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Tin compounds in food – their distribution and determination

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 Potravinarstvo Slovak Journal of Food Sciences

Potravinarstvo Slovak Journal of Food Sciences

vol. 13, 2019, no. 1, p. 369-377
https://doi.org/10.5219/1041
Received: 8 February 2019. Accepted: 12 March 2019.
Available online: 28 May 2019 at www.potravinarstvo.com
© 2019 Potravinarstvo Slovak Journal of Food Sciences, License: CC BY 3.0
ISSN 1337-0960 (online)

TIN COMPOUNDS IN FOOD – THEIR DISTRIBUTION AND DETERMINATION

Miroslav Fišera, Stanislav Kráčmar, Helena Velichová, Lenka Fišerová, Pavla Burešová,
Pavel Tvrzník

ABSTRACT
The aim of this work was optimization of the methods of trace- and ultratrace analysis, such as ICP-OES, ETA-AAS for
charting the resources of individual forms of tin in foodstuffs. Increase of the sensitivity of the method of ICP-OES was
achieved using the techniques of generation of hydrides, which was also optimized. Based on the information available on
the occurrence of the different forms of tin, it appears that many of these organometallic compounds are contained in
marine animals; attention has mainly focused on organisms such as marine fish, crustaceans, molluscs and algae. Tin
compounds of predominantly inorganic origin can be found in foods and beverages which are packed in cans with
a protective tin coating, too. The above mentioned methods have been applied to the analysis of selected beverages with
low content of tin such as Coca Cola, Sprite, Fanta, Gambrinus 10°, PowerKing, and milk in the cans. Furthermore samples
of animal origin as Sardines in oil, and Hunter's salami were examined, too. Prior to the determination of tin, samples need
to be appropriately modified or analysed. Decomposition of the samples was done in the microwave system. Low pressure
ion exchange chromatography with on-line detection of ICP-OES was used for separation of inorganic tin compounds.
Separation of organically bound tin compounds was performed by HPLC on a column of ACE C-18, 3 µm,
15 cm × 1.0 mm with off-line detection by ETA-AAS. All of the above forms of tin compounds can be separated with this
column. Due to the improvement in the detection of organically bounded tin, HPLC with identical ACE C-18 column
coupled online for example with ICP-MS or spectrofluorimetry could be recommended.
Keywords: foods; tin; speciation of organotin; HG-ICP-OES; HPLC-ETA-AAS

INTRODUCTION destruction of pests in agriculture, where it gets into

One of the indicators of the toxicological quality of food agricultural products and from there into the food. Toxic
is the content of toxic mineral compounds. Lead, effects of tin are known, but its use is increasing.
cadmium, mercury and arsenic belong among the most Humans can absorb tin from food, during breathing, and
toxic elements. In higher concentrations trace elements through the skin. Absorption of tin can enter human
such as, tin, chromium, cobalt, copper, molybdenum, organism in the digestive system, thus food control has
nickel, selenium, vanadium, and others may show toxic been emphasized quite intensively recently.
effects. For these elements, the maximum allowed The average content of tin in the Earth's crust is about
quantity, the permissible maximum quantity or special 3.0 mg.kg-1. In nature, tin occurs as the mineral cassiterite
dose are specified in food legislation in the Czech (stannic oxide SnO2,) and as an ingredient in some
Republic. sulphides.
For humans or for other animals, tin is an essential Metal tin is an important component of common alloys
element, but in larger quantities it appears as toxic. Its (bronze). The tinplate cans are made of steel sheets used in
biological importance for humans has not yet been fully the food industry. Consumption of tinplate in food
elucidated; it is assumed that it is indispensable for optimal packaging is still growing and the largest share goes to the
growth and the formation of blood. Tin compounds are production of cans for the distribution of beer and other
primarily located in the Earth's crust and also due to the beverages (Greenwood and Earnshaw, 1993).
human activities in the air and water flow. A large quantity of tin is consumed for the production of
The most dangerous form of tin are the compounds organometallic compounds. Tin is used as a component of
where tin is organically bounded in organometallic special paints for ships and other bodies subjected to the
compounds. In spite of its potential toxicity, tin is used in long-term effects of the sea water. Tributyltin compounds
large quantities in plastic and canning industry and for are used for the preservation of wood. Tributyltin oxide

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 Potravinarstvo Slovak Journal of Food Sciences
O(SnBu3)2 is an excellent agent for protection of the wood. Tin cans contain mainly canned vegetables, fruits, juices
R3SnX is also used as an antimicrobial agent to and other beverages, fruits in sweet pickle, mixed fruits in
exterminate of slime mould in the paper and pulp. brine, canned milk and pickled mushrooms (Figure1).
Triphenyltinacetate and triphenyltinhydroxide are applied For the determination of trace elements as well as for
in agriculture as fungicides. For example, Bu2SnOH and detection of tin in foodstuffs, it is necessary to choose the
Ph3SnOAc inhibit the growth of fungi, such as potato analytical methods, which are able to detect very low,
blight and similar infections, in sugar beet, peanuts and trace amounts of analyte. Atomic Spectrometry methods –
rice. Tin also serves as a mite-killer on apple and pear atomic absorption, emission and mass spectrometry are
trees. Other R3SnX compounds are effective at killing suggested for analyses of tin in food.
insects as chemosterilant or by killing of larves (Velíšek, The most common method is atomic absorption
1999). spectrometry (AAS). When you use flame atomization the
Dibutyldilaurate and analogue octyltin compounds are limit of detection is on the level of 0.1 mg.L-1; using the
used as stabilizers for plastics (PVC). The most effective electrothermal atomization even decreases this limit.
stabilizer compounds (R2SnX2 – R = octyl-, X = laurate, Additional options for the determination are represented
maleate). For the packaging of food products, the by different extractants (e.g. with hexane, toluene,
polymeric cis-butenedioic and (Oct2SnOCOCH = chloroform r methanol), conversion of the compounds into
CHCOO)n and Oct2Sn(SCH2COO Oct)2, with S,S´-bis volatile derivatives (by reaction with Grignard´s reagents
(isooctyl-mercaptoethanolate), which is used in cases or reaction with NaBH4 result in volatile hydrides usable
where a colorless, non-toxic, highly transparent material is for atomic absorption spectrometry determination) and
essential, were approved. separation by gas chromatography. It is also possible to
Another no less important application of organotin use liquid chromatography with mass spectrometer with
compounds is their use as curing agents in vulcanization of ICP (inductively coupled plasma).
silicone under normal temperature (Greenwood and These methods offer for many elements excellent limit of
Earnshaw, 1993). detection, so they are suitable for the determination of
On other hand, the inorganic forms of tin are less toxic trace amounts of elements in biological materials.
for human organism. Inorganic tin is just difficult to be Comparable results are achieved using sensitive
absorbed by the organism and is usually excreted in the electroanalytical methods, mainly a modification of
urine. According to the study from 1997, tin (II) is more polarography and voltamperometry, electrogravimetry or
toxic than tin (IV). Due to the presence of humic acids in fluorescence.
the ground waters that reduce tin (IV) on tin (II) its For the determination of organically bounded forms of
concentration is increasing (Pawlik-Skowronska, tin, in particular of tributyltin compounds (including
Kaczorowska and Skowronski, 1997; Rüdel, 2003). degradation products – di- and monobutyl derivatives) are
Inorganic tin is not carcinogenic or teratogenic. also used the above methods (AAS, ICP-OES and ICP-
Tin in all organic industrial compounds is tetravalent. MS), in connection with sepraing in on-line or off-line
Organic alkyl or aryl groups are groups that are covalently arrangement (Figure 4).
bonded with the central atom of tin. Mono-, di- and To determine total tin detection of different forms
trisubstituted butyltin, phenyltin, and their derivatives are (separation of inorganic and organically bound forms of
considered its most important compounds. The solubility tin) is performed both via complete mineralization of
of organically bounded tin compounds depends on pH, samples and in dry (combustion and subsequent
ionic strength and temperature of environment. dissolution in acid) or wet way (oxidation reactions in the
Degradation of organotin compounds occurs in biotic or strongly acidic environment). Mineralization by the wet
abiotic processes. The transformation is similar for both way can be further performed under the hood in an open or
cases (Rüdel, 2003) it leads through the dealkylation or closed system. Mineralization in a closed system can be
dearylation on inorganic tin compounds (Hoch, 2001). done under high or low pressure and either common or
The European Union (EU) limits maximum levels for
certain contaminants with a view to reduce the content of
these substances in foods at such a low level, which is yet
to be achieved in compliance with the good manufacturing
or agricultural practices. The aim is to achieve a high level
of public health protection, especially for vulnerable
groups of the population: children, allergies, etc.
(Commission Regulation (EC), 2006).
Tin gets into tinned food via further decomposition of the
inner walls of tinned food cans. The decomposition of
tinplate is dependent on the food matrix, pH, the presence
of oxidizing substances (anthocyanines, nitrates, ions of
iron and copper), and the presence of air (oxygen) in the
area of food, time and storage temperature.
Nowadays, corrosion and dissolution of tin cans will be
suppressed by a varnish, which greatly reduces the Figure 1 The most frequently observed types of
penetration of tin in food products. canned food on the tin content (Perring and Basic-
Dvorzak, 2002).

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microwave heating can be employed (Mader and External calibration was prepared from stock solution of
Čurdová, 1997). tin of 1000 mg.L−1 (Astasol®). Also, 1000 mg.L−1 stock
If the determination of the different forms of tin is solutions organotin compounds were prepared from
required, treatment of samples keeping tin compounds in dibutyltin dichloride (97%), triphenyltin chloride (95%)
their original form is essential and also maintaining their and tributyltin chloride (95%), Sigma – Aldrich s.r.o. CR
initial relationship in the sample is crucial. For these and diluted according to the working range required. The
purposes very gentle procedures must be employed. They calibration curves were prepared in a suitable range of
are based on the extraction with helping of ultrasonic wave concentrations in accordance with the purpose.
or with the support of many microwaves in pH buffered Other reagents such as sodium tetrahydridoborate
environments. If the separation or isolation of the NaBH4, NaOH, KOH for hydride generation used and
individual forms in one step is impossible, it is necessary organic solvents and acids (methanol, acetonitrile, acetic
to use a multi-step extraction or specific extraction or the acid and triethanolamine) were HPLC grade from Sigma –
conversion of other forms, and then multi-step analysis Aldrich s.r.o. CR.
must be carried out (Simon et al., 2002). The glassware used in the experiments was previously
decontaminated with a nitric acid solution (10% v/v) for
Scientific hypothesis 24 h (Dantas et al., 2013), subsequently washed with
Since the determination of the tin compounds in foods is ultrapure water and dried at room temperature.
of great importance, particularly in terms of the occurrence
of organotin compounds that accumulate in human adipose Instrumentation
tissue, many techniques have been used for this purpose. For the analysis of the food samples an inductively
Studies using different techniques, such as graphite coupled plasma optical emission spectrometer with axial
furnace atomic absorption spectrometry (GF AAS) and view (ICP-OES, Thermo Jarrell Ash, IRIS/AP,USA) and
cold vapour atomic absorption spectrometry (CV AAS), an atomic absorption spectrometer with electrothermal
have been reported. atomisation (Thermo Elemental, Solaar M6, UK) were
The inductively coupled plasma optical emission used, and the operating conditions are detailed in Table 1
spectrometry (ICP-OES), which makes it possible and Table 2. For preparation of samples for total tin
simultaneous determinations on more different wavelength content analyses a microwave digestion system MLS 1200,
and allows rapid an effective analysis, is also reported. The Milestone it was used and for separation of organotin
design of experiments is an important approach and has forms an HPLC system (Dionex RS 3000 Ultimate, USA)
been successfully employed in sample preparation was used.
procedures to identify the optimum conditions and select
the proportions between the reactants, allowing a faster Optimization strategy and analysis of the data
acquiring of results, minimizing costs and time involved. In order to achieve the best working conditions providing
The use of diluted reagents in decomposition or extraction the lowest detection limit were performed an optimization,
procedures, which leads to media with reduced acidity and which includes the choice of the best wavelength for tin
also decreases the amount of corrosive substances, is an and appropriate instrument settings. Sensitive wavelengths
example of the experimental design application. for tin have been selected from a database of TEVA TM
Chemometric tools were used to establish the appropriate (Thermo Elemental Validated Analysis, ICP-OES
experimental conditions for determination of total tin software, v. 1.4.0. for controls the optical emission
content by CV AAS or by hydride generation atomic spectrometer with inductively coupled plasma). It was
emission spectrometry with inductive coupled plasma (HG tested a total of six wavelengths, which is able for the tin
ICP-OES) and combination of separation step (EC or determination. Of these six wavelengths were chosen two
HPLC) with the same methods of detection for (Table 2), which was the signal for tin the best response
determination of tin (II) and tin (IV) and organotin (SBR).
compounds in biological samples. Other parameters were setting the input of the plasma on
Thus, this paper purpose is a multivariate optimization of 1150 W, auxiliary gas flow 1 L.min-1, the uptake of the
an analytical method through all parameters outside the sample to the nebulizer 1.85 mL.min-1.
device parameters conclude selection the most suitable
wavelength, concentrations of reagent solutions, correction Statistic analysis
of interferences and inlet flows of gases and solutions to Validation of analytical method
determine the individual species of tin employing ICP- The precision of the method was evaluated via the
OES. repeatability and can be expressed as the relative standard
deviation (RSD) of a set of measurements. Accuracy
MATERIAL AND METHODOLOGY expresses the difference between the value found
Material and reagents experimentally and a reference value. In this study, Trace
All reagents used were analytical grade, and solutions elements in CRM material fish tissue (NIES-11) was used
were prepared with ultrapure deionized water obtained to establish the accuracy through the values calculated
from a reverse osmosis water purification system and using the Eq. (1). This approach is directly related to
ultrapure system (Aqua Osmotic 02 Tisnov, CR and international standards.
Purelab ULTRA, Elga, UK). The nitric acid (68%),
hydrochloric acid (37%) and hydrogen peroxide (31%) Recovery (%) = [found value/certified value] x 100 (1)
used were of Analpure Ultra (Analytika, s.r.o., CR).

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 Potravinarstvo Slovak Journal of Food Sciences
Where found value is the analyte concentration expressed only at this wavelength. The results of the
determined by the proposed method and the certified value optimization steps with a concentration of 100.0 ppb tin
is the concentration value of the analyte reported in the are presented in Table 3 and Table 4.
SRM certification document. The precision and accuracy
expressed as RSD (%) and recovery (%), respectively, Calibration of hydride technique for the determination of
obtained for the optimized analytical method calculated on different form of tin
the certified values and the found values for CRM. The The calibration solutions of standards of different forms
recovery between the certified values and the found values of tin were measured at wavelengths 189.989 and
ranged from (87.0 ±1.0) % (for tributyl tin) and about 242.949 nm. The concentration of the calibration solutions
(92.0 ±5.0) % for total tin content, and the RSD values was selected 50; 100; 150 µg.L-1 and as blank was used
obtained were better than 5% (n = 3). a 0.25 M solution of HCl. The calibration solutions of Sn
The tin content in different samples of foods was (IV) species were prepared from standard calibration
measured by HG-ICP-OES. Samples before the solution 1.0 g.L-1 in 0.25 M of HCl solution into the
determination were decomposed in the microwave device 100 mL flasks. Calibration solutions of Sn (II) were
by mineralization step. As samples were selected common prepared by loading the appropriate amount of
beverages: Coca Cola, Sprite, Fanta, Gambrinus 10°, SnCl2.2H2O. This amount was transferred to 100 mL
PowerKing and picnic in the cans. It was also determined volumetric flask and fill up with deionised water. From
a total content of the tin in caned Sardines in vegetable oil this stock solutions have been further prepared calibration
and in the hunter salami as a potential possible source of solutions of the above concentration.
organotin compounds.
Samples of drinks before mineralisation step in the Evaluation of the operating conditions obtained for the
ultrasonic bath were degassed. For the decomposition of ICP-OES
samples of beverages and foodstuffs was take up 10 mL or This procedure made it possible to select the more
1.0 g of samples and added 8 ml of HNO3 and 2 mL of sensitive lines, free of interference (Table 1), that were
HCl. After this operation the sample was evaporated to used to calculate the limits of detection (LOD) and the
near dryness, almost added to it 1 mL of HCl and volume limits of quantification (LOQ) through the background
was fill up on 10 mL. Values measured during both the equivalent concentration (BEC) and the signal-to-
wavelengths used are listed in Table 8. background ratio (SBR). The LOD and LOQ values were
The analysis of the data obtained from the experimental calculated using the BEC and the SBR, according to
design was performed using Statistica® 12.0 software International Union of Pure and Applied Chemistry
(StatSoft, USA). The measurements were performed in (IUPAC); BEC = Cstandard / SBR, where SBR = (Istandard −
triplicate and the data are expressed as mean ±95% Iblank) / Iblank; Cstandard is the reference element
confidence interval (CI). concentration in the solution; and Istandard and Iblank are
the emission intensities for the reference element and
RESULTS AND DISCUSSION blank solutions, respectively at the selected wavelength
Optimization of the hydride technique (Da Costa et al., 2013, Schiavo et al., 2009).
The hydride generation technique was used for the The LOD was then calculated as (3 × RSD blank × BEC /
reduction of the limit of detection. This technique based on 100) and the LOQ as (3.3 × LOD), where RSDblank is the
reaction of NaBH4 with acid to produce hydrogen, which relative standard deviation of ten measurements of the
generate volatile hydride with suitable ions of metal. These emission intensity of the blank solution.
ions are then carried into the carrier gas stream into
discharge of the ICP. If we compare the direct method of Separation of inorganic forms of tin by ICP-OES method
measuring tin and the hydride generation technique we can Ion-exchange chromatography
change measurement extent from the range ppm (mg.L-1) Forms of tin were separated by ion-exchange
to ppb (µg.L-1) levels. The optimization of the chromatography with on-line detection of ICP-OES. The
concentration of sodium tetrahydroborate for the hydride measurement was done by using the time scan module in
generation for the correct determination was performed. the TEVA software. Before choosing a suitable sorbet is
Optimization of the concentration range NaBH4 was necessary to find out as much as possible information
selected on the literature (Hosick, Ingamells and about samples, which considered the properties of the
Machemer, 2002) where the optimum of concentration matrix and the analyte, and based on this knowledge, then
was about 2.4% of NaBH4. Therefore, the optimization of choose the type of phase and size of columns. Offer of
reducing reagents at concentrations of 0.5; 1; 1.5; 2; 2.5; 3; sorbents is similar as for filling for liquid chromatography.
3.5; 4; 5% of the NaBH4 dissolved in 0.1% KOH was All sorbents, which were used, had to be activated at first.
performed. Activated sorbents under reduced pressure using the
Similarly for the acidification of the samples has been sorption apparatus were implemented in polypropylene
used 0.10; 0.25; 0.50; 0.75; 1.0 M hydrochloric acid. columns. After filling the columns were washed up with
As the most sensitive appeared wavelength of tin deionised water.
189.989 nm (with the highest ratio of intensities (IR), Tin in the compounds occurs in the form cations Sn (II)
which is the ratio of full intensity to the intensity of and Sn (IV). Therefore ion changers were selected as
background or blank on the same selected wavelength), cation exchangers. The most appropriate cation exchanger
therefore the final optimization was carried out and the is like this the tin ions are relatively closely retained and
final results of processing of the content of tin was they are not washed up with water. Another important
parameter is the selection of appropriate eluent reagents.

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 Potravinarstvo Slovak Journal of Food Sciences
Due to the stability of the plasma is not appropriate use of According to literature (Chen et al., 1996), where it was
elution agents containing higher amount of organic performed by optimizing the working conditions for the
compounds or high concentrations of salts. determination of Sn by ETA AAS method. For
In work were tested exchangers Amberlite IRC 50, background correction a Zeeman correction method has
Cellulose CM 23, Servacel CM 3, Dowex 50WX, been selected and as matrix modifier a combination of
Trisacryl M CM and Sephadex CM 50 with elution Palladium and Ascorbic acid was used. The unit was
reagents 1 M HCl and 0,5 M NaOH. The most of them - setting to the basic working conditions recommended by
Amberlite IRC 50, Cellulose CM 23, Trisacryl M CM and the manufacturer (Table 6 and Table 7).
Sephadex CM 50 – were suitable for separation of Sn (IV).
Perfect separation of Sn (II) and Sn (IV) ions is Application of optimized method to food samples
complicated how is describe in literature (White et al., After settinµ the optimal conditions a calibration method
1998) that the solutions of salts of Sn (II) ions are very for different forms of tin was performed. Calibration
unstable, easily oxidized by air and especially on light. solutions were measured at a wavelength of 224.6 nm with
Therefore, the study was focused on time dependency of calibration functions y = 0.0073x + 0.0502 and
Sn (IV) conversion on Sn (II) species on the light. In the R² = 0.9977 for tributyltin chloride; y = 0.006x + 0.0524
previous chapter, it was found that when using a column and R² = 0.9975 for dibutyltin dichloride and
filled with exchanger Amberlite IRC 50, tin in the form Sn y = 0.004x + 0.0457, R² = 0.9962 for triphenyltin chloride.
(II) is washed out at the sampling and Sn (IV) is retained The concentration of the calibration solutions 10, 30,
on the exchanger and washed out with 1 M HCl. This 50 µg.L-1 has been prepared. A solution of 50 µg.L-1 of
phenomenon was used for determining the time conversion different forms of tin with the addition of 0.5 ml 65%
dependency Sn (II) on Sn (IV) species. The functional HNO3 into a 50 ml volumetric flask and added a mixture
range of the pH for ion exchanger which was used of MeOH: H2O (40: 10) has been prepared from standard
Amberlite IRC 50 is 5-14, in order to the pH of the sample solutions (Schiavo et al., 2009). As blank and dilution
is not need regulate. Results of measuring dependences of solution 0.65% HNO3 has been used. As a matrix modifier
peak areas on time in derivation and logarithmical modes a solution of Pd(NO3)2 and 1% solution of ascorbic acid
are shown in Table 5 and Figures 2 and 3. were used. This mixture with sample by autosampler was
sampled to the ELC of ETA AAS.
Determination of tin compounds by ETA–AAS method Due to the improvement of the detection of organically
Optimization of method bound tin and streamlining of analysis would be suitable
For the determination of tin in samples by electrothermal HPLC with column ACE C-18 connect in on-line
atomisation in graphite furnace an ELC (Extended Life arrangement, for example with ICP-MS or fluorimeter
Cuvette) and Sn hollow cathode lamp has been used. (Gonzáles-Toledo et al., 2001).

Table 1 Characteristics and operating conditions used for analysis by ICP-OES with axial view.
Parameter Characteristics
Radio frequency power (W) 1150
Plasma gas flow rate (L.min−1) 15.0
Auxiliary gas flow rate (L.min−1) 1.5
Sample uptake rate (mL.min−1) 1.85
Nebulizer gas flow rate (L.min−1) 1.00
Nebulizer type Concentric
Spray chamber Type cyclone
Replicates 3
Injector tube diameter (mm) 2.0
Signal integration time (s) 1.0
Wavelength (nm) Tin 189.989
242.949

Table 2 Wavelengths suitable for determination of tin.

Wavelength  [nm] Spectral order relative intensity
189.989 136 150,000
242.949 107 100,000

Table 3 Values obtained for BEC, LOD and LOQ in the analysis of liquid samples of beverages by ICP-OESa.
Analytical Sn(II) 189.989 nm Sn(IV) 242.949 nm Sn(II) 189.989 nm Sn(IV) 242.949 nm
parameter Direct method Direct method Hydride generation Hydride generation
BEC (mg.L−1) 0.2185 0.9422 0.0298 0.0967
LOD (mg.L−1) 0.0036 0.0232 0.0006 0.0011
LOQ (mg.L−1) 0.0107 0.0697 0.0017 0.0033
Note: a For solid samples values of LOD and LQD is necessary multiplied with factor for mass of 1.00 g of samples
and completed to 10.0 mL with deionised water and expressed in mg.kg-1.

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Table 4 Dependency of intensity ratios (IR) on the concentration of NaBH4 in the solution.
% NaBH4 IR % RSD
0.5 13.57 0.6973
1.0 32.95 0.8726
1.5 49.96 0.8841
2.0 64.77 1.3630
2.5 80.50 0.7996
3.0 90.37 0.6808
3.5 78.21 0.7758
4.0 73.77 1.6490
5.0 18.40 5.5600

Table 5 Dependence of the peak area at the time by ICP-OES method in time scan model.
Peak area
t [s] Sn (II) Sn (IV)
20 6659.5 10211.0
420 2929.5 13678.0
780 1720.5 14204.0
1140 620.5 15217.0
1560 417.0 15450.0
1920 145.5 16006.5

Table 6 Working conditions for determination of tin by ETA-AAS method.

Parameter Setting
Wavelength 224.6 nm
Background correction Zeeman effect
Time of measurement 3s
Slit 0.5 nm
HCL current 75% Imax

Table 7 Temperature – time programme for ETA AAS.

Phase Temperature Time Flow of Ar
Ramp [ºC.s-1]
[ºC] [s] [L.min-1]
1 100 30 10 0.2
2 120 10 50 0.2
3 800 20 150 0.2
4 2300 3 0 0
5 2600 3 0 0.2

Table 8 Content of tin in food samples obtained HG-ICP-OES method.

c [mg.L-1]
Sample 189.989 nm
Coca Cola 0.1766 ±0.0629
Sprite 0.0903 ±0.1159
Fanta 0.0275 ±0.0390
Gambrinus 10° − beer 0.0360 ±0.0100
PowerKing 0.0227 ±0.0015
Piknik 0.3758 ±0.0078
Sardines in vegetable oil 1.0791 ±0.0892
Hunter salami 0.7016 ±0.1250

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Figure 2 Time dependence of conversion Sn (II) on Sn (IV) – time scan model.

Sn II
Sn(II)
16000
SnIV
SnIV

14000 y = 1230.3ln(x) + 6412.2

R² = 0.9868
12000

10000
Peak area

8000

6000

4000
y = -1445ln(x) + 11152
R² = 0.9846
2000

0
0 500 1000 1500 2000
t [s]
Figure 3 Logarithmical dependence of conversion of Sn (II) on Sn (IV).

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Dibutyltin dichloride Triphenyltin chloride Tributyltin chloride

0.36

0.33

0.3

0.27

0.24
Absorbance

0.21

0.18

0.15

0.12

0.09

0.06
15 30 45 60 75 90 105 120 135 150 165 180 195 210 225 240 255 270 285 300 315 330 345
t [s]

Figure 4 Dependence of absorbance on time for the separation of organotin compounds in the mixture by off-line ETA-
AAS method.

CONCLUSION occurrence of the forms of tin, it appears that many of

In this work were simultaneously developed and tuned these organometallic compounds are contained in marine
the three parts of the methodology on the determination of animals, attention was necessary mainly focused on
different forms of tin in food and beverages. The method organisms such as marine fish, crustaceans, molluscs and
for determination of total tin content in food materials by algae. Based on these findings and the results of this work
ICP-OES has been tuned. Increase the sensitivity of the on the optimization of analytical procedures and the
method of ICP-OES was achieved using the techniques of preparation of samples for analysis (homogenization, the
generation of hydrides, which was also optimized. Hydride selection of reagents and techniques for the extraction of
generation technique reduces the limit of detection, so it individual forms, other modifications, such as pH
can be used for samples with low content of tin. This adjustment, adding specific reagents, etc.) it will be
method has been applied to the analysis of real samples. possible to measure samples of the food and beverages by
Selected samples with low content of tin were drinks Coca using this methodology that are created and optimized for
Cola, Sprite, Fanta, Gambrinus 10°, PowerKing and picnic the determination of the different forms of tin.
in the cans. Furthermore, Sardines in vegetable oil, and
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