Determination of Tin in Canned Foods by Atomic Absorption ...

Determination of Tin in Canned Foods by Atomic Absorption ... Determination of Tin in Canned Foods by Atomic Absorption ...

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Czech J. Food Sci. Vol. 27, 2009, Special Issue Determination of Tin in Canned Foods by Atomic Absorption Spectrometry J. KnápeK 1* , V. Herman 2 , r. BuCHtoVá 1 and D. VošmeroVá 1 1 Czech agriculture and Food Inspection authority, 603 00 Brno, Czech republic; 2 the Secondary technical School of Chemistry, 614 00 Brno, *e-mail: jan.knapek@szpi.gov.cz Abstract: Atomic absorption spectrometry is a powerful technique for determination of tin in canned foods. Homogenous samples of syrup and solid parts were digested by means of microwave digestion system MLS 1200 MEGA where hydrochloric and nitric acid were used as reagents. The measurements were carried out using a Perkin-Elmer AAnalyst 700 atomic absorption spectrometer. Detection limit was 4 mg/kg in nitrous oxide and acetylene flame. There were analysed 222 samples of 26 various kinds of canned fruit (e.g. pineapple, peach, mandarin), vegetables (e.g. bean, mushroom, tomato) and meat (sea products) in this work. The analytical results indicated tin total concentrations from under 4 mg/kg to 353 mg/kg. Different concentrations of tin between syrup and fruit were observed. The concentration of tin was higher in solid parts than in syrup. Relationship between the concentration and time period after opening was studied. The corrosion of the tinplate surface was accelerated by air and the amount of dissolved tin was significantly increasing in syrup as well as fruit when cans were opened and stored for two days at 6°C. Keywords: tin; canned food; atomic absorption spectrometry InTroDuCTIon The acute toxicity of inorganic tin is manifested as gastric irritation, nausea, vomiting and abdominal discomfort. Inorganic tin salts are poorly absorbed by the gastrointestinal tract and rapidly excreted. Nevertheless, there are several case reports of gastric irritation and vomiting in humans consuming canned foods or beverages, particularly sour fruit products packaged in tinplate cans and containing high levels of tin. Food and especially canned food represent the main source of human exposure to tin. Maximum level of tin in canned foods is 200 mg/kg for canned foods other than beverages and 100 mg/kg for canned beverages, including fruit and vegetable juices (Commission Regulation EC No 1881/2006). Techniques that are most commonly used for determining tin are UV/VIS spectrophotometry (Huang et al. 1997), X-Ray fluorescence spectrometry (Mino 2006), inductively coupled plasma atomic emission spectrometry (Perring & Basic-Dvorzak 2002) and electrothermal atomic absorption spectrometry (Chiba 1987). In this work, we describe determination of tin by flame atomic absorption spectrometry in various kinds of canned foods. MATerIAlS AnD MeThoD Materials. A total of 222 samples of can (from years 2004–2008) made from 26 different kinds of fruit, vegetables and meat were analysed. All reagents were of analytical purity grade or higher. Method. Tin in total amount was determined by flame atomic absorption spectrometry (F-AAS). The samples of syrup were digested in MLS 1200 MEGA (Milestone, Italy) microwave digestion system. The 1 g homogenate of syrup or fruit was added to 4 ml nitric acid (Merck, Germany) and 4 ml hydrochloric acid (Lachema, Czech Republic). The digested samples were transfered to tube with 1.2 ml of potassium chloride as an ionisation buffer and adjusted to the volume of 15 ml with ultrapure water. The measurements were carried out using a Perkin-Elmer AAnalyst 700 type atomic absorp- S407

Czech J. Food Sci. Vol. 27, 2009, Special Issue<br />

<strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> <strong>T<strong>in</strong></strong> <strong>in</strong> <strong>Canned</strong> <strong>Foods</strong> <strong>by</strong> <strong>Atomic</strong><br />

<strong>Absorption</strong> Spectrometry<br />

J. KnápeK 1* , V. Herman 2 , r. BuCHtoVá 1 and D. VošmeroVá 1<br />

1 Czech agriculture and Food Inspection authority, 603 00 Brno, Czech republic; 2 the<br />

Secondary technical School <strong>of</strong> Chemistry, 614 00 Brno, *e-mail: jan.knapek@szpi.gov.cz<br />

Abstract: <strong>Atomic</strong> absorption spectrometry is a powerful technique for determ<strong>in</strong>ation <strong>of</strong> t<strong>in</strong> <strong>in</strong> canned foods. Homogenous<br />

samples <strong>of</strong> syrup and solid parts were digested <strong>by</strong> means <strong>of</strong> microwave digestion system MLS 1200 MEGA<br />

where hydrochloric and nitric acid were used as reagents. The measurements were carried out us<strong>in</strong>g a Perk<strong>in</strong>-Elmer<br />

AAnalyst 700 atomic absorption spectrometer. Detection limit was 4 mg/kg <strong>in</strong> nitrous oxide and acetylene flame.<br />

There were analysed 222 samples <strong>of</strong> 26 various k<strong>in</strong>ds <strong>of</strong> canned fruit (e.g. p<strong>in</strong>eapple, peach, mandar<strong>in</strong>), vegetables (e.g.<br />

bean, mushroom, tomato) and meat (sea products) <strong>in</strong> this work. The analytical results <strong>in</strong>dicated t<strong>in</strong> total concentrations<br />

from under 4 mg/kg to 353 mg/kg. Different concentrations <strong>of</strong> t<strong>in</strong> between syrup and fruit were observed. The<br />

concentration <strong>of</strong> t<strong>in</strong> was higher <strong>in</strong> solid parts than <strong>in</strong> syrup. Relationship between the concentration and time period<br />

after open<strong>in</strong>g was studied. The corrosion <strong>of</strong> the t<strong>in</strong>plate surface was accelerated <strong>by</strong> air and the amount <strong>of</strong> dissolved t<strong>in</strong><br />

was significantly <strong>in</strong>creas<strong>in</strong>g <strong>in</strong> syrup as well as fruit when cans were opened and stored for two days at 6°C.<br />

Keywords: t<strong>in</strong>; canned food; atomic absorption spectrometry<br />

InTroDuCTIon<br />

The acute toxicity <strong>of</strong> <strong>in</strong>organic t<strong>in</strong> is manifested as<br />

gastric irritation, nausea, vomit<strong>in</strong>g and abdom<strong>in</strong>al<br />

discomfort. Inorganic t<strong>in</strong> salts are poorly absorbed<br />

<strong>by</strong> the gastro<strong>in</strong>test<strong>in</strong>al tract and rapidly excreted.<br />

Nevertheless, there are several case reports <strong>of</strong><br />

gastric irritation and vomit<strong>in</strong>g <strong>in</strong> humans consum<strong>in</strong>g<br />

canned foods or beverages, particularly<br />

sour fruit products packaged <strong>in</strong> t<strong>in</strong>plate cans and<br />

conta<strong>in</strong><strong>in</strong>g high levels <strong>of</strong> t<strong>in</strong>. Food and especially<br />

canned food represent the ma<strong>in</strong> source <strong>of</strong> human<br />

exposure to t<strong>in</strong>. Maximum level <strong>of</strong> t<strong>in</strong> <strong>in</strong> canned<br />

foods is 200 mg/kg for canned foods other than<br />

beverages and 100 mg/kg for canned beverages,<br />

<strong>in</strong>clud<strong>in</strong>g fruit and vegetable juices (Commission<br />

Regulation EC No 1881/2006).<br />

Techniques that are most commonly used for determ<strong>in</strong><strong>in</strong>g<br />

t<strong>in</strong> are UV/VIS spectrophotometry (Huang<br />

et al. 1997), X-Ray fluorescence spectrometry (M<strong>in</strong>o<br />

2006), <strong>in</strong>ductively coupled plasma atomic emission<br />

spectrometry (Perr<strong>in</strong>g & Basic-Dvorzak 2002)<br />

and electrothermal atomic absorption spectrometry<br />

(Chiba 1987). In this work, we describe determ<strong>in</strong>ation<br />

<strong>of</strong> t<strong>in</strong> <strong>by</strong> flame atomic absorption spectrometry<br />

<strong>in</strong> various k<strong>in</strong>ds <strong>of</strong> canned foods.<br />

MATerIAlS AnD MeThoD<br />

Materials. A total <strong>of</strong> 222 samples <strong>of</strong> can (from<br />

years 2004–2008) made from 26 different k<strong>in</strong>ds <strong>of</strong><br />

fruit, vegetables and meat were analysed. All reagents<br />

were <strong>of</strong> analytical purity grade or higher.<br />

Method. <strong>T<strong>in</strong></strong> <strong>in</strong> total amount was determ<strong>in</strong>ed <strong>by</strong><br />

flame atomic absorption spectrometry (F-AAS). The<br />

samples <strong>of</strong> syrup were digested <strong>in</strong> MLS 1200 MEGA<br />

(Milestone, Italy) microwave digestion system. The<br />

1 g homogenate <strong>of</strong> syrup or fruit was added to 4 ml<br />

nitric acid (Merck, Germany) and 4 ml hydrochloric<br />

acid (Lachema, Czech Republic). The digested samples<br />

were transfered to tube with 1.2 ml <strong>of</strong> potassium<br />

chloride as an ionisation buffer and adjusted to the<br />

volume <strong>of</strong> 15 ml with ultrapure water.<br />

The measurements were carried out us<strong>in</strong>g a<br />

Perk<strong>in</strong>-Elmer AAnalyst 700 type atomic absorp-<br />

S407


Vol. 27, 2009, Special Issue Czech J. Food Sci.<br />

tion spectrometer. The 286.3 nm resonance l<strong>in</strong>e<br />

was generated <strong>by</strong> a Perk<strong>in</strong>-Elmer electrodeless<br />

discharge lamp with 300 mA <strong>in</strong>put current and the<br />

transmitted spectral <strong>in</strong>terval 0.7 nm. The samples<br />

were nebulised <strong>by</strong> a high sensitivity nebuliser to<br />

nitrous oxide and acetylene flame (rate <strong>of</strong> flow<br />

11.9/5.0 l/m<strong>in</strong>). The accuracy <strong>of</strong> measurement<br />

was checked <strong>by</strong> us<strong>in</strong>g Certified Reference Material<br />

T07103 Tomato paste – assigned value 306 ±<br />

42 mg/kg, measured value 302 ± 60 mg/kg.<br />

Table 1. Concentrations <strong>of</strong> t<strong>in</strong>, determ<strong>in</strong>ed <strong>by</strong> F-AAS<br />

(mg/kg)<br />

S408<br />

n M<strong>in</strong>imum Maximum<br />

Aloe vera 1 < 4.0<br />

Apricot 10 5.30 154<br />

Artichoke 1 89.2<br />

Asparagus 2 < 4.0 26.6<br />

Bamboo 2 < 4.0<br />

Bean 14 < 4.0 353<br />

Can meat 5 < 4.0 8.85<br />

Coconut milk 2 < 8.0<br />

Fruit cocktail 9 6.30 166<br />

Grapefruit 5 44.3 311<br />

Kiwi 1 < 4.0<br />

Lychee 3 68.8 138<br />

Maize 4 < 4.0 5.43<br />

Mandar<strong>in</strong> 27 34.5 142<br />

Mango 6 < 4.0 39.9<br />

Mushrooms 14 < 4.0 189<br />

Papaya 4 < 4.0 7.88<br />

Peach 17 30.5 209<br />

Pear 8 < 4.0 97.8<br />

Peas 12 < 4.0 10.1<br />

P<strong>in</strong>eapple 42 24.1 238<br />

Rambutan 2 56.9 73.4<br />

Raspberry 3 < 4.0 5.55<br />

Soya shoot 2 < 4.0<br />

Strawberry 20 < 4.0 6.00<br />

Tomato 6 5.80 109<br />

n = number <strong>of</strong> samples<br />

reSulTS AnD DISCuSSIon<br />

Table 1 shows the results <strong>of</strong> total amount <strong>of</strong> t<strong>in</strong><br />

from monitored cans <strong>by</strong> atomic absorption spectrometry.<br />

The analytical results <strong>in</strong>dicated t<strong>in</strong> total<br />

concentrations from under 4 mg/kg to 353 mg/kg.<br />

Maximum permissible level <strong>of</strong> t<strong>in</strong> 200 mg/kg<br />

was exceeded <strong>in</strong> cases <strong>of</strong> beans (353 mg/kg) and<br />

grapefruit (311 mg/kg). An enhanced amount <strong>of</strong><br />

t<strong>in</strong> was observed for example <strong>by</strong> canned apricots,<br />

mushrooms, mandar<strong>in</strong>s, peaches, p<strong>in</strong>eapple, fruit<br />

cocktail and tomatos. However, maximum level<br />

was not exceeded with regard to expanded uncerta<strong>in</strong>ty<br />

<strong>of</strong> measurement. The very low amount (less<br />

than 4 mg/kg) <strong>of</strong> t<strong>in</strong> was observed for example <strong>in</strong><br />

strawberries, raspberries, and canned meat. The<br />

higher 200content<br />

<strong>of</strong> t<strong>in</strong> was observed <strong>in</strong> cans with<br />

sour products Syrup P<strong>in</strong>eapple<br />

and products <strong>in</strong> uncoated cans.<br />

150 Fruit<br />

200<br />

Syrup P<strong>in</strong>eapple<br />

100<br />

150 Fruit<br />

200<br />

50<br />

100 Syrup P<strong>in</strong>eapple<br />

150<br />

0 Fruit<br />

50<br />

100 0 1 3 6 24 48<br />

0<br />

50 0 1 3 6 24 48<br />

Concetration�<strong>of</strong>�t<strong>in</strong><br />

Concentrion�<strong>of</strong>�t<strong>in</strong>�<br />

Concentration <strong>of</strong> t<strong>in</strong> Concetration�<strong>of</strong>�t<strong>in</strong> Concetration�<strong>of</strong>�t<strong>in</strong><br />

Concentrion�<strong>of</strong>�t<strong>in</strong>� Concentrion�<strong>of</strong>�t<strong>in</strong>� Concentration�<strong>of</strong>�t<strong>in</strong> Concentration�<strong>of</strong>�t<strong>in</strong><br />

Concentration Concentration�<strong>of</strong>�t<strong>in</strong><br />

<strong>of</strong> t<strong>in</strong> Concentration <strong>of</strong> t<strong>in</strong><br />

(mg/kg)<br />

(mg/kg)<br />

(mg/kg)<br />

(mg/kg) (mg/kg)<br />

(mg/kg) (mg/kg)<br />

(mg/kg) (mg/kg) (mg/kg) (mg/kg)<br />

0<br />

300<br />

0 1 3 6<br />

Mandar<strong>in</strong><br />

24 48<br />

250<br />

200<br />

300<br />

150<br />

250<br />

Mandar<strong>in</strong><br />

200<br />

100<br />

150 300<br />

50<br />

100 250<br />

0<br />

Mandar<strong>in</strong><br />

200 50<br />

150 0<br />

0 1 3 6 24 48<br />

100 0 1 3 6 24 48<br />

50<br />

120<br />

0<br />

100<br />

120<br />

80<br />

100<br />

60<br />

80<br />

0 1<br />

Peach<br />

Peach 3 6 24 48<br />

40<br />

60<br />

120<br />

20<br />

Peach<br />

40<br />

100<br />

0<br />

20<br />

80<br />

0<br />

0 1 3 6 24 48<br />

60<br />

Time�(h)<br />

0 1 3 6 24 48<br />

40<br />

Time�(h)<br />

Figure 1. Dependence 20 <strong>of</strong> stand<strong>in</strong>g <strong>in</strong> an opened can (at<br />

6°C) on t<strong>in</strong> 0content<br />

<strong>in</strong> syrup and fruit<br />

0 1 3 6 24 48<br />

Time�(h)


Czech J. Food Sci. Vol. 27, 2009, Special Issue<br />

Different concentrations <strong>of</strong> t<strong>in</strong> between syrup<br />

and fruit were observed. Samples <strong>of</strong> canned mandar<strong>in</strong>s<br />

and p<strong>in</strong>eapple were used for this experiment.<br />

The content <strong>of</strong> can was separated <strong>in</strong>to syrup and<br />

solid parts. Some amount <strong>of</strong> t<strong>in</strong> was determ<strong>in</strong>ed<br />

<strong>in</strong> both. 52–64 mg/kg <strong>of</strong> t<strong>in</strong> for syrup samples and<br />

65–133 mg/kg <strong>of</strong> t<strong>in</strong> were observed for solid part.<br />

The concentration <strong>of</strong> t<strong>in</strong> was higher <strong>in</strong> solid part<br />

than syrup. As syrup <strong>of</strong> p<strong>in</strong>eapple conta<strong>in</strong>ed very<br />

small parts was filtered and amount <strong>of</strong> t<strong>in</strong> was<br />

determ<strong>in</strong>ed <strong>in</strong> pure syrup and small part from the<br />

filter. The amount <strong>of</strong> t<strong>in</strong> <strong>in</strong> syrup was 48 mg/kg,<br />

but <strong>in</strong> the filtered parts 728 mg/kg. However, these<br />

small parts composed less than 1% <strong>of</strong> total content<br />

<strong>of</strong> can. These results might be accounted for <strong>by</strong><br />

the adsorption capacity <strong>of</strong> t<strong>in</strong> on the surface.<br />

Relationship between the concentration and<br />

time period after open<strong>in</strong>g was studied. For this<br />

experiment were used samples <strong>of</strong> canned mandar<strong>in</strong>s,<br />

p<strong>in</strong>eapple and peaches. The content <strong>of</strong><br />

can was separated <strong>in</strong>to two parts. In the first part<br />

was immediately determ<strong>in</strong>ed concentration <strong>of</strong> t<strong>in</strong><br />

<strong>in</strong> syrup and fruit. The second part <strong>of</strong> can was<br />

stored at 6°C. The concentration <strong>of</strong> t<strong>in</strong> <strong>in</strong> syrup<br />

after 1, 3, 6 and 24 h was determ<strong>in</strong>ed <strong>by</strong> duration<br />

<strong>of</strong> experiment. Amount <strong>of</strong> t<strong>in</strong> <strong>in</strong> both parts was<br />

determ<strong>in</strong>ed after 48 hours. All results are summarised<br />

<strong>in</strong> Figure 1. The corrosion <strong>of</strong> the t<strong>in</strong>plate<br />

surface was accelerated <strong>by</strong> air and the amount <strong>of</strong><br />

dissolved t<strong>in</strong> was significantly <strong>in</strong>creas<strong>in</strong>g <strong>in</strong> syrup<br />

as well as fruit when cans were opened and stored<br />

for two days at 6°C.<br />

ConCluSIon<br />

The results <strong>of</strong> this work showed that more than<br />

98% <strong>of</strong> <strong>in</strong>vestigated canned food samples conta<strong>in</strong>ed<br />

less than 200 mg/kg. The highest concentrations<br />

<strong>of</strong> t<strong>in</strong> were found <strong>in</strong> canned sour fruits and vegetables<br />

and products <strong>in</strong> uncoated cans.<br />

r e f e r e n c e s<br />

Chiba M. (1987): <strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> t<strong>in</strong> <strong>in</strong> biological<br />

materials <strong>by</strong> atomic absorption spectrometry with<br />

a graphite furnace. Journal <strong>of</strong> Analytical Toxicology,<br />

11: 125–130.<br />

Commission Regulation (EC) No 1881/2006 <strong>of</strong> 20 December<br />

2006, Sett<strong>in</strong>g maximum levels for certa<strong>in</strong> contam<strong>in</strong>ants<br />

<strong>in</strong> foodstuffs. Official Journal <strong>of</strong> European<br />

Communities L364: 5–24.<br />

Huang X., Zhang W., Han S., Wang X. (1997): <strong>Determ<strong>in</strong>ation</strong><br />

<strong>of</strong> t<strong>in</strong> <strong>in</strong> canned foods <strong>by</strong> UV/visible spectrophotometric<br />

technique us<strong>in</strong>g mixed surfactants.<br />

Talanta, 44: 817–822.<br />

M<strong>in</strong>o Y. (2006): <strong>Determ<strong>in</strong>ation</strong> <strong>of</strong> t<strong>in</strong> canned foods <strong>by</strong><br />

X-Ray fluorescence spectrometry. Journal <strong>of</strong> Health<br />

Science, 52: 67–72.<br />

Perr<strong>in</strong>g L., Basic-Dvorzak M. (2002): <strong>Determ<strong>in</strong>ation</strong><br />

<strong>of</strong> total t<strong>in</strong> <strong>in</strong> canned food us<strong>in</strong>g <strong>in</strong>ductively coupled<br />

plasma atomic emission spectroscopy. Analytical and<br />

Bioanalytical Chemistry, 374: 235–243.<br />

S409

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