European International Journal of Science and Technology
Vol. 6 No. 3
April 2017
HEAVY METALS AND TRACE ELEMENTS CONTENT OF DIFFERENT PROPOLIS TYPES
Nuray ŞAHİNLER1, Aziz GÜL2 and Suat ŞAHİNLER3
1
Usak University, Faculty of Agriculture and Naturel Science, UŞAK, TURKEY Email:
[email protected] 2 Mustafa Kemal University, Faculty of Agriculture, HATAY, TURKEY Email:
[email protected] 3 Usak University, Faculty of Economics and Administrative Sciences, UŞAK, TURKEY Email:
[email protected]
Corresponding author: Nuray ŞAHİNLER Usak University, Faculty of Agriculture and Naturel Science, UŞAK, TURKEY Email:
[email protected]
Abstract In this research, trace elements and heavy metal contents of propolis samples, which were collected from different regions and different botanical origin in Turkey were evaluated. The presence of Al, Ba, Cd, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb and Zn, Ca were determined with ICP AES. The highest value of Cu, Fe, K contents were found in propolis samples collected from Samsun Provinces in Black See Region with a levels of 7.38,5.15, 1570.19, mg kg–1 respectively. The highest level of Cr, Al, Mg (4.34, 791.86, 663.66 mg kg –1) were found in propolis samples collected from Erzurum provinces in East Anatolia Region. The highest level of Ba, Na, Ca were determined in propolis samples collected from Konya in Central Anatolia Region with a level of 223.07, 268.73 and 3263 mg kg –1 respectively. Key Words: Propolis / Heavy Metals / Minerals 21
European International Journal of Science and Technology
ISSN: 2304-9693
www.eijst.org.uk
1. Introduction Propolis is a mixture of various amounts of bees wax and resins collected by the honeybee from plants, particularly from flowers and leaf buds. Since it is difficult to observe bees on their foraging trips the exact sources of the resins are usually not known. Bees have been observed scraping the protective resins of flower and leaf buds with their mandibles and then carrying them to the hive like pollen pellets on their hind legs and bring them back to the hive to cover the cracks and crevices, reduce the hive entrance and coat the large insects like moths, butterfly, beetles, cicadas etc. (Greenaway, 1990; Ghisalberti, 1979; Sahinler and Kaftanoğlu,2005). Anatolia is an enormous geographical area, which fit snugly into each other the two most important gene center among the subtropical countries in terms of plant diversity (Lieberman and Bruning, 1990; Davis, 1965, 1988; Asmaz, 1992; Gemici and Şık, 1992; Kence, 1992). There have been over 10.000 plant species endemic to Anatolia. This study was conducted to determine, the trace elements and the heavy metals contents in propolis samples produced different geographical regions in Turkey. 2. Material and Methods 2.1. Propolis samples The propolis samples, which were freshly harvested were picked up from various beekeepers in 6 geographic region (Table 1). The original samples were collected between 2005 and 2006. The samples were analyzed immediately after collected. Table 1. Botanical and Geographical Origin and Number of Propolis Samples. Region Mediterranean Region East Anatolia Region Black See Region Marmara Region Aegean Central Anatolia Total 6 region of Turkey
City Hatay, Maraş Malatya, Sivas, Erzurum, Tunceli Samsun, Gümüşhane, Kastamonu Kocaeli Bursa Çanakkale Aydın, İzmir, Muğla Kayseri, Konya, Ankara 18 Provinces
Number of Samples 2 4 3 3 3 3 18 samples
2.2. Determination of Trace element and Heavy Metals Approximately 1 g samples were placed into microwave tubes with 10 ml nitric acid and solved by microwave at 190 ºC. After, solvent completed to 25 ml with deionize water and filtered. ICP-AES (Varian Model- Liberty series II) was used to determine the elements which Al, Mg, Cu, K, Ba, Mn, Fe, P, Ca, Na, Co, Cd, Ni, Sn, Pb, Zn. Macro and trace element concentrations were calculated in mg kg –1 on wet weight basis. Macro and trace element concentrations and wavelength are given below. Measurement of wavelengths are Al (396,152 nm), Mg (279,533 nm), Cu (324,754 nm), K(766,49 nm), Ba (455,403 nm), Mn (257,61 nm), Fe (259,94 nm), P (213,618 nm), Ca (317,933 nm), Na (588,995 nm), Co (238,892 nm), Cd (228,802 nm), Ni (231,604 nm), Sn (189,926 nm), Pb (220,353 nm), Zn (213,856 nm). Operational Parameters for ICP AES as fallow: Power: 650 V, Rinse Time: 10 s, Plasma gas flow rate l/min: 15, Auxiliary Flow lmin-1: 1.5, Sample up take delay : 30 sec. 22
European International Journal of Science and Technology
Vol. 6 No. 3
April 2017
2.4. Statistical Analysis Data were analyzed by using ANOVA and MANOVA of SPSS univariate and multivariate statistical analysis of variance methods software (Tabachnick and Fidell, 1996; Sahinler et al., 2005). Means were compared using Duncan Multiple Range Test. 3. Results and Discussions 3.1. Results 3.1. Results of trace and macro element contents in different honey types Trace and Macro element contents of 18 propolis samples collected from different regions are given in Table 1.
Table 2. The Means And Standard Errors Of Means ( x S.E.) For Each Elements In Propolis Samples According To Region. Regions Minerals Ba Cd Cr Cu Mn Na Ni Pb Zn Al Ca Fe K Mg
Mediterranean East Anatolia Black See Region Region Region 2.39±0.34 a 3.31±1.80 a 94.82±56.67 b 0.03±0.00 a 0.06±0.02 a 0.06±0.01 a 3.66±0.12 a 2.29±0.90 a 1.42±0.44 a 4.60±0.51 a 3.06±0.61 a 4.12±1.63 a 4.97±0.55 a 8.10±1.53 a 5.70±0.72 a 86.27±2.08 a 56.28±21.58 a 47.47±16.36 a 4.24±1.25 a 36.99±28.43 a 37.08±12.87 a 0.98±0.16 a 0.84±0.21 a 1.19±0.28 a 25.72±2.45 a 18.71±9.11 a 14.06±4.64 a 454.14±27.92 a 323.81±183.77 a 111.88±32.33 a 2078.44±454.39 1225.69±166.89 948.90±136.95 a bc ab 1.75±0.11 a 1.74±0.26 a 2.82±1.17 a 944.40±238.16 a 799.67±160.74 a 1087.28±336.21 a 462.09±57.93 a 384.97±114.06 a 297.94±4.92 a
Marmara Region 27.66±15.59 ab 0.05±0.02 a 1.40±1.09 a 2.62±0.45 a 16.76±8.96 a 66.04±32.01 a 10.26±2.95 a 2.36±2.04 a 19.61±5.12 a 73.55±10.80 a
Aegean Central Anatolia Region Region 7.68±0.69 a 193.11±34.10 c 0.13±0.09 a 0.06±0.02 a 2.04±0.71 a 1.13±0.02 a 3.74±1.21 a 3.99±0.82 a 11.26±2.89 a 10.89±0.18 a 45.55±9.28 a 139.65±66.23 a 7.03±2.55 a 11.60±4.73 a 2.49±2.02 a 1.34±0.29 a 17.27±9.46 a 35.67±5.94 a 351.59±48.30 a 244.05±70.50 a 1229.07±115.86 192.82±217.19 ab 2356.35±94.44 c ab 2.80±0.43 a 3.09±0.53 a 2.30±0.47 a 957.69±137.75 a 555.57±131.86 a 914.74±236.03 a 383.08±49.45 a 363.07±16.10 a 382.10±18.34 a
Mean (ppm) 54.83±18.20 0.07±0.03 1.99±0.55 3.69±0.87 9.61±2.47 73.54±24.59 17.87±8.80 1.53±0.83 21.84±6.12 259.84±62.27 1505.21±264.29 2.42±0.49 876.56±206.79 378.88±43.47
Regarding to the geographical origin of this propolis groups, Mediterranean samples contained high levels of Al, Cu, Cr, and Mg (454.11, 4.60, 3.66, 462,09 mg kg-1); Central Anatolia Region have higher level of Ba, Na, Zn and Ca (193.11, 139.65, 35.67, 2356.35 mg kg-1); Aegean Region have higher level of Cd, Pb, Fe (0.13, 2.49, 3.09 mg kg-1); Black see Region have higher level of Ni and K (37.08, 1087.28 mg kg-1); Marmara Region have higher level of Mn (16.76 mg kg-1). The lowest value minerals and heavy metal content were found in Propolis samples collected from East Anatolia Region and Marmara Region respectively Table 2. The Ba content was found between 193.11 mg kg-1 (in Central Anatolia samples)- 2.39 mg kg1 (in Mediterranean samples); The highest level of Cd was found in samples collected from Mediterranean samples. The content of Cr changed between 3.66 mg kg-1 (in Mediterranean samples) - 1.13 mg kg-1 (in Aegean samples). The highest level of Cu was found in (4.60 13 mg kg-1) Mediterranean samples and also lowest level (2.6213 mg kg-1 )in Marmara Region. The Mn level was found between 16.76 mg kg-1 (in Marmara region)- 4.97 mg kg-1 (in Mediterranean Region). The highest level of Na was found in samples collected from Central Region. The highest value of Cu, Fe, K contents were found in propolis samples collected from Samsun Provinces in Black See Region with a levels of 7.38,5.15, 1570.19, mg kg–1 respectively. The highest level of Cr, Al, Mg (4.34, 791.86, 663.66 mg kg –1) were found in propolis samples collected from 23
European International Journal of Science and Technology
ISSN: 2304-9693
www.eijst.org.uk
Erzurum provinces in East Anatolia Region. The highest level of Ba, Na, Ca were determined in propolis samples collected from Konya in Central Anatolia Region with a level of 223.07, 268.73 and 3263 mg kg –1 respectively. 4. Discussion The average levels of Na, K, Ca, Mg, N, Cu and Zn of propolis samples originating from different geographic locations of Turkey were investigated by Doğan et al (2006). They reported that Sodium was the most abundant element in the samples. The Calcium level was found between 0.1180.0793 mg g (-1). The highest magnesium content was found in samples from Yozgat region, whereas the lowest was in those of Adana region. Potassium content changed between 0.121-0.364 mg g (-1). The copper and zinc content changed between 0.045-0.096 mg g (-1), 0.176-0.676 mg g (-1), respectively. The Ca was the most abundant element in this research also Copper and Zinc content were higher than previous research. Finally mineral content of Turkish propolis was generally within safe limits. 6. References Asmaz H. (1992) Biyolojik zenginliklerimiz ve koruma stratejisi. Tarım ve Köy. Tarım ve Köyişleri Bakanlığı Dergisi, 74, 7–10. Davis P.H. (1965) Flora of Turkey and East Aegean Islands, 1–10. Davis P.H. (1988) Flora of Turkey and East Aegean Islands, 1–10. Dogan M., Silici S., Saraymen R., İlhan I.O. (2006) Element content of propolis from different regions of Turkey. Acta Alimentaria 35 (1): 127-130. Ghisalberti E.L. (1979) Propolis: a review, Bee World, 60, 59–84. Gemici Y., Şık L. (1992) Türkiye Florasında Endemizim. Tarım ve Köy. Tarım ve Köyişleri Bakanlığı Dergisi, 74, 11–12. Greenaway W., Scaysbrook T., Whatley F.R. (1990) The composition and plant origins of propolis. A report of work at Oxford, Bee World, 71, 107–118. Kence A. (1992) Biylojik zenginlikler Sorunlar ve Öneriler. Tarım ve Köy. Tarım ve Köyişleri Bakanlığı Dergisi, 74, 13–16. Lieberman S., Bruning N. (1990) The Real Vitamin & Mineral Book. Avery Publishing Group, Inc. N.Y. Sahinler, N., Kaftanoğlu, O. “Natural Product Propolis: Chemical Composition,” Natural Product research, 19(2), 183-188 (2005).
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April 2017
Sahinler, S., A. Sahin, O. Gorgulu, (2005). Assessing the possible effects of ferula eleaochytris powder effects in layer diet on feed intake and some egg parameters by using a multivariate analysis method for repeated measures, J. Appl. Anim. Res., 28, 29-33. Tabachnick B.G., Fidell, L.S. (1996) Using Multivariate Statistics. Harper Collins College Publish. California State University, Northridge. 1996.
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