Altundag 2011
Altundag 2011
Comparison of dry, wet and microwave digestion methods for the multi
element determination in some dried fruit samples by ICP-OES
Huseyin Altundag a,⇑, Mustafa Tuzen b
a
Sakarya University, Faculty of Science and Arts, Chemistry Department, 54187 Sakarya, Turkey
b
Gaziosmanpasßa University, Faculty of Science and Arts, Chemistry Department, 60250 Tokat, Turkey
a r t i c l e i n f o a b s t r a c t
Article history: The aim of this study was used to investigate the level of trace metals (Ba, Pb, Cd, Mn, Cr, Co, Ni, Cu, Mn,
Received 3 June 2011 Zn, Sr and Fe) in some dried fruits (Prunus domestica L., Ficus carica L., Morus alba L., Vitis vinifera L., Prunus
Accepted 30 July 2011 armeniaca L., and Malus domestica) samples from Turkey. Trace elements were determined by ICP-OES
Available online 6 August 2011
after dry, wet and microwave digestion methods in dried fruit samples. Validation of the proposed
method was carried out by using a NIST-SRM 1515-Apple Leaves certified reference material. Element
Keywords: concentrations in dried fruit samples were 0.33–1.77 (Ba), 0.12–0.54 (Cd), 0.25–1.03 (Co), 0.45–2.30
Dried fruit
(Cr), 0.43–2.74 (Cu), 0.56–4.87 (Mn), 0.61–2.54 (Ni), 0.40–2.14 (Pb), 2.16–6.54 (Zn), 0.83–12.02 (Al),
Dry ashing
Wet ashing
11.82–40.80 (Fe) and 0.16–6.34 (Sr) lg/g. The analytical parameters show that the microwave oven
Microwave digestion digestion procedure provided best results as compared to the wet and dry digestion procedures. The
Trace element results were compared with the literature values.
ICP-OES Ó 2011 Elsevier Ltd. All rights reserved.
0278-6915/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fct.2011.07.064
H. Altundag, M. Tuzen / Food and Chemical Toxicology 49 (2011) 2800–2807 2801
of fruits and vegetables can help replace foods high in saturated prior to use. Aliquots of an ICP multi element standard solution
fats, sugar and salt and thus improve the intake of most micronu- (10 lg/mL) containing the analyzed elements (Ba, Pb, Cd, Mn, Cr,
trients and dietary fiber. However, these foods may contain trace Co, Ni, Cu, Mn, Zn, Sr and Fe) was used in the preparation of calibra-
levels of toxic trace metals such as cadmium, lead, mercury and tion solutions. These solutions were prepared by serial dilution
nickel, so it is important to monitor the levels of these toxic metals with 0.2% (v/v) HNO3 to the required concentrations with UHQ
in these foods (Robards and Worsfold, 1991). water prior to use. For calibration, commercially available standard
Various analytical techniques have been used to quantify met- solutions were used. The ranges of the calibration curves (6 points)
als following in the analysis of heavy metals in plant materials were selected to match the expected concentrations (10–320 lg/L)
and food samples atomic absorption spectrometry (GFAAS, FAAS) for all the elements of the sample studied by ICP-OES.
(Dundar and Altundag, 2004, 2006; Duran et al., 2008), ICP-OES
(Bakircioglu et al., 2011) is reported the most frequently. Elements
2.3. Sampling
such as iron, copper, zinc and manganese are essential elements
since they play an important role in biological systems, whereas
50 g dried fruit samples (Table 3) were acquired from the sellers
lead and cadmium are non-essential elements as they are toxic,
of medicinal herbs in Sakarya, Turkey, in 2010 and were dried
even in traces (Saracoglu et al., 2009).
again for analysis at 105 °C for 24 h. Dried samples were grinded
The present work aimed was to estimate the trace element
and homogenized using an agate homogenizer and stored in poly-
(Ba, Pb, Cd, Mn, Cr, Co, Ni, Cu, Mn, Zn, Sr and Fe) contents of some
ethylene bottles until analysis. The city of Sakarya is in the north-
dried fruits commercially available in Sakarya, Turkey. Trace
west part of Anatolia, Turkey, which is situated close to the biggest
element contents in dried fruit samples were determined by ICP-
and highly industrialized city of Turkey, Istanbul. Its adjacent prov-
OES after dry, wet and microwave digestion methods.
inces are Kocaeli to the west, Bilecik to the South, Bolu to the
southeast and Duzce to the east. The capital of Sakarya is Adapaz-
2. Experimental ari. The weather conditions of the city are characterized as hot and
humid summers and mild and rainy winters. Temperature typi-
2.1. Apparatus cally ranges between 5 and 37 °C.
Table 4
The results of analysis with dry, microwave and wet digestion procedures of NIST SRM 1515 Apple Leaves certified reference material (lg/g), N = 4.
Element Certified value Wet ashing RSD (%) Microwave digestion RSD (%) Dry ashing RSD (%)
Barium 49 ± 2 47 ± 0.4 0.85 48 ± 0.3 0.63 45 ± 0.3 0.67
Cadmium 0.013 ± 0.002 0.045 ± 0.002 4.44 0.040 ± 0.001 2.50 0.033 ± 0.005 15.2
Cobalt (0.09)a 0.11 ± 0.01 9.09 0.07 ± 0.01 14.3 0.08 ± 0.01 12.5
Chromium (0.3)a 0.50 ± 0.02 4.00 0.41 ± 0.02 4.87 0.25 ± 0.02 8.00
Copper 5.64 ± 0.24 5.97 ± 0.18 3.02 5.47 ± 0.23 4.20 5.17 ± 0.12 2.32
Manganese 54 ± 3 52 ± 3.6 6.92 50.0 ± 4.4 8.80 46.0 ± 4.5 9.78
Nickel 0.91 ± 0.12 1.02 ± 0.07 6.86 0.87 ± 0.11 12.6 0.80 ± 0.04 5.00
Lead 0.470 ± 0.024 0.51 ± 0.06 11.8 0.44 ± 0.05 11.4 0.41 ± 0.03 7.32
Zinc 12.5 ± 0.3 12.7 ± 1.7 13.4 13.1 ± 1.9 14.5 11.5 ± 2.2 19.1
Aluminum 286 ± 9 277.0 ± 13.4 4.84 289.0 ± 15.4 5.33 263 ± 12.5 4.75
Iron 83 ± 5 81.0 ± 5.6 6.91 89.0 ± 6.7 7.52 78 ± 4.2 5.38
Strontium 25 ± 2 23.0 ± 3.9 16.9 24.0 ± 4.1 17.1 17 ± 1.6 9.41
a
The values in the parenthesis is not certified.
Element Sample name: yellow plum Element Sample name: yellow plum
2803
2804 H. Altundag, M. Tuzen / Food and Chemical Toxicology 49 (2011) 2800–2807
6.34 ± 2.64
6.01 ± 1.36
5.46 ± 2.19
0.57 ± 0.18
2.46 ± 0.43
2.51 ± 0.24
1.29 ± 0.13
1.02 ± 0.12
1.87 ± 0.21
2.13 ± 0.36
1.92 ± 0.27
0.64 ± 0.12
0.51 ± 0.06
0.42 ± 0.03
2.66 ± 0.30
1.33 ± 0.07
0.43 ± 0.04
0.29 ± 0.03
0.43 ± 0.08
0.32 ± 0.07
0.16 ± 0.02
(Ba), 0.12–0.54 (Cd), 0.25–1.03 (Co), 0.45–2.30 (Cr), 0.43–2.74
Strontium
14.02 ± 4.45
13.98 ± 3.32
12.59 ± 2.42
12.16 ± 1.96
12.29 ± 3.14
37.45 ± 3.78
40.80 ± 5.45
36.17 ± 3.56
40.36 ± 4.19
38.67 ± 3.87
35.57 ± 4.43
28.13 ± 2.12
27.44 ± 2.93
25.68 ± 3.14
20.16 ± 1.13
21.25 ± 2.14
19.47 ± 2.67
14.89 ± 4.7
12.65 ± 3.4
11.82 ± 2.6
The barium value of Ficus carica L. (Fig. 3) was maximum and
the barium value of Vitis vinifera L. was minimum (Fig. 5). In the lit-
Iron
1.14 ± 0.12
2.78 ± 0.18
2.95 ± 0.36
2.86 ± 0.21
1.53 ± 0.08
1.60 ± 0.07
1.03 ± 0.08
0.98 ± 0.08
0.83 ± 0.07
0.96 ± 0.06
1.22 ± 0.09
11.86 ± 4.1
11.61 ± 3.7
12.02 ± 3.0
Aluminum
2.85 ± 0.16
2.16 ± 0.25
6.54 ± 0.45
6.23 ± 0.36
5.90 ± 0.38
4.06 ± 0.28
3.55 ± 0.34
2.79 ± 0.07
3.86 ± 0.30
Anonymous, 2002). The cadmium value of Malus domestica
(Fig. 7) was maximum and the cadmium value of Black plum
Zinc
0.54 ± 0.13
0.48 ± 0.11
0.72 ± 0.12
0.81 ± 0.16
0.91 ± 0.14
0.81 ± 0.11
2.01 ± 0.32
2.14 ± 0.41
0.62 ± 0.17
0.54 ± 0.18
0.68 ± 0.08
0.56 ± 0.08
0.58 ± 0.04
0.41 ± 0.06
0.44 ± 0.05
0.40 ± 0.02
0.77 ± 0.06
0.67 ± 0.08
1.45 ± 0.20
0.67 ± 0.06
ranges of 0.16–0.24 mg/g dry mass in legumes and dried fruit sam-
ples (Yebra and Cancela, 2005), 0.65–1.34 lg/g dry weight in dried
1.13 ± 0.19
0.74 ± 0.16
2.46 ± 0.21
2.54 ± 0.29
2.26 ± 0.31
1.98 ± 0.16
2.12 ± 0.11
2.18 ± 0.35
1.41 ± 0.16
2.13 ± 0.22
1.97 ± 0.32
1.51 ± 0.36
2.05 ± 0.14
1.44 ± 0.19
1.06 ± 0.09
0.95 ± 0.07
0.65 ± 0.07
0.61 ± 0.10
2.34 ± 0.04
2.31 ± 0.09
2.43 ± 0.09
1.52 ± 0.28
1.41 ± 0.16
1.35 ± 0.14
4.36 ± 0.34
4.25 ± 0.23
4.16 ± 0.45
3.23 ± 0.14
3.02 ± 0.31
2.87 ± 0.25
4.65 ± 0.34
4.14 ± 0.21
1.67 ± 0.10
1.29 ± 0.07
4.87 ± 0.40
0.91 ± 0.07
0.73 ± 0.06
0.56 ± 0.04
1.65 ± 0.16
1.49 ± 0.21
1.53 ± 0.14
1.26 ± 0.32
1.23 ± 0.14
2.54 ± 0.14
2.37 ± 0.19
2.17 ± 0.21
2.74 ± 0.36
2.21 ± 0.14
1.88 ± 0.04
2.10 ± 0.07
1.89 ± 0.10
1.28 ± 0.07
1.31 ± 0.09
2.53 ± 0.30
1.13 ± 0.07
0.80 ± 0.04
0.43 ± 0.06
and the cobalt value of F. carica L. was minimum (Fig. 3). In the lit-
Copper
0.89 ± 0.25
0.94 ± 0.26
0.96 ± 0.12
0.58 ± 0.12
0.78 ± 0.12
0.61 ± 0.19
2.30 ± 0.43
2.12 ± 0.23
1.65 ± 0.12
1.16 ± 0.32
0.98 ± 0.21
0.75 ± 0.04
1.16 ± 0.08
1.05 ± 0.07
0.79 ± 0.30
0.65 ± 0.09
0.45 ± 0.02
0.67 ± 0.06
1.36 ± 0.10
Chromium
Trace element contents (lg/g) in dried fruit samples after dry, wet and microwave digestion, N = 3.
0.51 ± 0.12
0.45 ± 0.23
0.50 ± 0.15
1.03 ± 0.21
0.79 ± 0.23
0.78 ± 0.14
0.67 ± 0.19
0.53 ± 0.03
0.59 ± 0.07
0.44 ± 0.06
0.35 ± 0.07
0.33 ± 0.06
0.25 ± 0.08
0.36 ± 0.04
0.43 ± 0.09
0.35 ± 0.07
0.84 ± 0.06
0.51 ± 0.08
1.36 ± 0.15
1.16 ± 0.12
1.28 ± 0.08
1.34 ± 0.09
1.04 ± 0.04
0.66 ± 0.07
1.68 ± 0.20
1.42 ± 0.09
0.54 ± 0.08
0.51 ± 0.06
0.36 ± 0.04
0.54 ± 0.09
0.45 ± 0.07
0.33 ± 0.05
0.91 ± 0.10
0.77 ± 0.07
0.37 ± 0.08
0.91 ± 0.08
needed for each if they are to function properly. The copper value
Barium
Microwave
Microwave
Microwave
Microwave
Microwave
Microwave
Wet
Wet
Wet
Wet
Wet
Wet
Dry
Dry
Dry
Dry
Dry
Dry
Dry
(Sattar et al., 1989), in fruits from the Egyptian markets have been
reported in the range 1.22–18.3 mg/kg (Radwan and Salama,
2006), 1.68–4.52 lg/g dry weight (Duran et al., 2008). The lowest
Prunus armeniaca L.
Black plum
Manganese is one of the vital important elements. Manganese is concentrations of nickel were 2.30 and 5.83 lg/g, respectively (Sar-
both to be in structure of some enzymes and active to some acoglu et al., 2009) and 7.50 mg/kg in apricots of Pakistan (Zahoor
enzymes. The manganese value of P. armeniaca L. (Fig. 6) was et al., 2003).
maximum and the manganese value of M. domestica was minimum Lead is well known for its toxic and adverse effects on human
(Fig. 7). In the present study, manganese contents in samples were health (WHO, 1993). The lead value of P. armeniaca L. (Fig. 6)
below 4.87 lg/g. Manganese levels may also be affected by food was maximum and the lead value of F. carica L. was minimum
processing. Manganese contents in the literature have been re-
ported in the range 2.14–17.23 lg/g dry weight in dried fruits com-
monly consumed in Pakistan (Sattar et al., 1989), 4.74–25.5 lg/g
(Duran et al., 2008). The mean of manganese contents in apricot
samples was 4.68 lg/g (Saracoglu et al., 2009). According to Turk-
ish standards (Anonymous, 2002), there is no information on the
carcinogenicity of manganese. The intake of Mn in our investigated
samples is below the tolerable daily upper limit of 11 mg per day.
The US National Academy of Sciences recommended 2.5–5 mg per
day manganese, and the WHO (World Health Organization) recom-
mended 2–9 mg per day for an adult (WHO, 1994).
The nickel value of F. carica L. (Fig. 3) was maximum and the
nickel value of Black plum was minimum (Fig. 2). Nickel contents
in the literature have been reported in the range of 1.0–8.9 mg/kg
in summer fruits from Pakistan (Zahoor et al., 2003). There is no
information about maximum nickel levels in dried fruits in
Turkish standards. However, the maximum nickel levels in some
food samples are reported as 0.2 mg/kg (Anonymous, 2002),
0.6–9.4 lg/g dry weight in dried fruits commonly consumed in
Kayseri, Turkey (Duran et al., 2008), the minimum and maximum Fig. 3. Amounts of elements in F. carica L.
Acknowledgment Kazi, T.G., Memon, A.R., Afridi, H.I., Jamali, M.K., Arain, M.B., Jalbani, N., Sarfrz, R.A.,
2008. Determination of cadmium in whole blood and scalp hair samples of
Pakistani male lung cancer patients by electro thermal atomic absorption
This work was supported partly by Sakarya University Scientific spectrometer. Sci. Total Environ. 389 (2–3), 270–276.
Research Foundation with Project Number 2010-02-04-015. Memon, A.R., Kazi, T.G., Jamali, M.K., Afridi, H.I., Arain, M.B., Jalbani, N., 2007.
Evaluation of zinc status in biological samples (whole blood and scalp hair) of
female cancer patients. Clin. Chim. Acta 379, 66–70.
Meunier, P.J., Roux, C., et al., 2004. The effects of strontium ranelate on the risk of
References vertebral fracture in women with postmenopausal osteoporosis. N. Engl. J. Med.
350 (5), 459–468.
Aberoumand, A., Deokule, S.S., 2009. Determination of elements profile of some Puglisi, M.J., Mutungi, G., Brun, P.J., McGrane, M.M., Labonte, C., Volek, J.S.,
wild edible plants. Food Anal. Methods 2, 116–119. Fernandez, M.L., 2009. Raisins and walking alter appetite hormones and
Afridi, H.I., Kazi, T.G., Jamali, M.K., Arain, M.B., Jalbani, N., Baig, J.A., 2008. plasma lipids by modifications in lipoprotein metabolism and up-regulation
Distribution of zinc, copper and iron in biological samples of Pakistani of the low-density lipoprotein receptor. Metabolism 58 (1), 120–128.
myocardial infarction (1st, 2nd and 3rd heart attack) patients and controls. Rainey, C.J. et al., 1999. Daily boron intake from the American diet. J. Am. Diet.
Clin. Chim. Acta 389 (1–2), 114–119. Assoc. 335, 40.
Anonymous, Regulation of setting maximum levels for certain contaminants in Radwan, M.A., Salama, A.K., 2006. Market basket survey for some heavy metals in
foodstuffs. 16 October 2002. Official Gazette Issue 24908. Egyptian fruits and vegetables. Food Chem. Toxicol. 44, 1273–1278.
Awad, M.A., Jager, A., Westing, L.M., 2000. Flavonoid and chlorogenic acid levels in Rauha, J.P., Remes, S., Heinonen, M., Hopia, A., Kahkonen, M., Kujalan, T., Pihlaja, K.,
apple fruit: characterization of variation. Sci. Hortic. 83, 249–263. Vuorela, H., Vuorela, P., 2002. Antimicrobial effects of Finnish plant extracts
Bakircioglu, D., Kurtulusß, Y., Ucar, G., 2011. Determination of some traces metal containing flavonoids and other phenolic compounds. Int. J. Food Microbiol. 56,
levels in cheese samples packaged in plastic and tin containers by ICP-OES after 3–12.
dry, wet and microwave digestion. Food Chem. Toxicol. 49, 202–207. Robards, K., Worsfold, P., 1991. Cadmium: toxicology and analysis, a review. Analyst
Commission of the European Communities, 2001. Commission Regulation (EC) No. 116, 549–568.
221/2002 of 6 February 2002 amending regulation (EC) No. 466/2002 setting Rodushkin, I., Engstroem, E., Soerlin, D., Baxter, D., 2008. Levels of inorganic
maximum levels for certain contaminants in foodstuffs. Off. J. Eur. Commun. constituents in raw nuts and seeds on the Swedish market. Sci. Total Environ.
Crews, H.M., 1998. Speciation of trace elements in foods, with special reference to 392 (2–3), 290–304.
cadmium and selenium: is it necessary? Spectrochim. Acta, Part B 53, 213–219. Saracoglu, S., Tuzen, M., Soylak, M., 2009. Evaluation of trace element contents of
Divrikli, U., Horzum, N., Soylak, M., Elci, L., 2006. Trace heavy metal contents of dried apricot samples from Turkey. J. Hazard. Mater. 167, 647–652.
some spices and herbal plants from Western Anatolia-Turkey. Int. J. Food Sci. Sattar, A., Wahid, M., Durrani, S.K., 1989. Concentration of selected heavy metals in
Technol. 41, 712–716. spices, dry fruits and plant nuts. Plant Foods Hum. Nutr. 39, 279–286.
Dundar, M.S., Altundag, H., 2006. Investigation of heavy metal contaminations in Soceanu, A., 2010. Determınation of some trace metal concentrations in imported
the lower Sakarya riverwater and sediments. Environ. Monitor. Assess. 128, fruits by F-AAS and ICP-MS. Environ. Eng. Manage. J. 9 (8), 1039–1044.
177–181. Tuzen, M., Soylak, M., 2005. Trace heavy metal levels in microwave digested honey
Dundar, M.S., Altundag, H., 2004. Selenium content of Turkish hazelnut varieties: samples from Middle Anatolia, Turkey. J. Food Drug Anal. 13 (4), 343–347.
Kara Findik, Tombul and Delisava. J. Food Compos. Anal. 17 (6), 707–712. Yebra, M.C., Cancela, S., 2005. Continuous ultrasound-assisted extraction of
Duran, A., Tuzen, M., Soylak, M., 2008. Trace element levels in some dried fruit cadmium from legumes and dried fruit samples coupled with on-line
samples from Turkey. Int. J. Food Sci. Nutr. 59 (7–8), 581–589. preconcentration flame atomic absorption spectrometry. Anal. Bioanal. Chem.
Grzesik, E.B., Agata Jakó bik-Kolon, A.J., 2008. Leaching of cadmium and lead from 382, 1093–1098.
dried fruits and fruit teas to infusions and decoctions. J. Food Compos. Anal. 21, Ybanez, N., Montoro, R., 1996. Trace element food toxicology: an old and ever-
326–331. growing discipline. Crit. Rev. Food Sci. Nutr. 36 (4), 299–320.
Hakkinen, S., Heinonen, M., Karenlampi, S., Mykkanen, H., Ruuskanen, J., Torronen, Wagner, G.J., 1993. Accumulation of cadmium in crop plants and its consequences
R., 1999. Screening of selected flavonids and phenolic acids in 19 berries. Food to human health. Adv. Agron. 51, 173–212.
Res. Int. 32, 345–353. World Health Organization, 1993. Guide Lines for Drinking water Quality. WHO,
Hui, Y.H., 2006. Handbook of fruits and fruit processing, Blackwell Publishing. Geneva.
Oxford, UK (p. 81). World Health Organization, 1994. Quality Directive of Potable Water, 2nd ed. WHO,
Jamali, M.K., Kazi, T.G., Arain, M.B., Afridi, H.I., Jalbani, N., Kandhro, G.A., Shah, A.Q., Geneva (p. 197).
Baig, J.A., 2009. Heavy metal accumulation in different verities of wheat World Health Organization, Evaluation of certain food additives and contaminants,
(Triticum aestivum L.) grown in soil amended with domestic sewage sludge. J. In: Thirty-third Report of the Joint FAO/WHO Expert Committee on Food
Hazard. Mater. 164 (2–3), 1386–1391. Additives, WHO Technical Report Series, WHO, Geneva, 1989, 776, 26–27.
Karavoltsos, S., Sakellari, A., Dimopoulos, M., Dasenakis, M., Scoullos, M., 2002. WHO, 2003. Diet, Nutrition and the Prevention of Chronic Diseases. WHO, Geneva.
Cadmium content in foodstuffs from the Greek market. Food Additives Contam. Zahoor, A., Jaffar, M., Saqib, M., 2003. Elemental distribution in summer fruits of
19, 954–962. Pakistan. Nutr. Food Sci. 33, 203–207.