DETERMINATION OF HEAVY METALS IN HONEY IN ... - Springer Link

Environmental Monitoring and Assessment (2005) 109: 181–187 DOI: 10.1007/s10661-005-5848-2

c Springer 2005

DETERMINATION OF HEAVY METALS IN HONEY IN KAHRAMANMARAS¸ CITY, TURKEY 2,∗ ¨ ˘ FERYAL ERB˙IL˙IR1 and OZLEM ERDOGRUL

Department of Biology, Faculty of Science and Arts, University of Kahramanmaras¸ Sütçu¨ I˙mam, Kahramanmaras¸, Turkey; 2 Department of Food Engineering, Faculty of Agriculture, University of Kahramanmaras¸ Sütçu¨ I˙mam, Kahramanmaras¸, Turkey (∗ author for correspondence, e-mail: [email protected]) 1

(Received 26 April 2004; accepted 2 November 2004)

Abstract. Heavy metals in honey are of interest not only for quality control, but also for determination environmental contamination. The objective of this work was to determine distribution of the levels of selected heavy metals. Levels of copper (Cu), cadmium (Cd), manganese (Mn), Iron (Fe), magnesium (Mg) and nickel (Ni) in honey samples (21) in Kahramanmara¸s region were determined by atomic absorption spectrometer (AAS). The mean values for Cu, Cd, Mn, Fe, and Mg were 0.01, 0.32, 0.03, 0.36 and 10.45 ppm, respectively. Nickel was not detected in honey samples. Kahramanmara¸s honey samples were not free of heavy metals but the levels of them were found well below the permitted levels. The results suggested that honey may be useful for assessing the presence of environmental contaminants. Keywords: environmental marker, heavy metals, honey

1. Introduction From early times, honey was considered a delicious food. In addition, the result of a bio-accumulative process it is also useful for collecting information about the environment within the bees’ Forage area. Honeybees’ accretions are related to air, water and soil; they go from flower to flower, touch branches and leaves, drink water from pools and their hairy bodies collect aerosol particles. Bees are estimated to forage on plants growing in a relatively large area of more than 7 km2 (Bromenshenk and Carlson, 1985; Celli, 1984). If it is assumed that any hive includes and least 1000 worker-bees and that each of them forage on one thousand flowers per day, the honey produced daily can be considered the outcome of at least one million interactions. In this way, the forage area is effectively sampled for trace elements and the concentration in honey of heavy and transition metals reflecting levels in the forage area (Bariˆsić et al., 1999; Hoefel, 1985; Jones, 1987; Kump et al., 1996; Leita et al., 1996). Turkey has an important place among the honey producing countries, since it is suitable for apiculture in terms of the flowers. Turkey produces about 80.000 tons of honey per year (Anonymous, 1997). Apiculture in Turkey has been in a state of expansion since 1993, with a yearly increase of 4.1% (Anonymous, 1995).

¨ . ERDOGRUL ˘ F. ERB˙IL˙IR AND O

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Honey is mainly produced in the middle and west of Turkey (Anonymous, 1994). Nowadays in Kahramanmara¸s city, belonging to the East Mediterranean region, honey production has increased. But different parameters about the quality of this honey in this region have not been studied yet. Human activities increase the level of heavy metals circulating in the environment. Heavy metal pollution of the biosphere has been accelerated rapidly since the onset of the industrial revolution and heavy metal toxicity poses major environmental problems. Mineral contents of Turkish honey were studied briefly by Sevimli et al. (1992). They determined K, Br, As, Sb, Fe, Zn, Cr and Co contents of five different honey samples. Though the mineral content has been largely ignored until now, it seems to be of interest to determine this parameter in Turkish honey samples. Heavy metal content in honey, however, has not been investigated until now in this area; hence it seems to be of interest to determine this parameter. Honey can be used as indicator for the general level of contamination, and thus it is useful to assess potential health risks associated with the intake of honey. In the sampling area, there are several potential sources of pollution around the city: paper, textile, oil, and milk industries. The objective of this work was to determine the distribution levels of selected heavy metals (Cu, Cd, Mn, Fe, Mg, Ni).

2. Materials and Methods 2.1. H ONEY

SAMPLES

Twenty-one natural liquid honey samples (100 g) in Kahramanmara¸s city, Turkey, were collected from different beekeepers in February–March 2004. Kahramanmara¸s is a city in Turkey in East Mediterranean region (Figure 1).

Figure 1. Sampling place: Kahramanmara¸s city, Turkey.

DETERMINATION OF HEAVY METALS IN HONEY

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The honey samples were stored in glass jars. Each jar contained about 100 g of honey. The honey samples were kept at room temperature and in the dark until analyzed. All the natural samples examined were unprocessed honeys of random (mixed) floral type. 2.2. ANALYTICAL

DETERMINATIONS

Ash contents were determined by heating 10 g of honey precedence 100 ◦ C to moisture amount decrease, after 500 ◦ C to constant weight dry up with an infra-red lamp to prevent foaming (AOAC, 1984). Six selected metals copper (Cu), cadmium (Cd), manganese (Mn), iron (Fe), magnesium (Mg) and nickel (Ni) were measured using Perkin Elmer 3110 Atomic Absorption Spectrophotometer (AAS). Solutions containing Cd, Cu, Mn, Fe, Mg and Ni ions were obtained by dissolution of ash in 10 ml percholic acid (60%) and nitric acid (65%) (Merck Darmstadt, Germany). The weight of the ash of the honey samples were measured and filtered by Whatman No 41 filter paper. Cd, Cu, Mn, Fe, Mg and Ni were determined directly in the ash solution by atomic absorption spectrometer (Perkin Elmer 3110 AAS). The instrument response was periodically checked with known standards. An airacetylene flame and hollow cathode lamp were used for all samples. Calibration curves were prepared using dilutions of stock solutions. The samples (honey and blind samples) were read three times and the mean values and the relative standard deviations were computed. The following wavelengths were used for the studied metals: copper 324.8 nm, cadmium 228.8 nm, manganese 279.5 nm, iron 248.3 nm, magnesium 285.2 nm, and nickel 232.0 nm. Analytical procedures have been described in detail in Anonymous (1982). Measurements were made without delay after the solvent extraction. All measurements were made twice. 3. Results Mean heavy metal contents (ppm wet weight) with the standard deviations and range are shown in Table I. The mean, minimum, maximum and standard deviation of ash content of 21 honey samples were 0.21, 0.05, 0.56 and 0.16 respectively. The copper (Cu) contents, out of 21 honey samples, 19 were below the sensitive detection limit. The range values of the copper content were between 0.0–0.09 ppm. The mean and the range values were 0.32, 0.31–0.34 for Cd, 0.03, 0.0–0.09 for Mn, 0.36, 0.04–1.21 for Fe, 10.45, 2.03–111.36 for Mg, respectively. Nickel (Ni) was not detected in the honey samples that studied. 4. Discussion It can be seen that the honey samples of Kahramanmara¸s city generally have lower ash contents, for example, than those reported from the Aegean region of Turkey


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TABLE I Heavy metal content (ppm) in honey samples in Kahramanmara¸s region, Turkey Metals (ppm) in honey samples (21)

Mean

Range

Standard deviation

Sensitivity detection limit (ppm)

Cu Cd Mn Fe Mg Ni

0.01 0.32 0.03 0.36 10.45 NDa

0.0–0.09 0.31–0.34 0.0–0.09 0.04–1.21 2.03–111.36 –

0.02 0.01 0.02 0.36 23.36 –

0.077 0.028 0.052 0.1 0.3 0.14

a

ND = Not determined.

¨ urk et al. (1989), south–eastern Anatolia of Turkey by Yılmaz and Yavuz by Ozt¨ (1999), north–west Spain by Rodriguez-Otero et al. (1994), and from Italy by Lower (1987). Honey normally has low ash content and it depends on the material collected by the bees during foraging on the flora (Abu-Tarboush et al., 1993). The ash content (0.05–0.56%) was within the allowed limit by Turkish Alimentarus Codex (Anonymous, 2003). As can clearly be seen from the Table I, the metal contents were low. From previous studies, it was seen that industry, mining, automobile exhaust gases, etc., may cause cadmium contamination in honey (Morse and Lisk, 1980; D’Ambrosio and Marchesini, 1982; Bogdanov et al., 1985; Gajek et al., 1987). Honey that comes into contact with metal containers or equipment during storage, processing or shipping, may have elevated levels of iron (Morse and Lisk, 1980; Gajek et al., 1987). In the study of Morse and Lisk (1980), 16 elements were determined in honeys from the United States, Mexico, El Salvador and China. They reported rather high levels of some trace elements. Concentration ranges of some of these elements as ppm were: Cd 0.102–0.267, Fe 5.80–183, Ni 0.304–1.25. The source of these metals was considered as steel or galvanized containers used in processing, shipping or storage. Crane (1975) determined the concentrations of Mg, Fe, Cu, Mn, and other minerals in flower honeys and honeydew honeys. Mean values of minerals as ppm for flower honeys were: Mg 19, Fe 2.4, Cu 0.29, and Mn 0.30. The mean values for honeydew honeys as ppm were: Mg 35, Fe 9.4 Cu 0.56, and Mn 4.1. The mean and the range values of cadmium (Cd) content of the honey samples were 0.32, 0.31–0.34, respectively. These values were higher than in previous report (Przybyl owski and Wilczyńska, 2001). The mean and the range values of iron (Fe) content of the honey samples were 0.36, 0.04–1.21, respectively. Iron content was lower than in previous reports (Ivanov and Chervenokova, 1984; Sevimli et al., 1992, Latorre et al., 1999), but similar to those in Lazio (Central Italy) honeys (Conti, 2000). The copper (Cu) contents, out of 21 honey samples 19, were below the sensitive detection limit. The copper values were lower than those reported previously


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(Rodriguez-Otero et al., 1992; Yılmaz and Yavuz, 1999; Latorre et al., 1999; Conti, 2000). The mean and the range values of manganese (Mn) content of the honey samples were 0.03, 0.0–0.09, respectively. These values were below the sensitive detection limit of AAS. The contents were also lower than those reported previously (Rodriguez-Otero et al., 1992; Latorre et al., 1999; Conti, 2000). The mean of magnesium content (10.45 ppm) was also lower than those reported previously in Southeastern Anatolia honey (Yılmaz and Yavuz, 1999), in Spanish honey (Rodriguez-Otero et al., 1992), and in Lazio honey (Conti, 2000). In none of the samples nickel (Ni) was detected. Ni findings were similar within the previous reports (Yılmaz and Yavuz, 1999; Latorre et al., 1999). There are few reports of environmental pollution by heavy metals. Experiments, carried out in Poland show big fluctuations in contents of particular heavy metals (Buliński et al., 1995; Dobrzański et al., 1994). Few tested samples were free of them. Large amounts of heavy metals were found in honey from hives located near extra urban crossroads and steelworks. According to some Italian workers, honey may be viewed as an environmental marker (Leita et al., 1996). They found large ¨ amounts of Cd in honey. In a study of Uren et al. (1998), the mean levels of Cd (ppb), Fe (ppm), Cu (ppm), Mn (ppm), Mg (ppm) in honeydew honey from Turkey were 10.8, 10.4, 1.05, 0.752, 55, respectively. It is concluded that Kahramanmara¸s honey samples were not free of heavy metals but the levels of them were found well below the permitted levels. Kahramanmara¸s Turkey honey is considered among the less polluted foods. It shows that the apiaries are located at a distance which is far from any possible pollution source(s) (i.e. highways with intense traffic) in Kahramanmara¸s city. The results of this first regional survey show the good quality of honey analyzed in relation to the studied parameters. The determination of reliable, reference background levels was considered very useful for both the constant monitoring and the prevention of future problems due to the emission of heavy metals in the environment. Also the results suggested that honey may be useful for assessing the presence of environmental contaminants. References Abu-Tarboush, H., Al-Kahtani, H. and El-Sarrage, M.: 1993, ‘Floral type identification and quality evaluation of some honey types’ Food Chem. 46, 13–17. Anonymous: 1982, ‘Analytical methods for Atomic Absorption Spectrophotometer’, Perkin Elmer Manuel, Fish Products, 4–5. Anonymous: 1994, Encyclopedia Britannica, Encyclopedia Britannica Inc., Chicago (in Turkish). Anonymous: 1995, ‘Annual statistics of Republic of Turkey for 1994’, D˙IE, Devlet ˙Istatistik Enstitüsü Ankara, Turkey (in Turkish). Anonymous: 1997, D˙IE, Devlet ˙Istatistik Enstitüsü, Ankara, Turkey (in Turkish). Anonymous: 2003, ‘Honey Rescript’, Turkish Alimentarus Codex, The official gazette of the Republic of Turkey, 25180 (in Turkish).

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