Migration of Toxic Metals from Epoxy Coated Tinplate Cans to

Meat Products
Vesna Antić1, Branislav Stojanović2, Ljubica Radović3, Milica Balaban4, Saša Janković5 and Vesna Đorđević5
Faculty of Agriculture, Nemanjina 6, 11080 Zemun, Serbia (vantic@agrif.bg.ac.rs);
1

2
Ministry of Defence, Republic of Serbia, Birčaninova 5, Belgrade, Serbia;
3
Military Technical Institute, Ratka Resanovića 1, Belgrade, Serbia;
4
University of Banja Luka, Mladena Stojanovia 2, Banja Luka, Bosnia and Herzegovina;
5
Institute of Meat Hygiene and Technology, Kaćanskog 13, Belgrade, Serbia.

INTRODUCTION: EXPERIMENTAL:
In the armies worldwide, canned food based on meat is one of the strategic foods thanks to good The concentrations of the metals (Cr, Mn, Fe, Cu, Zn, As, Se, Cd, Sn, Hg and Pb) in the canned foods
sustainability and high nutritional value. However, interaction between food and metal packaging might be were determined by Inductively Coupled Plasma with Mass Spectrometry (ICPMS). The samples of
a potential source of toxic elements release, which if ingested by humans can cause harmful effects. The canned meat products were manufactured for the needs of the Serbian Armed Forces, according to the
aim of this study was to investigate the content of the metals and sensory properties of canned meat Regulation on the quality of meat products [4], in industrial facilities of various manufacturers. The
products at different storage periods, produced under the same military demands, but from different products were preserved by sterilization and stored in typical military facilities that provide prescribed
manufacturers. The meat products were packaged in cans made of electrolytic tinplate, protected inside microclimate requirements. Sterilized meat products are one of the strategic foods in the Serbian Army
and outside with epoxy-phenolic coating [1]. The structure of the coating, shown in Fig. 1, was previously due to their high nutritional value and long-term sustainability. Content of the metals was determined in
examined by IR spectroscopy and 1H NMR [2, 3] . beef goulash, pork ragout, spam, liver pate and meatballs in tomato sauce, stored minimally 3 months
and maximally 6 years. The storage period of the meat products was within their shelf life and longer.
The concentration of the metals obtained under this study were compared with the EU maximum
RESULTS AND DISCUSSION: permitted levels [5] as well as the Serbian legislation [6].
Sensory assessment was performed by quantitative descriptive analysis. The following sensory properties were examined: the outer
appearance of the packaging, the appearance and composition of the cross-section, the color, odor and taste, texture and/or succulence.
Each of the features was rated by scores of 1 (unsatisfactory) to 5 (excellent). In addition, in order to obtain marks for the overall sensory
quality, the marks for each sensory property were multiplied by the coefficient of significance: the outer appearance and/or the condition of
the packaging - 2; appearance and composition of the section - 4; color and color sustainability - 3; smell and taste of meat - 4; smell and
taste of side dishes - 3; texture and/or jussiness of meat - 2; texture and/or jussiness of inset - 2. In cans that do not contain inset (meat
steak and liver pate), the coefficient of significance for smell and taste, for both types of cans, is 7, while the coefficient of significance for
texture for spam is 4, and for liver pate it is 5. After adding the corrected marks, the obtained value was divided by 20 (the sum of the
coefficients), which gives the mark for the total sensory quality of the cans in the range of 1 (unsatisfactory) to 5 (excellent). The
dependence of the overall (total) sensory marks on the content of micro and toxic elements during a certain storage period is shown.
Table 2. Changes in can content during storage

Period of Type of meat can

storage
Beef goulash (BG)
Parts of meat with
inappropriate shape. Lesser
0-3
percentage of connective
months tissue.
Figure 1. Protection of tinplate can with epoxy-phenolic coating Parts of meat with
6–12 inappropriate shape and
Table 1. Changes on cans during storage months size. Lesser percentage of
connective tissue.
While shelf life
Meatballs in tomato
Pork ragout (PR) Spam (SP) Liver pate (LP)
sauce (MB)
Parts of meat with
inappropriate shape.
Representation of - - nd
connective tissue and
tendons.
Parts of meat with Bigger parts of fat. Slightly -
inappropriate shape. softer consistency.
nd
Dominant flavor of spice
pepper.

Type of meat can Flavor of meat and inset is sour

Period of storage 1 -2 and adust. Texture dry, solid.
(year/month = y/m) BG PR SP LP MB - - nd nd
years Inset lumpy, distinctively red
colored.
0y/1m-2y/6m nd nd nd nd nd Consistency slightly Flavor of meat and inset is
While shelf life

2 -3 sticky. metal, sour and adust. Texture

2y/6m – 3y/0m nd nd nd corrosion corrosion nd nd nd
years too solid and dry. Inset lumpy,
marbling, insignificant insignificant solid, distinctively red colored.
3y/0m – 3y/6m - - Metal flavour of meat and Metal flavour of meat Separation of jelly and fat. Separation of jelly and fat. Flavor of meat and inset is
corrosion damages damages
inset. Dark colour of meat. and inset. Muddy inset. Uneven look of section. Cavities bigger than 2mm. inappropriate for product,
3y/6m – 4y/0m - nd - - corrosion 3 -4 Muddy inset. Yellow- Bad colour sustainability. Consistency slightly metal, sour and adust. Texture
marbling, years brown colour of tallow. Stale, sour smell. Soft sticky. too solid and dry. Inset dense,
4y/0m – 4y/6m nd - - -
Expired shelf life

corrosion texture. lumpy, solid, distinctively red

colored.
4y/6m – 5y/0m - - corrosion corrosion - Metal flavor of meat and Metal flavour of meat Soft texture. Stale, sour Separation of liquid, jelly
5y/0m – 5y/6m nd corrosion corrosion corrosion -
inset. Dark colour of meat and inset. smell. Metal flavour. and fat. Cavities bigger
4-5 and inset. Yellow-brown than 2 mm. Consistency
insignificant -
Expired shelf life

5y/6m – 6y/0m nd nd nd - years colour of tallow. Rotten sticky and inappropriate.

damages smell. Poor colour sustainability.
nd= changes not detected Metal flavour.
Metal flavour of meat and Metal flavour of meat Uneven cross section. Separation of liquid, jelly
Table 1. Metals content and overall sensory marks during storage inset. Dark-red colour of and inset. Metal flavour. Soft texture. and fat. Cavities bigger
5-6 inset. than 2 mm. Consistency
-
Period of Concentration of microelements [mg/kg] Concentration of toxic elements Overall years soft-lubricant and sticky.
Meat
storage sensory
Poor colour sustainability.
(y/m) mark
product
Cr Mn Fe Cu Zn Se
As, Cd, Sn, Hg, Pb, Metal flavour.
µg/kg µg/kg mg/kg µg/kg µg/kg
nd= changes not detected
0/3 0.12 0.39 20.60 0.77 44.72 0.12 4.00 1.00 < 0.4 <1 <4 4.68
0/11
2/2
0.04
0.09
0.18
0.24
18.43
23.69
0.62
0.74
40.43
51.99
0.18
0.14
<4
10.00
<1
1.00
< 0.4
< 0.4
<1
<1
<4
<4
4.17
4.88
CONCLUSIONS:
3/2 3.84
BG

0.12 0.21 22.93 0.66 47.38 0.06 5.37 <1 < 0.4 6.71 <4
4/0 0.10 0.24 28.80 0.73 37.15 0.11 5.22 1.55 0.52 4.58 <4 3.55  The content of toxic metals in canned meat products, which were stored in typical military facilities that provide prescribed
5/1 0.05 0.46 20.50 0.88 42.36 0.08 5.13 <1 0.68 9.48 <4 4.46 microclimate requirements, was below the legally permissible concentration.
5/9 0.06 0.31 20.19 0.62 40.06 0.10 5.19 <1 0.41 8.48 6.00 4.49
In all LP samples, as well as in some SP samples, the Fe concentration was above 30 mg/kg, which is a significantly high
0/3 0.03 0.26 11.41 0.82 28.62 0.16 <4 1.00 < 0.4 <1 <4 4.62
0/6 0.05 0.20 11.90 0.76 28.28 0.14 <4 <1 < 0.4 <1 <4 4.81 value. The concentration of Fe in some samples of the BG was between 20 mg/kg and 30 mg/kg (the borderline value according
2/2 0.04 0.21 9.02 0.86 29.72 0.11 <4 <1 < 0.4 <1 <4 4.50 to Serbian legislation), which can significantly alter the sensory characteristics of food.
3/2 4.63
Hg concentration increased in some samples of the BG, PR, SP and LP, with the highest value of 15.04 µg/kg for the sample of
PR

0.02 0.52 11.83 0.84 26.34 0.14 <4 <1 < 0.4 6.49 <4
4/0 0.03 0.36 9.90 1.05 26.42 0.09 <4 <1 1.57 11.72 <4 4.49
5/1 0.16 0.27 11.20 0.74 24.92 0.09 <4 2.18 1.27 15.04 8.00 4.19 PR. Also, Cd concentration increased in some LP samples, with the highest value of 35.39 µg/kg.
5/9 0.13 0.30 13.10 0.77 24.44 0.06 9.33 2.03 0.90 8.29 <4 4.45 In most cases, low sensory ratings were associated with an increased concentration of toxic and microelements.
0/8 0,06 0,24 10.96 0.73 20.90 0,11 <4 <1 < 0.4 <1 <4 4.55

REFERENCES:
1/1 0.27 0.30 8.70 1.25 14.56 0,06 5.66 3.50 < 0.4 5.10 <4 4.81
2/1 0.09 0.65 14.04 0.78 19.94 0,07 <4 1.16 0.53 2.12 6.00 4.39
3/1 2.90
SP

0.23 0.61 14.38 1.54 21.99 0,09 4.58 13.28 0.49 11.44 5.00
4/4 0.16 0.70 29.25 1.02 18.05 0,08 <4 1.55 0.42 <1 <4 4.42 1. R. H. Good, Recent Advances in Metal Can Interior Coatings, American Chemical Society, Washington, DC, 1988.
5/0 3.96
0.10 1.03 42.52 0.99 19.61 0,06 <4 1.00 0.40 <1 <4 2. B. Stojanović, Lj. Radović, D. Natić, M. Dodevska, G. Vraštanović-Pavičević, M. Balaban, S. Lević, T. Petrović, V. Antić, Journal of the Serbian Chemical Society,
6/0 4.65
0.06 0.44 26.59 1.00 24.56 0,06 4.96 1.49 0.81 4.56 <4
84 (2019) 377.
0/7 0.04 1.18 32.42 3.09 19.84 0.21 <4 6.00 < 0.4 <1 <4 4.90
1/1 4.90
3. B. Stojanović, Lj. Radović, D. Natić, M. Dodevska, G. Vraštanović-Pavičević, M. Balaban, Z. Stojanović, V. Antić, Migration of bisphenol A into food simulants
0.05 1.05 32.45 3.95 18.67 0.17 5.47 2.48 < 0.4 1.72 <4
2/4 0.09 1.37 41.02 3.88 24.11 0.18 <4 10.20 < 0.4 7.01 <4 4.10 and meat rations during initial time of storage, Packaging Technology and Science (2019) DOI: 10.1002/pts.2485.
3/0 3.74 4. RS Official Gazette, No. 94/15 of 17 November 2015: Regulation on the quality chopped meat, semi-products from meat and products from meat (in
LP

0.34 1.88 46.80 4.42 26.98 0.13 4.70 35.91 3.94 6.63 4.00
4/4 0.26 1.98 44.32 4.13 24.88 0.19 <4 11.13 0.45 <1 <4 3.53 Serbian).
5/0 0.05 1.19 47.59 3.67 19.72 0.13 <4 8.00 0.40 <1 <4 4.06 5. Commission Regulation, (EC) 1881/2006 setting maximum levels for certain contaminants in foodstuffs, issued by the European Commission, Official
6/0 0.45 1.01 41.68 3.90 20.90 0.20 <4 6.71 0.55 3.55 <4 4.51 Journal of the European Union, L364/5, 2006.
0/1 4.10
0.021 0.38 10.54 0.51 20.18 0.117 <4 3.00 < 0.4 <1 <4 6. RS Official Gazette, No. 22 of March 20, 2018, 90 of November 21, 2018, 76 of October 25, 2019: Regulations on the maximum levels of residues of plant
1/10 0.032 0.67 10.08 0.75 21.36 0.074 <4 7.00 < 0.4 <1 <4 3.45
protection products in food and animal feed and on food and feed for which maximum residue levels of plant protection products are determineted (in
MB

2/8 0.021 0.53 14.24 0.68 23.38 0.106 5.00 4.00 4.50 <1 <4 3.89
3/9 3.58
Serbian).
0.021 0.58 15.38 0.61 24.85 0.079 <4 2.00 4.82 <1 <4