However, because of
acid rains and its generalised use in water treatment, in cooking
utensils and food containers, in cosmetics and medicines, the
amount of aluminium uptake by humans have increased and is
now of great concern. A high level of aluminium was found in
the brain of Alzheimer patients, and although it is not clear the
role that aluminium uptake can play in this and other diseases as
Parkinson’s disease, osteomalacia and anaemia, and safety lev-
els were not established, it is important that its sources become
clearly identified. Although data from chronic toxicity studies
are still lacking [1], provisional tolerance weekly intake (PTWI)
of 7 mg/kg body weight have been recommended based on short
term toxicity studies [2]. Besides the expected revision of the
PTWI, it is known that absorption and tissue accumulation are
greatly influenced by nutrients as iron, calcium, zinc and addi-
tives as citrate, and therefore must be corrected for population
nutrition conditions and habits [1].
∗ Corresponding author. Tel.: +351 234370722; fax: +351 234370084.
E-mail address: mtgomes@dq.ua.pt (M.T.S.R. Gomes).
minium in healthy persons it is not known the limit of this
elimination capacity and it is certain that people suffering from
chronic renal failure do not possess the ability to excrete it. Fatal
brain encephalopathies have occurred in dialysed patients.
The use of aluminium salts, often sulphate, in water treatment
as coagulants of the organic matter, to reduce colour, turbid-
ity and microorganisms, increase the aluminium level which is
known to be difficult to control in small facilities [3]. However,
except for people who regularly ingest antacids and analgesics,
food is the main source of aluminium intake. Besides food addi-
tives, several products, as potatoes, spinach and tea, are known
to have high aluminium content.
Aluminium leaching from cookware is also an important
source, which is highly dependent on the pH, and the presence
of complexing species. According to Bi [4] the Al leaching pro-
cesses can be explained by the following chemical reaction that
occurs on the surface of the aluminium utensils in contact with
water:
Al2 O3 + 6H+ = 2Al3+ + 3H2 O
where Al2 O3 is a protective film. The free aluminium in solutions
reacts with organic acids found in food, like citric, oxalic and
acetic acids, and other complexing ligands like fluoride ion and
hydroxyl. These reactions may take place simultaneously and
promote each other.

0925-4005/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.snb.2006.04.061
 M.I.S. Verı́ssimo et al. / Sensors and Actuators B 118 (2006) 192–197
Regardless the type of food that is being cooked, the recipe
and the way of preparing the food must play an important role
on the aluminium leaching levels.
The interaction between food and aluminium packaging can
also be a potential source of aluminium release which can con-
tribute to aluminium ingestion. Aluminium packaging in the
food industry is very popular because it is impermeable, grease-
proof, non-absorptive, inert, highly formable with excellent dead
fold characteristics, and easily recyclable.
In this work several ways of preparing recipes will be dis-
cussed and the aluminium analyzed by a piezoelectric quartz
crystal sensor. The aluminium sensor was developed following
previous methodologies already applied to the development of
other metal sensors [5], and including an aluminium ionophore
synthethizised in the laboratory. The reliability of the sensor
was proved by comparing its results with the ones obtained with
other analytical methodologies.
The development of the aluminium sensor is now presented
as well as the analytical results obtained when cooking red cab-
bage with pieces of the aluminium used in the manufacture of
the pans. It is known that the colour of the cabbage is pH depen-
dent, and no cook would like to present a blue-grey cabbage. In
order to preserve its red/purple colour, vinegar or lemon juice
is always added. The cabbage was cooked in water with two
types of vinegar (wine and cider vinegar) and lemon juice, with
nitric acid and sulphur dioxide, and the aluminium content of
the cooked cabbage and water analysed. Tomato sauce was also
cooked with aluminium plates, with and without white sugar,
and analyzed fresh, and stored for 2 days in aluminium contain-
ers kept in a refrigerator.
2. Experimental
2.1. Reagents and aluminium plates
The membranes were prepared in tetrahydrofuran (THF,
Merck 8114) with PVC (Fluka 81388), and o-nitrophenyloctyl
ether (NPOE, Fluka 73732) as plasticizer. The ionophore
for aluminium, bis(5-phenylazo salicylaldehyde) 2,3-naphatene
diimine, was synthethizised according to the procedures
described by Abbaspour et al. [6] and Khandar et al. [7]. To some
of these membranes potassium tetrakis(p-chlorophenyl) borate
(KTpClPB, Fluka 60591) was added. Standard solutions were
prepared in Milli-Q water by weighing the appropriate amount
of aluminium nitrate p.a. (Riedel-deHaën 31154).
Citric acid was p.a. grade (Fluka 27490) and nitric acid used
in sample digestions was 69% p.a. (Riedel deHaën 30702).
Aluminium plate, in accordance to the European standard for
fabrication of articles in contact with food (EN 602:2004), was
obtained through a manufacturing aluminium cookware indus-
try.
2.2. Apparatus
The analysis of aluminium in acid digested food samples
were performed by flow injection analysis, using a coated 9 MHz
quartz crystal. Fig. 1 shows the flow injection (FIA) methodol-
193
Fig. 1. Experimental layout: A, frequency counter; B, cell; C, pressure regulator;
D, milli-Q water; E, nitrogen; F, injection port; H, waste.
ogy used, where water carries the metal solution into the crystal
cell. Experimental setup has been described elsewhere [5]. The
frequencies of oscillation of the crystal were obtained with a
frequency counter Leader 823A and recorded on a PC.
Aliquots of the same samples were also analysed by UV–vis
spectroscopy in a scanning spectrophotometer Shimadzu, UV-
2101 PC.
2.3. Procedure
The quartz crystals were coated on one side with a solution of
the membrane prepared with 33% of PVC, 66% of the plasticizer
and 1% of the ionophore. Several crystals were prepared with
membranes with different contents in the lipophilic salt. The
coated crystals were then allowed to dry for 48 h. Those crystals
were then evaluated in terms of selectivity to aluminium over
other metals.
In order to perform the analysis, the crystal with 30% salt was
inserted into the cell and the coated face was then put under a
constant flow of water. Fixed quantities of 0.5 mL of aluminium
solutions of several concentrations were injected. The differ-
ences in the frequency of the crystal before injection, while
milli-Q water was flowing through the cell, and the minimum
frequency observed after each sample injection, were recorded.
Baseline stability and complete recover from previous exper-
iment were assured, and no standard or sample was injected
before a constant reading, corresponding to the baseline fre-
quency was attained.
Samples were prepared by slicing an amount of 100 g of red
cabbage to a glass vessel, to which 500 mL of milli-Q water
were added. An aluminium plate of 18.0 cm × 15.5 cm, cut in
16 equal pieces, and known volumes of lemon juice, wine vine-
gar, cider apple vinegar or nitric acid were added. The pH was
measured. In order to accurately assess the contribution of the
cookware to the aluminium content found in the food, standard
size aluminium plates obtained from the same lot were used in
all the experiments, and blank experiments, without aluminium,
were always performed in parallel.
The aluminium plates were preferred over aluminium utensils
having different geometries due to the constant surface topog-
raphy of the former.
194 M.I.S. Verı́ssimo et al. / Sensors and Actuators B 118 (2006) 192–197
The food with the aluminium pieces was then allowed to boil
for 60 min. The aluminium plates were then removed and heat-
ing was maintained until the liquid was reduced approximately
to 100 mL. The cooked red cabbage, with all the cooking liq-
uid, was then transferred to the plastic cup of a food processor,
where the cabbage was grinded until a homogeneous sauce was
obtained. The samples were digested with nitric acid in a furnace
for 24 h.
In order to study the effect of prolonged use of aluminium
pans, the same pieces of the aluminium plate were reused in four
consecutive cooking processes with new cabbage samples.
Since E220, the food additive code for sulphur dioxide, is
used as a preservative and it is present in a wide range of foods,
as sausages, soft drinks, burgers, dried fruit, vegetables, beers,
wine and vinegars, a sample of red cabbage was cooked as before
with aluminium plates, and nitric acid until pH 3.1, under sulphur
dioxide bubbling.
Six hundred grams of tomato samples were also cooked for
60 min in the presence of aluminium plates, with and without
20 g of white sugar, normally used in tomato sauce recipes. One
half of each sample was digested following the usual procedure,
and the other half was stored in an aluminium container, at 10 ◦ C
for 2 days (48 h). All the samples were analysed for aluminium
in order to study the role of sugar as well as the effect of the
storing time.
All samples and standards were shortly kept in plastic bottles
while waiting to be analysed both by the piezoelectric quartz
crystal sensor and by the UV–vis spectrophotometer.
The conventional UV–vis methodology used to quantify the
aluminium was based on the principle that aluminium solutions,
buffered to a pH of 6.0, and with Eriochrome cyanine R dye,
produced a red to pink complex with a maximum absorption at
535 nm, and the maximum absorption occurs after 15 min and
starts decreasing [8].
3. Results and discussion
Fig. 2 shows the selectivity coefficients of interfering ions
relative to aluminium ions, calculated by the fixed interference
method, for the membranes with several salt/ionophore ratios,
and Fig. 3 shows the calibration curves, for aluminium, of those
membranes. Although none of the membranes is completely
specific, the addition of salt equivalent to 30% of the weight
of the membrane allows decreasing the response to the tested
interferents. Fig. 3 shows that the membrane with 30% of salt
is also good in terms of sensitivity to aluminium. As we can see
Fig. 2. Selectivity coefficients for aluminium over some other metals, obtained with membranes with several salt/ionophore ratios.
Fig. 3. Response to aluminium of sensors with several salt contents.
in Fig. 2 the amount of salt does produce a dramatic change in
the selectivity.
Interference from other elements present in the aluminium
plates is not expected, as according to EN 602:2004, maximum
permissible content of elements in wrought aluminium used for
foodstuff application are: iron and silicon ≤1.0%; chromium,
magnesium, manganese, nickel, zinc, titanium and tin ≤0.10%
each; copper ≤0.10% (copper is permitted in proportion greater
that 0.10 but not more than 0.2% and provided that neither
chromium nor manganese content exceeds 0.05%), and other
elements ≤0.05% each.
Possible source of interferences can arise either from chemi-
cal manipulation or from food itself. Although selectivity of the
sensor assures a certain degree of confidence on the results, the
comparison of the analytical results with those obtained with a
different methodology was performed in order to confirm that
the performance of the proposed method is not affected by other
constituents of the sample.
Fig. 4 shows a typical frequency variation observed injecting
an aluminium standard of 40 mg L−1 . As it can be seen, both
frequency decrease response and recovery of the sensor are fast,
even for signals as large as the one displayed (100 Hz).
For the sample analysis, a linear calibration line F = 3.5873
[Al3+ ] + 0.0762, where F is expressed in Hz and Al3+ con-
centration in mg L−1 , was used in the range between 2.7 and
7.2 mg L−1 of aluminium. All samples were buffered to pH
6.0 before the analysis. Whenever necessary, the samples were
diluted to a concentration as close as possible to the centroid
 M.I.S. Verı́ssimo et al. / Sensors and Actuators B 118 (2006) 192–197 195

Table 2
Acidic additive volume (mL) vs. aluminium content determined by quartz crystal
methodology (100 g red cabbage)
Wine vinegar (mL) Quartz crystal
microbalance [Al] mg

10 4.2 ± 0.2
50 4.8 ± 0.3
100 5.2 ± 0.4

Table 3
Aluminium (mg) vs. pH for several acidic additives used to cook 100 g of red
cabbage

Fig. 4. Typical frequency variation for a 40 mg L−1 Al3+ injected standard. Additive pH Quartz crystal
microbalance [Al] (mg)

of the linear calibration curve. The quantification limit for the Lemon juice (50 ml) (Al:1 sheet in 2.6 3.8 ± 0.2
quartz crystal method was calculated as 0.12 mg L−1 . eight pieces)
Lemon juice (50 ml) (Al: 1 sheet in 2.6 5.1 ± 0.2
For the UV–vis methodology, a linear calibration line of
16 pieces)
Abs = 0.0706[Al3+ ] + 0.1233 was obtained, and the method Wine vinegar (50 mL) (Al: 1 sheet in 3.2 4.8 ± 0.3
presents a quantification limit of 0.10 mg L−1 of aluminium. 16 pieces)
The Eriochrome Cyanine R method has been used for determin- Cider vinegar (50 mL) (Al: 1 sheet in 3.1 4.2 ± 0.2
ing aluminium in steel, copper alloys, zinc, biological materials, 16 pieces)
Lemon Juice until pH 3.1 (Al: 1 sheet 3.1 4.6 ± 0.2
food and water [9].
in 16 pieces)
Table 1 shows the results, in terms of aluminium quanti- Nitric acid until pH 3.1 (Al: 1 sheet 3.1 4.1 ± 0.2
ties obtained for different experiments, obtained with the two in 16 pieces)
methodologies. Five replicates were analysed from each sam- Nitric acid until pH 3.1 with SO2 3.1 4.4 ± 0.2
ple. (Al: 1 sheet in 16 pieces)
Comparing the results obtained by both methodologies, no
statistical significant differences (α = 0.05) were found both in
the average of the replicate analysis nor in the precision of the Table 3 shows aluminium concentration found with 50 mL
results. The results obtain for the samples without aluminium of the different acidic additive added to 100 g of red cabbage.
plates with or without vinegar, were all below the quantification The table also presents the pH of other mixtures of water-acidic
limit of both methodologies. It is also possible to observe that the additives used in the experiments.
aluminium leached decreased with the prolonged use of the same Comparing the samples with the same amount of lemon juice,
aluminium pieces, just as expected, according to the Neelam et with 8 and 16 pieces of aluminium, it is possible to observe that,
al. [1] work, where they showed that new vessels appeared to as expected, the highest the aluminium contact area, the highest
be much more easily attacked by foods when compared to old the amount of aluminium leached.
ones. For all the samples cooked with 16 pieces of aluminium, it
Table 2 shows that the aluminium content obtained cooking is possible to observe that lemon juice, which gives rise to the
100 g of red cabbage with the aluminium pieces, with several lowest pH, is the more effective in leaching the aluminium.
amounts of vinegar. These results show that the aluminium Table 3 shows also that the cider vinegar, which impairs a
leaching depends on the quantity of the acidic additive added, more acidic pH than wine vinegar, does not promote such a high
increasing from 4.2 to 5.2 mg, for samples with 10–100 mL, leaching of the aluminium. These results show that other factors
respectively, of wine vinegar. The aluminium found had its ori- besides pH are important in the leaching of aluminium.
gin on the aluminium plate, as the red cabbage cooked in the glass The presence of food additives can be important and the cit-
vessel without aluminium showed aluminium content lower than rate role cannot be forgotten in this case. It is known that citric
the quantification limits of the methods of analysis. acid is one of the most efficient organic species for complex-

Table 1
Aluminium determined by both quartz crystal and UV–vis methodologies (100 g red cabbage)
Wine vinegar until pH 3.1 Quartz crystal microbalance [Al] (mg) UV–vis spectrophotometer [Al] (mg)

Al plates first use 4.9 ± 0.2 4.9 ± 0.2

Al plates second use 4.46 ± 0.2 4.4 ± 0.2
Al plates third use 3.8 ± 0.2 3.8 ± 0.2
Al plates fourth use 3.7 ± 0.2 3.7 ± 0.2
Without Al plates <0.12 <0.10
Without Al plates and without vinegar <0.12 <0.10
196 M.I.S. Verı́ssimo et al. / Sensors and Actuators B 118 (2006) 192–197
Fig. 5. Aluminium concentration of tomato cooked, with and without sugar,
freshly and stored in new Al containers.
ing aluminium [10] and it is present in large scale in lemon
juice.
Table 3 shows that samples with same pH (3.1), same num-
ber of pieces (16) and with different acid added, namely lemon
juice and nitric acid, have different aluminium contents. The
sample with lemon juice shows more aluminium leaching than
the one prepared with nitric acid. It is well known that Al–citrate
complexes are very stable, and citrate alone evidently chelates
trace Al3+ in the diet. Slanina et al. [11] showed that aluminium
concentration in human blood of patients who were taking
Al(OH)3 -based antacids, have increased substantially by cit-
rate intake. Besides, citrate solubilizes Al3+ , and an appreciable
fraction occurs as a neutral complex that may pass through mem-
branes and provide a vehicle for Al3+ absorption into the body.
This shows that people should not take aluminium-containing
antacids with citrus fruit or juices [10].
Table 3 also shows that red cabbage sample prepared with an
excess of sulphur dioxide, showed an increase in the aluminium
content.
Fig. 5 shows the aluminium content found in tomato samples
cooked, with the aluminium plates, with and without sugar, fresh
and stored for 2 days in a refrigerator. For tomato without sugar,
4.8 mg Al/100 g tomato were found. It is worth to say that 100 g
of tomato is the serving portion of tomato in a regular meal. The
stored sample shows a higher medium value of 5.0 mg Al/100 g
tomato, which it is not statistically different from the fresh one.
Keeping acid food stored in aluminium containers, for at least
48 h, in a refrigerator, seems not lead to a significantly increase
on aluminium concentration. Other authors [1] published that
increasing temperature of stored food, or even leaving it at room
temperature, could lead to an increase of the aluminium leach-
ing, but in this work it was not possible to test it, because
tomato sauce left at room temperature for 24 h is improper to
consume.
For tomato cooked with sugar 2.8 mg Al/100 g tomato were
found, while the sample stored in the refrigerator showed 2.9 mg
Al/100 g tomato. Again, results from the same cooked sample
with sugar, but digested and analyzed with a 48 h difference,
showed no statistical difference. However, it is easily observed
that the sugar presence helps to decrease aluminium leaching.
Fimreite et al. [12] have already reported similar results when
cooking black currant juice and postulated a possible explana-
tion for sugar role. According to Fimreite, since sugar has no
alkaline or acid neutralization properties, a possible explana-
tion can be that the sugar may have formed a sort of coating
that reduce the contact between the acids in the juice and the
aluminium surface.
4. Conclusions
From this work it can be concluded that cider apple vinegar
seems to be the best choice for decreasing aluminium leaching
when cooking red cabbage.
Preparing tomato sauce with white sugar could also decrease
aluminium leaching and therefore decrease aluminium intake
from food. Keeping acidic food in aluminium containers, for
48 h in refrigerators, do not significantly increase Al leaching,
suggesting that storing food at low temperatures for 2 days
is not a cause of concern. Comparing the analytical method-
ologies, it can be said that the quartz crystal methodology is
faster than the UV–vis methodology. Quartz crystal frequency
response and recovery occurs within 2 min, while colour devel-
opment reaction takes 15 min to reach the maximum absorbance.
Besides, absorbance rapidly decays with time, which obliges
the analyst to prepare a single sample each time, as absorbance
readings must be made at very precise times after reagent
mixing. This problem does not exist using the quartz crys-
tal sensor, as no developing colour reaction needs to take
place.
Besides, the quartz crystal sensor is so stable, that if never
taken out of the cell, its calibration curve does not vary signifi-
cantly during a period of 2 months.
Comparing the results obtained with both methodologies, no
statistical significant differences (α = 0.05) were found both in
the average of the replicate analysis nor in the precision of the
results.
Acknowledgments
This project was financed by the Portuguese Foundation for
Science and Technology (FCT), POCTI and FEDER.
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Biographies
Marta I.S. Verı́ssimo has a post-doc position at the University of Aveiro. She
received a BS degree in chemistry in 1998 from the University of Aveiro and
a PhD in analytical chemistry in 2003 from the same University. Her current
research interests are in chemical sensors.
João A.B.P. Oliveira is an associate professor at the University of Aveiro. He
received his BS degree in chemical engineering from the Technical University of
Lisbon in 1976 and a PhD in analytical chemistry from the University of Virginia
in 1985. His current research interests are chemical sensors, chemometrics, and
laboratory automation.
M. Teresa S.R. Gomes is an associate professor at the University of Aveiro. She
received her BS degree in chemical engineering from the University of Coimbra
in 1983 and a PhD in analytical chemistry from the University of Aveiro in 1997.
Her current interests are chemical sensors and analytical chemistry.