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Food Control 19 (2008) 746749 www.elsevier.com/locate/foodcont

Heavy metal content of black teas from south India

Subbiah Seenivasan
a

a,*

, Natarajan Manikandan a, Narayanan Nair Muraleedharan a, Rajagopal Selvasundaram b

UPASI Tea Research Foundation, Tea Research Institute, Nirar Dam BPO, Valparai 642 127, Coimbatore, Tamil Nadu, India b Chemtura Chemicals India (Pvt.) Limited, Mumbai, India Received 19 March 2007; received in revised form 15 July 2007; accepted 20 July 2007

Abstract Tea is the most popular beverage in the world. Since tea contains several essential nutrients, drinking of tea is considered benecial for human health. The presence of heavy metals in trace level in tea has received special attention because they are directly related to health. A basket survey was conducted in the tea districts of south India to generate a data base on the presence of heavy metals in black tea. A total of one hundred black tea samples, collected from the tea growing regions of Valparai and Nilgiris in Tamil Nadu, Vandiperiyar, Wayanad and Munnar in Kerala and Karnataka state were analyzed for heavy metals. The results of analysis showed that the mean level of Cu was 24.07 2.25 mg kg1, Cr 4.76 1.27 mg kg1, Ni 2.53 1.01 mg kg1, Cd 0.14 0.06 mg kg1 and 0.81 0.32 mg kg1. Under the Prevention of Food Adulteration Act (PFA) of India the tolerance limits have been xed only for copper and lead. The present database could be used for xing tolerance limits of the other heavy metals in tea. The contents of copper and lead in tea were below the permissible limit under the PFA act. 2007 Elsevier Ltd. All rights reserved.
Keywords: Black tea; Heavy metals; Survey; Tolerance limit

1. Introduction Tea is one of the most popular beverages in the world and its health benets have been well documented. Stagg and Millin (1975) have emphasized the therapeutic action of tea. Tea could be an important source of manganese and the large amount of potassium in that could be benecial for hypertensive patients. The intake of food contaminated by heavy metals is harmful to human health and several countries have imposed food laws to restrict the presence of heavy metal concentration in food and beverages. Various reports have discussed the potential health implications of trace metals in tea, since the tea bush is known to accumulate them (Bosque, Schumacher, &

Corresponding author. Tel.: +91 4253 235301/303; fax: +91 4253 235302. E-mail address: upasitri@satyammail.com (S. Seenivasan). 0956-7135/$ - see front matter 2007 Elsevier Ltd. All rights reserved. doi:10.1016/j.foodcont.2007.07.012

Domingo, 1986; Anonymous, 1999). Natesan and Ranganathan (1990) studied the contents of various elements in dierent parts of the tea plant such as shoot, mature leaf, small stem, tick wood and root, in black tea manufactured by the crushtearcurl and orthodox processes, and the tea brew. A few publications are available on the presence of heavy metals in tea and the analytical diculties associated with their separation from tea leaves (Marcos, Fisher, Ree, & Hill, 1998). The main sources of heavy metals in plants are their growth media, nutrients, agro inputs and soil. Other sources may include pesticides and fertilizers. Elevated heavy metal levels cause damage to plants such as delayed owering, lower chlorophyll content and reduction in the number and quality of shoots (Setia, Kaur, & Setia, 1989). We have hardly many information on the heavy metal content of black tea produced in south India, which produces about 230 million kg of tea annually and nearly fty percent of this is exported. About hundred tea sam-

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ples, produced in dierent factories in southern India were collected and analyzed for the content of heavy metals such as nickel, chromium, lead, cadmium and also copper. Many elements play a vital role in the metabolic processes and in the general well being of humans. Trace level of copper is essential for human health. Tea leaves are source of mineral elements such as zinc, manganese, iron, copper, magnesium, titanium, aluminium, strontium, bromine, sodium, potassium, phosphorous, iodine and uorine. The tea infusion contains very little protein, vitamins and carbohydrates but may be a source of essential dietary metals and metal binding polyphenols. 2. Materials and methods 2.1. Sample collection A total of 100 black tea samples were collected from the tea factories in Valparai taluk (Coimbatore Dist., Tamil Nadu), Coonoor, Kotagiri, Ooty, Gudalur (Nilgiris Dist., Tamil Nadu), Wayanad Dist. (Kerala), Munnar, Vandiperiyar, Peermedu (Idukki Dist., Kerala) and Chikmagalur Dist. (Karnataka). The tea samples included both CTC (Crush, Tear, Curl) and orthodox types of teas. 2.2. Sample preparation The glassware and polyethylene containers used for analysis were washed with tap water, then soaked over night in 6 N HNO3 solution and rinsed several times with ultra pure water to eliminate absorbance due to detergent (Cabrera, Gallego, Lopez, & Lorenzo, 1994). The standard procedure described in AOAC (2000) was followed for the preparation of samples for analysis of heavy metals. Accurately weighed (0.5 g) made tea sample was transferred in to a silica crucible and kept in a mue furnace for ashing at 450 C for 3 h and then 5 ml of 6 M HCl was added to the crucible. Care was taken to ensure that all ash came into contact with acid. Further, the crucible containing acid solution was kept on a hot plate and digested to obtain a clean solution. The nal residue was dissolved in 0.1 M HNO3 solution and made upto 50 mL. Standard solutions were prepared according to the PerkinElmer Pure Atomic Spectroscopy Standards guidelines (NIST traceable CRM, PerkinElmer Corporation, USA and Merck Germany). Working standard solutions were prepared by diluting the stock solution with 0.1 M nitric acid for checking the linearity. 2.3. Analytical procedure Cu, Cr, Ni, Cd and Pb in tea samples were analyzed using atomic absorption spectrophotometer (AA Analyst 800, PerkinElmer Corporation, USA) equipped with ame and graphite furnace. Air-acetylene ame was used for determination of metal content. The instrument was operated with the following conditions in ame mode: acet-

Table 1 Analytical characteristics of the AASGF and ame determination Metal Cu Cr Ni Cd Pb k (nm) 324.8 357.9 232.0 228.8 283.3 Working range (lg ml1) 0.075 0.084 0.104 0.0050.1 0.0050.1 Correlation coecient (r) 0.9999 0.9999 0.9999 0.9985 0.9992

ylene 2 ml/min, air 17 ml/min for Cu, Ni, and Cr and in a graphite furnace mode (Pb and Cd) the inert argon gas ow and the temperature parameters were followed as recommended by manufacturers (Perkin-Elmer, 2000). The absorption wavelength for the determination of each metal together with its linear working range and correlation coefcient of calibration graphs are given in Table 1. Data were rounded o suitably according to the value of standard deviation from measurements in triplicate. 3. Results and discussion The results of analysis of tea samples are presented in Table 2. The mean values in mg kg1, were 24.07 for copper, 4.76 for chromium, 2.53 for nickel, 0.14 for cadmium and 0.81 for lead in tea. There was wide variation in the heavy metal content of black teas collected from the dierent regions of south India. The results indicated that the contents of Cu, Cr, Ni, Cd and Pb in tea were dierent for the dierent agroclimatic regions. In south India, places such as Valparai, Wayanad, Gudalur, Vandiperiyar and Karnataka are in mid-elevation at 5001500 m above MSL while Coonoor, Kotagiri and Ooty in Nilgiris and Munnar are at 15002500 m above MSL. Though in all the regions the soils are latosol, the clay content, water holding capacity, the contents of organic matter, iron and aluminium oxides and base exchange capacity are dierent for the various regions. Based on the yield per hectare and organic matter content the dosage of fertilizers as well as the timing and number of applications vary (Ranganathan, 1977). The number and frequency of application of fungicides, especially copper oxychloride for blister blight disease control in tea were not consistent due to variations in disease incidence. In southern India blister blight incited by Exobasidium vexans Massee is the most important leaf disease of tea, causing heavy crop loss. The pathogen is an obligate parasite without any alternate host and it completes its life cycle within a period of 11 to 28 days. Since the climatic conditions prevailing during the monsoon are conducive for the growth of the pathogen, the crop has to be protected with frequent applications of fungicide throughout the season. Blister blight disease is a major problem in all the tea areas except in the high elevation areas of Kotagiri and Coonoor (Nilgiris) which receive the north east monsoon and very little of the south west monsoon. In these areas, foliar application of fungicides is very much limited.

748 Mean S.Da

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Although the judicious use of copper fungicides may not cause problems of public health and environmental contamination the indiscriminate use will lead to the presence of undesirable levels of copper content in black tea. Analysis of copper content in made tea samples indicated that the mean value of copper ranged between 15.9 and 32.2 mg kg1. Copper is one of the native metals found in tea, central to polyphenol oxidase enzyme. It is one of the major elements next to Al and Zn in tea. The lowest value of copper was found in Nilgiris tea and the highest in Gudalur tea samples. Cu content in made tea was also reported by Xie, Bohlen, Klockenkamper, Jian, and Gunter (1998), Ferrara, Montesanoa, and Senatore (2001). It was evident from this study that the Cu content of all the made tea samples were less than 30 mg kg1, which is well below the permissible limit of 150 mg kg1 under Prevention of Food Adulteration Act, 1954 (PFA), India. The content of chromium in all the black tea samples ranged between 2.5 and 11.4 mg kg1. The lowest and highest contents of Cr were found in Karnataka and Munnar (High Range) samples, respectively. Cr is considered as a local contaminant and comes mainly through the CTC rollers during the manufacturing of black tea. In orthodox processed black tea samples, chromium content was lower and ranged between 1.1 and1.6 mg kg1. Since most of the CTC factories are located in Valparai and Vandiperiyar and Peermedu areas the value of Cr in these areas was also marginally higher. The levels of chromium in made tea samples in Nilgiris are lower where 90% of the factories are adopting orthodox manufacturing process. Since the rollers used in CTC tea manufacturing are made of stainless steel containing chromium (17% w/w), CTC processed black teas contained higher level of Cr whereas in orthodox processed tea the Cr content was lower as the machinery employed are made up of gun metal having only trace level of chromium. Ferrara et al. (2001) reported that chromium in black tea samples ranged between 17.9 and 115.4 mg kg1. Nickel in made tea was in the range of 1.1 to 5.3 mg kg1. The lowest nickel (Ni) content was found in Nilgiris teas and highest in tea from Vandiperiyar and Peermedu. Marcos et al. (1998) had reported that nickel in the made tea sample ranged between 2.89 and 22.6 mg kg1. Franklin, Duis, Brown, and Kemp (2005) reported that potassic fertilizers contained 2.7 to 16 mg kg1 nickel as impurity while commercial phosphatic fertilizers contained 19 to 24 mg kg1 Ni. He also reported manganese sources containing 340613 mg kg1 of Ni, zinc sources containing 2412,399 mg kg1 of Ni, boron sources containing 39 mg kg1 of Ni and magnesium sources containing 77 mg kg1 of Ni content. It is clearly evident that nickel mainly comes through the foliar and soil application of low quality fertilizers and micro nutrients. Since Ni is a toxic element, not having any tolerance limit in tea, the agro inputs used in tea elds will have to be analyzed for heavy metal impurity.

Mean S.Da Cd Mean S.Da Range Ni Range

1.54.6 0.41.7 1.22.5 1.24.6 1.49.2 1.72.1 0.92.1 Valparai CoonoorKotagiriOoty (Nilgirs) Gudalur (Nilgiris) Wyanad (VandiperiyarPeermedu) Munnar Karnataka Mean S.Da
a

3.1 1.32 1.1 0.50 1.9 1.27 2.9 1.26 5.3 1.46 1.9 0.49 1.5 0.75 2.53 1.01 The quoted SD values are on the basis of range of elemental concentration determined in dierent tea samples. 20 16 14 13 12 15 10 16.338.5 12.519.3 20.244.1 18.932.2 18.836.8 12.541.3 12.122.1 27.4 2.49 15.9 1.75 32.2 3.10 25.6 1.95 27.8 3.69 26.9 1.58 17.1 1.25 24.07 2.25 1.48.1 1.24.9 2.04.1 2.53.9 2.57.9 1.621.2 1.13.9 4.8 1.37 3.1 0.92 3.1 0.55 3.2 0.74 5.2 2.13 11.4 2.64 2.5 0.57 4.76 1.27

Heavy metal content (mg kg1 of black tea)

Cr

Table 2 Heavy metals in black teas from south India

Region

Number of samples

Range

Cu

Mean S.Da

Range

Mean S.Da

0.010.09 0.010.18 0.060.18 0.060.15 0.060.69 0.060.12 0.090.15

0.05 0.02 0.10 0.05 0.12 0.07 0.11 0.09 0.38 0.15 0.09 0.01 0.12 0.04 0.14 0.06

0.260.83 0.041.19 0.801.17 0.831.23 0.631.36 0.140.82 0.821.18

Range

Pb

0.55 0.24 0.62 0.46 0.99 0.55 1.03 0.41 1.00 0.18 0.48 0.14 1.00 0.28 0.81 0.32

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The levels of cadmium in black tea was between 0.05 and 0.38 mg kg1. The lowest level of Cd was found in tea samples from Valparai and highest from Vandiperiyar and Peermedu. Ferrara et al. (2001) found that cadmium in tea was below the detection limit in tea samples collected from the dierent countries of the world. However, in the present study cadmium was detected and quantied. Mengel and Kirby (1987) noted that certain plants accumulated Cd without exhibiting any toxic symptoms. Further they claimed that the availability of cadmium in soils was inuenced positively by the addition of rock phosphate. In tea, rock phosphate is applied annually. Franklin et al. (2005) reported 4.95.5 mg kg1 of Cd in phosphatic fertilizers and 11.850.9 mg kg1 in zinc sources. It appears that contaminated phosphatic and zinc fertilizers were the sources of Cd in tea. The Pb content in tea samples varied between 0.48 and 1.03 mg kg1. The lowest content was found in the made tea samples collected from Munnar and the highest from Wayanad. The tea samples from NilgirisWyanad and Karnataka regions also showed marginally higher levels of lead. Potassic fertilizers, phosphatic fertilizers, NPK blends, manganese, zinc, boron and magnesium sources contain lead (Franklin et al., 2005). Zinc is the only micronutrient whose deciency is widely noticed in tea and zinc sulphate is given as a foliar spray to supply zinc. Zinc sulphate contaminated with lead, when foliar applied, Pb may enter the tea plant. Spraying of copper fungicides with heavy metal impurities may increase the accumulation of Pb and Cd in tea. Copper oxychloride is considered as one of the main sources Pb contamination (Semu & Singh, 1996). Tea soils are acidic and this condition favours solubility of heavy metals. Tea bushes adjacent to heavy trac gets exposure to Pb and Cd through fallout from automobile exhaust and dust. (Michie & Dixon, 1977; Tsushida & Takeo, 1977). The average Pb level in the Chinese black tea samples was 1.42 mg kg1 (Xie et al., 1998). In our study, Pb content in all the made tea samples was less than 10 mg kg1, the limit prescribed under the PFA Act. 4. Conclusions A database generated for heavy metals in black tea from south India showed that the levels of Cu and Pb were below the PFA limit of 150 and 10 mg kg1, respectively. For other heavy metals such as chromium, nickel and cadmium, the data generated could be utilized for xing tolerance limits in tea.

Acknowledgements The authors are grateful to the Tea Board, Govt. of India for the nancial assistance for this work under the X ve year plan. References
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