Food and Chemical Toxicology 47 (2009) 571577

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Food and Chemical Toxicology

journal homepage: www.elsevier.com/locate/foodchemtox

A simple pre-treatment of aluminium cookware to minimize aluminium transfer to food

Rim Karbouj *,1, I. Desloges, P. Nortier
LGP2 UMR 5518 (CNRS, Grenoble INP, AGEFPI, CTP), 461 rue de la Papeterie, BP. 65, 38402 Saint Martin dHres cedex, France

a r t i c l e

i n f o

a b s t r a c t
In this work, we studied aluminium leaching from cookware to food under the effect of citric acid that is commonly found in foods and beverages. The authors showed that boiling the cookware in water prior to cooking is suitable for the decrease of aluminium leaching into food by a factor up to sixty (with a corresponding decrease of the aluminium intake by consumers). The effect of the pre-treatment has been studied by scanning electron microscopy and X-Ray diffraction and the effect has been attributed to changes in the structure and morphology of the passivation layer, from an initial heterogeneous layer to a surface uniformly covered with ne needles of Boehmite (a-AlOOH). 2008 Elsevier Ltd. All rights reserved.

Article history: Received 26 August 2008 Accepted 15 December 2008

Keywords: Aluminium Leaching Food Treatment

1. Introduction Aluminium has been used extensively in foodstuffs, utensils and packaging (Baxter et al., 1989; Karbouj, 2007). Depending on the meal, the cooking in aluminium cookware can expose humans to the ingestion of important quantities of aluminium. In our human body, aluminium ion can inhibit different metabolism processes by competition reactions with other ions such as iron, magnesium, calcium, phosphor, uoride and others (Mahieu et al., 2004; Aikoh et al., 2005; Kaur and Gill, 2005). Aluminium (Al) is associated with anaemia, osteomalacia, and a neurologic syndrome known as dialysis encephalopathy (Malluche, 2002; Savory et al., 1986). Then, both in experimental animals and in human, aluminium is clearly identied as a potent neurotoxicant (Flaten et al., 1996; WHO, 1997). The World Health Organisation considered in 1986 that humans consumed about 30 mg of Al/day on average, through water, foods and drugs (WHO, 1986). In some conditions, the daily intake from food can be much larger than this average value (Karbouj, 2007). The Joint FAO/WHO Expert Committee on Food Additives (WHO, 1989) has established the Provisional Tolerable Weekly Intake of 7 mg/kg body weight (equivalent to 60 mg/day for an adult man).

The cooking in utensils like aluminium skillets, pressure cookers, roasting pans, pots, saucepans, frozen dinner trays, foils and wrappers provide an important amount of aluminium, especially in the case of acidic dishes as tomato sauce for example (Ranau anc ar et al., 2004; Karbouj, 2007). et al., 2001; c 1.1. Dissolution of aluminium In spite of the low redox potential (1.66 V versus S.H.E.), the corrosion of aluminium is inhibited at 4 < pH < 8.5 by the presence of a barrier layer of aluminium (III) (oxy)-hydroxide (Hollingsworth and Hunsicker, 1983). Transfer of aluminium to food during cooking can arise from two competitive mechanisms: slow uniform dissolution of the (oxy)-hydroxy layer at the solution interface, itself being regenerated by slow oxidation at the metal interface. Under cooking conditions, uniform dissolution of the aluminium (oxy)-hydroxide is kinetically controlled by the detachment of the hydrated aluminium ion, itself governed by the surface proton adsorption. The dissolution occurs at constant rate per unit area (Dietzel and Bhme, 2005; Karbouj, 2008). pitting corrosion consists in the localised formation of pits across the passivation and metal layers. It is promoted by different factors, including the presence of precipitates of some secondary phases (e.g. Al12Fe3Si2) in the aluminium matrix (Hollingsworth and Hunsicker, 1987). In this paper, we describe a simple treatment that can drastically decrease the leachability of aluminium cookware. For

Abbreviations: AD, Alzheimer disease; Al, aluminium; ICP-MS, inductively coupled plasma-mass spectrometry; S.H.E, Standard Hydrogen Electrode. * Corresponding author. Tel.: +33 4 76 49 01 85. E-mail address: karbouj_rim@hotmail.com (R. Karbouj). 1 Present address: 72 Avenue Rhin et Danube, 38100 Grenoble, France. 0278-6915/$ - see front matter 2008 Elsevier Ltd. All rights reserved. doi:10.1016/j.fct.2008.12.028

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Assemblage of the study of the aluminium transfer

1. Heating circulator bath 2. Peristaltic pump 3. Reactor 4. Aluminium sample 5. Sample Handler 6. Thermostat 7. WatsonMarlow Bredel Bioprene tubing 8. Solution 9. Refrigerant 10. pH-meter 11. Electrode 12. Temperature probe
Fig. 1. Experimental device.

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Dissolved total [Al] (mg/L)

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Fig. 2. Dissolved total [Al] (mg/L) as a function of the time and temperature of leaching (Citric Acid 10 mmol/L). (a) Without pre-treatment (leaching: 84 C); (b) With pre-treatment 5 h at 20 C (leaching: 84 C); (c) With pre-treatment 5 h at 94 C (leaching: 84 C); and (d) With pre-treatment 5 h at 94 C (leaching: 100 C).

Time of the pre-treatment (min)

Fig. 3. Dissolved total [Al] (mg/L) as a function of the time of pre-treatment at 84 C (Citric Acid 10 mmol/L). (a) Without pre-treatment (leaching: 84 C) and (b) With different pre-treatments time at 94 C pre-treatment.

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Fig. 4. Photographic images by SEM of the foil surface.

economical reasons, one cannot prevent peoples to use aluminium kitchen utensils such as pots, pans, and coffee percolators and others, but one can educate users to simple gestures that can contribute to reduce the total dietary intake of aluminium.

2. Materials and methods 2.1. Reagents Citric acid monohydrate (crystallized), was purchased from SIGMAALDRICH (St. Quentin Fallavier, France). Samples (2.5 15 cm2) were cut out of Aluminium Foil

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Intensity (Counts / 1000)

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Fig. 5. Spectres by XRD of the foil surface. (99.5% pure), from ALUPLUS dALFAPAC (Paris, France), purchased in a department store, verifying that all packages were from the same batch. For all leaching experiments, deionised water was used (Elga, Villeurbanne, France). 2.2. Instrumentation The experimental device included: a peristaltic pump (Sci-Q 323 E, WatsonMarlow, Falmouth, Cornwall, England), a pH-meter (Haana 211, Tanneries, France) and a heating circulator bath (Model C1-B3, HAAKE, Germany). Polypropylene aluminium-free bottles (WVR International GmbH, Darmstadt, Germany) were used for storage of all samples. (See Fig. 1) 2.3. Pre-treatment The aluminium foil was used either as such or pre-treated. Pre-treatment consisted in dipping the foil for a given time (0, 15, 30, 60 or 300 min) into water at ambient (20 C) or near-boiling temperature (94 C). 2.4. Dissolution experiments Samples of aluminium foil (2.5 cm 15 cm) were tested by the contact in a reactor together with 275 ml of citric acid 1.0 102 mol/L at near-boiling temperature (84 or 100 C), for 10, 30, 60 or 300 min. These times of reaction with citric acid were selected because they are different times of preparation or cooking of commonly consumed foods and beverages, like dairy products, berries and citrus fruits (i.e. lemon, black-currant, red-currant). The temperature was chosen as close as possible to the boiling point, considering practical limitations of the device. The ow rate in the reactor was set to 1.8 L/min, as preliminary experiments showed that the dissolution is not affected by mass transport at the corresponding velocity (Karbouj, 2008). 2.5. Analysis Aluminium content in water was measured at the Central Analytic Department of the National Centre for Scientic Research (Service Central dAnalyse, CNRS, Vernaison, France) using inductively coupled plasma-mass spectrometry (ICP-MS) analyses with an X7 series quadrupole instrument (Thermo Electron Corporation, Cergy-Pontoise, France). Scanning electron microphotographs were performed at the LGP2 on a QUANTA 200 from FEI, tted with an X PGT probe (Sahara SDD) for chemical analysis, data were treated using Spirit software. Crystalline phases on aluminium foil were determined by XRD at the Scientic Research Laboratory (Consortium des Moyens Technologiques Commun, CMTC) of Grenoble Institute of Technology using a PanAnalytical XPert Pro MPD Diffractometer. Additional chemical analysis were also realised at the CMTC using a Jeol 6400 SEM tted with Brker SDD EDS probe.

3. Results and discussion The amount of aluminium in solution after contact of non pretreated and pre-treated (20 or 94 C during 5 h) aluminium foil during typical cooking times at 84 and 100 C is depicted on Fig. 2. The Fig. 2 shows a very important effect of the pre-treatment at 94 C, which decreases the amount of dissolved aluminium by a factor from 20 to about 60, while the pre-treatment in cold water is ineffective. This protection of the foil by the pre-treatment is kept during leaching at higher temperature (100 C). The amount of aluminium in solution after contact of non pretreated and pre-treated aluminium foil for a given time (0, 15, 30, 60 or 300 min) near-boiling temperature (94 C) during typical cooking times at 84 C is depicted on Fig. 3. The Fig. 3 illustrates the effect of the time of a pre-treatment at 94 C on dissolution. We see that a short pre-treatment, of some minutes, already assures a decrease of the dissolved amount (Al leachability) by a factor of 3. Then, a pre-treatment of half an hour ensures a decrease of Al leachability by a factor of 9. 3.1. Characterisation of the aluminium passivation layer The most important feature from Fig. 2 is the drastic hindrance of dissolution by the pre-treatment in near-boiling water. The rate of dissolution of aluminium changes from 5.5 mg m2 min1 for no or cold water pre-treatment to 0.13 mg m2 min1 for a near-boiling water pre-treatment of 300 min.

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Fig. 6. Photographic images by SEM of the foil surface.

Fig. 7. Photographic images by SEM of the foil surface.

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Fig. 8. Spectres by XRD of the foil surface after treatment and leaching exhibiting bayerite.

This result is original, to our knowledge. Nevertheless, it is not so surprising: Alwitt (Alwitt, 1976) showed that the water born hydroxylated lm structure and texture undergo a transition around 90 C: below this temperature, the lm is made of two layers, the inner (close to the metal) layer being pseudoboehmite, the outer layer being bayerite. At a higher temperature, the lm is made of pseudo-boehmite only, and the porosity is lower (by a factor of about 20) than the porosity of low temperature lms. 3.1.1. Surface of the aluminium foil before acidic leaching Scanning electron microscope (SEM) observations of the foil surface state before and after pre-treatment and before acidic contact, are shown in Fig. 4ae. The virgin foil (Fig. 4b) shows an heterogeneous relief, rather smooth but including some macropores (diameter about 0.5 lm). On the contrary, the Fig. 4d and e shows the aspect of the surface of the Al pre-treated foil, exhibiting a wallpapered surface with ne curved needles (about 0.2 lm in their length and less than 50 nm in their thickness) delimiting mesopores. This morphology is classical of the boehmite or the pseudo-boehmite AlOOH polymorphs. As depicted in Fig. 5, the X-ray diffraction (XRD) only discerns Al and Al4.01MnSi0.74 crystallized phases on samples without pretreatment and with (5 h at 20 C) pre-treatment. On the contrary, the hot water pre-treated (5 h at 94 C) sample introduces the characteristic lines of the boehmite. 3.1.2. Surface of the aluminium foil after acidic leaching Non pre-treated surface. After leaching by citric acid (5 h, 84 C, 10 mmol/L), we observe in the Fig. 6 that the surface roughness of the non pre-treated foil (Fig. 6a and b) and the pre-treated foil (5 h in 20 C) (Fig. 6c) seems very high. The corrosion gures depicted on Fig. 6 are typical of pitting corrosion. Hot water pre-treated surface. The hot water pre-treated foil exhibits very few pittings and keeps on the whole the same morphology (paperwall of pseudo-boehmite needles) as the unleached foil (Fig. 7a).

We also notice in the Fig. 7b, on this pre-treated foil in 94 C during 5 h and subjected to sour leaching in 84 C during 5 h, the growth of crystals of which morphology is typical of the bayerite. The bayerite was also identied by XRD as depicted on Fig. 8. 4. Conclusion We studied the corrosion of alimentary aluminium foils by an aqueous solution of citric acid, simulating the conditions of cooking acidic ingredients as tomato sauce, lemon juice. . . Pitting corrosion was detected and can be favored by the presence of precipitates of a secondary phase Al4.01MnSi0.74. The pretreatment of the foils in boiling (or near boiling) water strongly modies the passivation layer, giving rise to the growth of a wallpaper of boehmite needles. During a subsequent cooking simulation, this layer inhibits the formation of pits and the main modication is the crystallisation of bayerite. Our results indicate that for reducing the leachability of aluminium from aluminium cookware into foods and per consequence, also to decrease the daily aluminium intake during the preparation of food, we must boil water in aluminium kitchen utensils (such as pots, pans, and coffee percolators and others) used for cooking the food. Per consequence, the daily aluminium intake will decrease. The pre-treatment of aluminium utensils for a certain time is very important to protect the public health. In conclusion, we recommend a change in foods and beverages cooking practices. This could also apply to storage materials.

Conicts of Interest statement The authors declare that there are no conicts of interest. Acknowledgements The authors wish to acknowledge collaboration of Dr. Stphane Coindeau at the CMTC (Grenoble INP) for EDX-SEM and XRD deter-

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minations, and of Mrs. Bertine Kheli at the LGP2 ESEM facility for SEM photographs. References
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