Tea, biological name is camellia sinensis from theaceae family, is most popular beverage worldwide may be after water with full of health benefits such as being antioxidant and tantimicrobial, anticarcinogenic and anti-inflammatory^{[1, 2, 3]}. Turkey is among the major tea growers in the country are grown only in the eastern Black Sea region of Turkey. Turkey is the fifth in an annual amount of tea grown in the world. It is grown in mostly eastern of Black Sea coastline from Giresun to Georgia in Turkey. Tea is a cultivated plant growing in humid climates. The most productive city is Rize where has 100% of Turkey’ s total tea production are obtained from this region. The harwest area is quite narrow and harwest time is four times in a year at 3 months periods.

The fact that tea is a consumed drink, especially the Turkish people, has made it an important issue to focus on the substances contained in the tea and its effects on human health. Tea, especially in China, is used for therapeutic purposes. Examples of diseases used for the treatment of tea include asthma, chest angina, peripheral vascular disease, and coronary artery disease. The tea is effective against the smell of breath and also shows antioxidant effect^{[3, 4, 5, 6, 7, 8, 9]}. Due to such crucial benefits of tea, it is needed to have knowledge of nutrients and element content in the tea. For this many techniques have been used such as atomic absorption spectroscopy (AAS)^[9], inductively coupled plasma atomic emission spectrometry (ICPAES)^[10], inductively coupled plasma mass spectrometry (ICP-MS)^[11], capillary electrophoresis^[12], and total reflection X-ray fluorescence spectrometry (TR-XRF)^{[13, 14]}.

In this study, tea leaves and their soils were collected from eastern of Black Sea cities Trabzon Rize and Artvin from 20 station to determine element levels of both soil and tea samples by using Energy Dispersive X-ray fluorescence spectrometry (ED-XRF) which is non-destructive for samples during the measurement.

The tea leaves and the soil samples were harvested at the beginning of spring from the areas where teas are grown from Trabzon, Rize and Artvin in Eastern Black Sea region of Turkey. The samples were dried at the temperature at 70 ℃ in a Heraeus oven. After grinding the powder samples, the powder samples were sieved through a 400 mesh sieve to reduce the particle size and stirred 20 minutes to obtain a good mixture for sampling. The samples were pressed under the pressure 20 ton by using boric acid stabilizer.

The tea leaves and the soils were collected from eastern Black Sea cities Rize, Trabzon, Artvin and their counties in Turkey. The determined elements were detected in the tea are Na, Mg, Al, P, S, K, Ca, Fe, Cu, Sr, Mn which are some essential minerals for human health as they are activators for enzyme-catalysing reactions^[15]. The soil elements were detected Mg, Al, Si, P, K, Ca, Ti, Fe, Sr, V, Cr, Mn, Rb in the cabbage collected region.

The elemental contents were worked out by using EDXRF3600 Spectrometer and the statistical analysis were done with the Arcmap program to determinate estimated element distribution of working region. Mostly abundant elements sampling stations as numbered are shown in Table 1 with the geographical properties as latitude, longitude and altitude which are important parameters for plant grown.

Table 1

Table 1

Table 1 The geographical properties of the station of the harvested tea samples Station Latitude-X Longtitude-Y Altidute P/Zn ratios Trabzon 1. Sü rmene 40.899 783 40.114 358 272 56.52 Trabzon 2. Caykara 40.728 809 40.230 995 543 58.38 Trabzon 3. Of 40.929 322 40.285 557 208 47.55 Rize 4. I˙yidere 41.008 827 40.360 814 33 40.61 Rize 5. Derepazarı 41.016 081 40.425 187 111 58.23 Rize 6. I˙kizdere 40.765 432 40.561 302 854 45.91 Rize 7. Gü neysu 40.971 478 40.616 289 247 58.26 Rize 8. Ç ayeli 41.085 577 40.736 471 171 44.51 Rize 9. Ç ayeli-Merkez 41.090 154 40.727 535 12 41.33 Rize 10. Ç ayeli- l˙ncesı rt 41.058 713 40.752 711 135 46.24 Rize 11. Cayeli-Aş ı klar 41.079 172 40.803 548 237 48.90 Rize 12. Ç ayyeli-Gü neykö y 41.130 911 40.813 504 75 31.14 Rize 13. Pazar 41.175 362 40.881 046 88 57.24 Rize 14. Ardeş en 41.189 973 40.991 327 10 40.952 38 Rize 15. Hemş in 41.047 591 40.900 021 345 46.370 37 Rize 16. Ç amlı Hemş in 41.045 232 41.007 275 335 45.271 32 Rize 17. Fı ndı klı 41.272 467 41.157 886 59 50.603 45 Artvin 18. Arhavi 41.350 554 41.326 954 82 53.877 55 Artvin 19. Hopa 41.392 679 41.442 387 231 58.461 54 Artvin 20. Borcka 41.352 969 41.664 743 602 54.379 56

Table 1 The geographical properties of the station of the harvested tea samples

In the plant one of the important parameter is (P / Zn)ratio. P / Zn ratio in plants; if (P / Zn)< 50, P is deficient , if (P / Zn)< 50200, Zn is sufficient , if (P / Zn)> 200 , Zn is deficient.The reason for the lack of Zn element is usually due to the excess phosphorus. The low level of useful zinc in the soil is related to low soil temperature, the presence of free lime, low organic matter, high phosphorus level. High levels of useful phosphorus in the soil, zinc in the medium level of the soil, at low temperatures, zinc deficiency in the plant causes, but at high temperatures, this deficiency is not seen. Zinc deficiency also prevents the leaves from taking their normal size and causes their shapes to change. In the case of zinc deficiency, the leaf system of the tree becomes sparse and the knot spacing becomes shorter. The efficiency of trees exposed to zinc deficiency is also decreasing^[19]. In our samples P/Zn ratios are Sufficient for Sü rmene, Ç aykara, Derepazarı , Gü neysu, Pazar, Fı ndı klı , Arhavi, Hopa, Borç ka but others (P/Zn) level is lover than 50% which are shown in bold in Table 1.

In Table 2, Mg, Al, Si, P, S, K, Ca, Ti, V, Mn, Fe elements on percent level, in the soil sample are presented. In Table 3 Mg, Al, Si, P, Cl, K, Ca, Ti, Mn, Fe in the tea leaves are presented. Al, Ca, K, Mg, Mn, Na, P and S are major constituents in tea^[18] and the elements in teas are Ni, Cr, Cu, Zn, Sr, Ba, Pb even they are below the detection limit.

Table 2

Table 2

Table 2 The soils of the tea collected stations Artvin Mg Al Si P S K Ca Ti V Mn Fe Zn Hopa 0.32 14.92 34.14 0.01 0.08 0.47 0.05 0.48 0.02 0.04 4.49 0.01 Borcka 1.21 11.40 25.32 1.56 0.48 0.61 2.88 0.55 0.04 0.13 5.68 0.04 Arhavi 0.48 16.75 33.92 0.24 0.18 0.52 0.10 0.61 0.03 0.13 6.27 0.01 Rize Ç amlı Hemş in 2.76 11.16 27.29 0.14 0.24 0.20 1.95 0.42 0.03 0.11 6.35 0.01 Ardeş en 0.28 4.78 14.12 0.40 0.25 0.33 0.98 0.22 0.01 0.19 3.11 0.02 Pazar 0.99 15.63 33.05 0.00 0.09 0.67 0.39 0.55 0.03 0.05 4.89 - Ç ayeli 1.44 12.11 21.14 0.43 0.10 0.51 1.19 0.55 0.04 0.13 6.93 0.02 Hemş in 1.47 12.43 20.32 0.20 0.16 0.39 0.77 0.61 0.05 0.13 7.60 0.01 Fı ndı klı 1.53 16.35 25.71 0.40 0.26 0.38 0.27 0.67 0.04 0.09 7.91 0.01 I˙kizdere 1.18 8.92 16.79 0.16 0.06 0.66 0.22 0.59 0.05 0.12 7.08 0.01 Gü neysu 2.20 11.26 23.33 1.59 0.05 0.75 0.98 0.60 0.04 0.11 6.20 0.01 Derepazarı 2.20 11.47 25.47 0.47 0.50 0.63 2.95 0.56 0.04 0.13 5.75 0.04 I˙yidere 1.25 13.02 26.66 0.22 0.24 0.59 0.36 0.59 0.04 0.08 6.36 0.01 Ç ayeli-Merkez 1.32 14.37 26.78 0.12 0.20 0.40 0.12 0.75 0.05 0.04 7.28 0.01 Ç ayeli-Aş ı klar 1.10 7.81 17.40 0.24 0.04 0.37 0.93 0.45 0.03 0.10 6.18 0.01 Ç ayeli-Gü neykö y 1.61 9.80 22.54 0.12 0.14 0.65 0.78 0.46 0.03 0.03 5.48 0.01 Ç ayeli- l˙ncesı rt 1.59 15.27 26.51 0.40 0.10 0.70 0.17 0.74 0.05 0.05 7.44 0.01 Trabzon Caykara 1.18 12.12 23.14 0.04 0.20 0.43 0.37 0.57 0.04 0.06 6.52 0.01 Of 1.78 9.28 21.09 0.03 0.07 0.67 0.76 0.49 0.04 0.00 6.09 0.01 Sü rmene 2.62 15.15 33.92 0.19 0.07 0.65 1.35 0.61 0.04 0.11 6.61 0.01

Table 2 The soils of the tea collected stations

Besides the graphical comparison the statistical mapping by used krigging method is also presented in Figure 1( a— c) with the numbered station and colored maps of Fe and Mg element distribution , from dark blue (less dense) to red (denser).

Fig.1(a)

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	Fig.1(a) The numbered map of the sampling areaby designing Krigging Method

Fig.1(b)

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	Fig.1(b) The numbered map of the sampling areaby designing Krigging Method

Fig.1(c)

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	Fig.1(c) Interpolation maps of Mg element distribution by designing Krigging Method

The Mg, Mn, Fe levels are quite different for Ç amlı hemş in, Ç ayeli, Ardeş en and Arhavi towns; Mg Level is higher in Ç amlı hemş in, Ç ayeli, Ardeş en and Arhavi towns have higher level for Mn content, Hopa and Borç ka have higher Fe content as seen in Table 3. due to the fertilizing method, rain fall in m², altitude and soil type shows difference for every station. Fertilizing specially Ammonium Sulfate included fertilizers increased the soil acidity which induce the adsorption of the elements easier by the plants^[16]. The increase in metal content of soil has a great influence for determining the soil quality and on human health through the plants growing on it ^[17] Tea plant intends to grow in the humid and acidic soils.

Table 3

Table 3

Table 3 Elemental distribution in the tea samples Trabzon Mg Al Si P S Cl K Ca Ti Mn Fe 1.Sü rmene 0.42 1.20 0.24 0.50 1.81 0.14 2.20 2.99 0.00 0.77 0.19 2.Caykara 0.12 0.85 0.29 0.61 1.20 0.20 3.55 3.11 0.02 0.51 0.16 3.Of 0.28 1.19 0.56 0.47 1.33 0.19 2.37 3.05 0.01 0.42 0.13 Rize 4. I˙yidere 0.12 0.43 0.20 0.67 0.83 0.08 2.99 1.74 0.01 0.44 0.08 5.Derepazarı 0.30 0.49 0.43 0.82 1.17 0.26 4.06 1.84 0.00 0.37 0.07 6. I˙kizdere 0.35 0.65 0.53 0.63 0.96 0.07 3.11 2.07 0.00 0.53 0.08 7.Gü neysu 0.12 0.41 0.28 0.77 0.80 0.06 3.82 1.74 0.01 0.25 0.07 8.Ç ayeli 0.52 1.28 0.13 0.54 0.98 0.15 3.84 2.50 0.00 0.42 0.08 9.Ç ayeli-Merkez 0.07 0.53 0.93 0.59 0.89 0.09 2.31 2.07 0.01 0.58 0.10 10.Ç ayeli- l˙ncesı rt 0.25 2.25 0.34 0.65 1.21 0.08 2.43 2.60 0.02 0.77 0.27 11.Cayeli-Aş ı klar 0.04 0.40 0.00 0.80 0.78 0.07 2.39 2.27 0.01 0.27 0.07 12.Ç ayyeli-Gü neykö y 0.03 1.09 0.05 0.36 0.80 0.18 2.34 4.51 0.01 0.54 0.17 13.Pazar 0.11 0.70 0.11 0.66 1.02 0.05 3.71 1.89 0.01 0.30 0.06 14.Ardeş en 0.29 1.29 0.43 0.60 0.98 0.08 2.02 3.00 0.01 1.46 0.17 15.Hemş in 0.45 0.87 0.20 0.63 1.26 0.10 2.87 3.08 0.01 0.43 0.02 16.Ç amlı Hemş in 0.70 0.58 0.23 0.58 0.86 0.11 1.68 4.41 0.01 0.47 0.09 17.Fı ndı klı 0.30 0.71 0.14 0.59 1.15 0.06 2.85 2.35 0.00 0.62 0.08 Artvin 18.Arhavi 0.13 0.67 0.21 0.79 1.02 0.09 3.94 1.76 0.08 1.64 0.06 19.Hopa 0.12 0.83 0.80 0.68 1.06 0.02 3.02 1.74 0.03 0.71 0.36 20.Borcka 0.27 0.60 0.51 0.75 1.12 0.08 3.49 2.17 0.03 0.83 0.35

Table 3 Elemental distribution in the tea samples

The tea leaves and their soils were collected from 20 stations in Rize, Trabzon, Artvin towns from tea fields, one of the best tea producer, of eastern of Black Sea region in Turkey. The elemental analysis were worked out by using EDXRF spectrometer and obtained results were evaluated by Kriging interpolation of geostatistical method that is one of the statistical interpolation method, to get elemental distribution in tea according to sampling stations. It seems that besides the other spectroscopy techniques EDXRF is also give significant results for soil and plant researcher as there is no necessity for a solution during the sample preparation, the samples can be directly measured if the need is only learning element content of element composition in the plant. In this study dried and grinded tea leaves and grinded soils measured by EDXRF Technique. According to the results the tea quality quite good if we consider the P/Zn ratio in tea leaves.