Food Chemistry 135 (2012) 29302933

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Food Chemistry
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Monitoring and risk assessment of pesticide residues in yuza fruits (Citrus junos Sieb. ex Tanaka) and yuza tea samples produced in Korea
Kwang-Geun Lee , Suk-Kyung Lee
Department of Food Science and Biotechnology, Dongguk University-Seoul, 26, 3-Ga, Pil-dong, Chung-gu, Seoul 100-715, Republic of Korea

a r t i c l e

i n f o

a b s t r a c t
The objective of this study was to establish an analytical method to measure pesticides used to cultivate yuza (Citrus junos Sieb. ex Tanaka) and to analyze pesticide residue levels of yuza and yuza tea samples. Risk assessments were also performed by calculating estimated daily intake (EDI) and acceptable daily intake (ADI). An excellent linear correlation was achieved with coefcient correlation values of 0.97500.9999. Percent recoveries were 80.4109.9% for most pesticides with a <6.9% relative standard deviation (RSD). The limits of quantication for the method were 0.100.67 lg/ml. The RSD of intraday and inter-day variability was <15.3%. Seven pesticides in yuza (n = 80) and yuza tea (n = 75) were analyzed with the optimized analytical method. Acequinocyl, spirodiclofen and carbendazim were detected in yuza samples in the concentration range of 0.070.15 lg/g, 0.111.89 lg/g, and 0.03 5.15 lg /g, respectively, whereas chlorpyrifos, prothiofos, phosalone, and deltamethrin were not detected in yuza or yuza tea. The concentrations of acequinocyl, spirodiclofen and carbendazim ranged from 0.18 1.05 lg/g, 0.130.29 lg/g, and 0.172.36 lg/g, respectively, in yuza tea samples. The percent ratios of EDI to ADI for acequinocyl, spirodiclofen, and carbendazim were 24.6%, 22.7%, and 58.5%, respectively. 2012 Elsevier Ltd. All rights reserved.

Article history: Received 19 March 2012 Received in revised form 26 May 2012 Accepted 26 June 2012 Available online 13 July 2012 Keywords: Pesticide Residue Yuza Yuza tea Risk assessment

1. Introduction Yuza, Citrus junos Sieb. ex Tanaka, is a citrus fruit harvested in Korea, China, and Japan. Particularly in Korea, the fruit is commonly processed into beverages and herbal medicines due to its special avor and effectiveness against colds. Most parts of yuza fruit such as the peel, juice, and seeds have been used (Kim et al., 2004; Lan-Phi et al., 2009). The benecial health effects of avonoids in yuza such as antioxidant, anti-carcinogenic, anti-viral, and anti-inammatory activities have been reported (Fujihara & Shimizu, 2003; Kato-Noguchi & Tanaka, 2006; Yoo et al., 2004). A number of pesticides have been widely using for pest control in crops and fruits at various stages of cultivation. Pesticides are used for better yields and quality during post-harvest storage. However, pesticide residues are of concern, because these substances are potential health hazards (Soler et al., 2007; Taylor et al., 2002). In particular, pesticide residues may persist in plant tissues and appear in the pulp and juice of fruits and vegetables. Determining pesticide concentrations is important, as people who eat relatively large quantities of these foods are more at risk than others (Radiic, Grujic, Vasiljevic, & Lauevic, 2008). In Korea, the pesticides authorized by the Korea Crop Protection Association
Corresponding author. Tel.: +82 2 2260 3372; fax: +82 2260 3372.
E-mail address: kwglee@dongguk.edu (K.-G. Lee). 0308-8146/$ - see front matter 2012 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.foodchem.2012.06.111

for yuza production are chlorpyrifos, prothiofos, phosalone, deltamethrin, acequinocyl, spirodiclofen and carbendazim (Korea Crop Protection Association, 2006). Pesticide residue monitoring of fruits and vegetables has been conducted to conrm the proper use and exact concentrations of pesticides. Maximum residue limits (MRLs) have been established for agricultural products in many countries to avoid the health hazard caused by pesticide residues. Health safety limits for human health are typically expressed as acceptable daily intake (ADI). The standard method to evaluate human exposure is based on the average consumption per person per day, Korean average adult weight, and pesticide residue data (Park et al., 2010). Although many scientists have analyzed pesticide residues in various fruits, the analysis of pesticides in yuza has been carried out only by a few studies. Yamamoto, Nutahara, and Taniguchi (1982) reported acaricide residue on yuza fruits grown in vinyl houses. Goto et al. (2003) reported a simple and rapid method to identify pesticides in citrus fruits by electro-spray ionization tandem mass spectrometry. Micro-extraction procedures were compared to determine pesticides in oranges using liquid chromatographymass spectrometry by Blasco, Font, and Pic (2002). The objective of this study was to establish an analytical method for seven pesticides often used for yuza and to analyze the pesticide residue levels in yuza and yuza tea produced in Goheung, Korea. A risk assessment of pesticides in yuza tea was also

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conducted by determining the out estimated daily intake (EDI) and ADI. 2. Materials and methods 2.1. Chemicals and instruments Chlorpyrifos [CAS 2921-88], prothifos [CAS 34643-46-4], phosalone [CAS 2310-17-0], deltamethrin [CAS 52918-63-5], acequinocyl [CAS 57960-19-7], spirodichlofen [CAS 148477-71-8], and carbendazim [CAS 10605-21-7] were purchased from Sigma Aldrich (Germany) and stored at room temperature. Standard stock solutions of acequinocyl, spirodichlofen, and carbendazim were prepared by dissolving each analytical standard in methanol to a concentration of 100 lg/ml. In the case of chlorpyrifos, prothifos, phosalone and deltamethrin, they were dissolved in acetone to a concentration of 100 lg/ml. Solvents such as acetonitrile, methanol, distilled water and dichloromethane were purchased as HPLC grade from Burdick & Jackson (USA). A blender (HR2860, Philips, Netherlands), homogenizer (Model 17506, Omni Co., USA), and ultrasonic mixer (Model 8200, Branson Co., USA), were used to homogenize the samples. The shaker used in the extraction process was obtained from Jeio Tech (Korea). A rotary evaporator (Rotavapor R110, Buchi Co., USA) and an analytical nitrogen evaporator (Model S-040, Tokyo rikak Co., Japan) were used to evaporate solvents. A solid-phase extraction vacuum manifold (Supelco, Italy) was used for sample clean-up. 2.2. Sampling and storage Yuza sampling was conducted from October to November 2009. Eighty yuza samples, grown in Goheung, Korea, were placed in polyethylene bags and transported to the laboratory immediately after harvest and stored at -20 C. Yuza teas samples (n = 25) were collected from Hansung Food Inc., Goheung, Korea during 2009 and 2010. 2.3. Extraction and purication 2.3.1. Method 1: Chlorpyrifos, prothiofos, phosalone, and deltamethrin Extractions were carried out, in part, according to the method described in the Korea Food Code (Korea Food and Drug Administration, 2008). Samples were prepared three times as replicates. After grinding the yuza in a blender (HMF-985, Hanil Co., Seoul, Korea), a 20 g portion was weighed in a beaker and extracted with 150 ml acetone and 50 ml distilled water for 5 min in shaker (RS-1, Jeiotech, Daejon, Korea). The homogenized mixture was ltered through the Buchner funnel using Whatman No.4 lter paper and the ltrate was transferred to a separatory funnel. The separatory funnel was placed on a shaker for 5 min with 50 ml of petroleum ether, 50 ml of dichloromethane, and 50 ml of saturated sodium chloride (36 wt.%). The phases were then allowed to separate and the organic layer was passed through about 20 g anhydrous sodium sulfate into a round-bottom ask. The remaining aqueous layer was re-extracted with another 50 ml of dichloromethane, and the organic layer was drained through anhydrous sodium sulfate. The organic fraction was evaporated to dryness at <40 C by rotary evaporator (R-124, Buchi, Flawil, Swiss). Solid phase extraction (SPE) Florisil cartridges (1 g, volume: 6 ml, Phenomenex, Torrance, CA, USA) were used to extract the pesticides from the samples. Cartridges were activated and conditioned with 5 ml of hexane and 5 ml of hexane:acetone (20:80, v/v). Sample extracts were re-dissolved with 5 ml hexane and transferred to a Florisil cartridge, which was activated and conditioned. After sample loading, the cartridge was eluted with

5 ml of hexane:acetone (20:80, v/v). This solvent was evaporated slowly to dryness at 3540 C under a gentle stream of nitrogen. The dried residue was re-dissolved in 2 ml acetone for GC-NPD and GCMS analysis. Chlorpyrifos, prothiofos, and phosalone are analyzed by GC-NPD. Deltamethrin is analyzed by GCMS. 2.3.2. Method 2: Acequinocyl This sample preparation method was the same as method 1 before SPE. Silica cartridges (1 g, volume:6 ml, Sep-Pak,Waters, Milford, MA, USA) were activated and conditioned with 5 ml of hexane and 5 ml of hexane: ethyl ether: acetic acid (9:1:0.2, v/v/ v). Five ml of hexane were added to the sample. This mixture was then transferred to a silica cartridge, which was activated and conditioned. After loading the sample, the cartridge was eluted with 10 ml hexane: ethyl ether: acetic acid (8:2:0.2 v/v/v). This solvent was evaporated slowly to dryness at 3540 C under a gentle stream of nitrogen. The dried residue was re-dissolved in 2 ml methanol for HPLC-PDA analysis. 2.3.3. Method 3: Sporpdiclofen and carbendazim After grinding the yuza in a blender, a 20 g portion was weighed in a beaker. The sample was homogenized in 50 ml of acetonitrile and 50 ml of distilled water for 5 min. The homogenized mixture was ltered through the Buchner funnel using Whatman No.4 lter paper and the ltrate was transferred to a separatory funnel with 10 g sodium chloride and 50 ml distilled water. The separatory funnel was placed on a shaker for 5 min. The phases were allowed to separate, and the organic layer was passed though anhydrous sodium sulfate into a round-bottom ask. The organic fraction was evaporated to dryness at <40 C. SPE NH2 cartridges (1 g, 6 ml, Phenomenex) were used to extract pesticides from samples. Cartridges were activated and conditioned with 5 ml of dichloromethane and 5 ml of dichloromethane:methanol (8:2, v/v). Five ml of dichloromethane:methanol (8:2, v/v) was added to the sample and then transferred to a cartridge. After loading the sample, the cartridge was eluted with 5 ml of dichloromethane:methanol (8:2, v/v). This solvent was evaporated slowly to dryness at 35 40 C under a gentle stream of nitrogen. The dried residue was re-dissolved in 2 ml methanol for HPLC-PDA analysis. 2.4. Analytical method Gas chromatography (GC) analyses were carried out on an Agilent Technologies Model 6890 N gas chromatograph with nitrogen phosphorus detector (NPD) and auto-sampler (Model 7683). Data acquisition and analysis were performed with the G1035 Wiley Library. Separation was performed on a DB-5 capillary column (30 m 0.250 mm i.d 0.25 lm lm thickness, Agilent Technologies). The injection temperature was held at 260 C. The injection mode and volume were split mode and 1 ll, respectively. Helium was used as the carrier gas at a ow rate of 1.0 ml/min. The oven temperature program was initially 120 C (hold 2 min), increased to 220 C at 10 C/min, increased to 250 C at 7 C /min, and then to 280 C at 7 C /min (hold 15 min). The NPD temperature was maintained at 280 C. Gas chromatography/mass spectroscopy (GC/MS) analyses were carried out on an Agilent Technologies Model 6890 N gas chromatograph with a mass selective detector (Model 5975, Agilent Technologies). Data acquisition and analysis were performed with the Chemstation (Agilent Technologies). Deltamethrin separation was performed on a DB-5 MS capillary column (30 m 0.250 mm i.d 0.25 lm lm thicknesses, Agilent Technologies). The injection temperature was held at 260 C. The injection port was heated to 260 C, and the splitless injection mode was used. The injection volume was 2 ll. Helium was used as carrier gas at a ow rate of 1.0 ml/min. The oven temperature program initially consisted of

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120 C (hold 2 min), increased to 220 C at 10 C /min, increased to 250 C at 7 C /min, and then to 280 C at 7 C /min (hold 15 min). The high performance liquid chromatography (HPLC) was carried out on a Waters Instrument Model 1525 consisting of an auto-sampler (Model 717, Waters) and a photodiode array detector (Model 2998, Waters). A C18 column (Zorbax Eclipse XDB, Agilent Technologies, 4.6 250 mm, 5 lm particle size,) was used for separation at 40 C. The injection volume of the sample was 10 ll. Acequinocyl separation was carried out with water and acetonitrile (13%:77%) at a ow rate of 0.8 ml/min for 30 min. The UV absorbance of acequinocyl was monitored at 250 nm. Sprodiclofen and carbendazim separation was performed by gradient elution with water (A) and methanol (B) at a ow rate of 1.0 ml/min. Spirodiclofen and carbendazim UV absorbance were monitored at 254 nm and 279 nm, respectively. The gradient elution program was as follows: initial 50% A; 045 min, 10% A; and a 4550 min return to the initial conditions. Processing of the raw chromatographic data and data collection was performed using the Empower 2 Pro program (Waters, Milford, MA, USA). 2.5. Method validation Sample preparation was validated in terms of linearity, repeatability, limits of detection (LOD) quantication (LOQ), and recovery. The evaluation of linearity was conducted by injecting a solution containing six standard chemicals (0.02, 0.1, 0.5, 1.0, 5.0, and 10.0 lg/ml). All standards were injected three times (n = 3). LOD was measured as the analyte concentration based on signal to-noise ratio of 3, and LOQ was dened as 3.3 LOD. To determine the recovery of pesticide, each pesticide standard solution (10.0 lg/ml) was spiked to the homogenized sample. The recovery rate was calculated as (pesticide weight in spiked samplepesticide weight in unspiked sample) 100/spiking pesticide weight Harris 2001 The assay procedure was repeated ve times, and the relative standard deviation values were obtained within the same day to evaluate intra-day precision. To evaluate the interday precision this assay was carried out over ve different days. 3. Results and discussion 3.1. Method validation Seven pesticides (chlorpyrifos, prothiofos, phosalone, deltamethrin, acequinocyl, spirodiclofen, and carbendazim) were chosen because of their frequent use during yuza cultivation. The maximum residue levels (MRLs) for yuza are shown in Table 1. The slopes, correlation coefcient values, LOD, and LOQ are summarized in Table 1 for the validation study. An excellent linear correlation was observed between the pesticide concentration and peak areas, with coefcient correlations values of 0.97500.9999. Percent recoveries were 80.4109.9% for all pesticides. The standard deviation of recovery rate were <6.9%, suggesting that the

extraction procedure was suitable for routine analysis of the targeted pesticide residues. The LOQs of the method were 0.06 0.33 lg/ml. The intra-day variability was assayed at ve replications on the same day. For inter-day variability the assay was carried out during 5 sequential days to test the precision of each pesticide. The relative standard deviation (RSD) of intra-day and inter-day variability was <15.9% and 16.9%, respectively (Table 1). 3.2. Pesticide levels in yuza and yuza tea samples Detailed data on the pesticide levels detected in yuza are shown in Table 2. Chlorpyrifos, prothiofos, phosalone, and deltamethrin were not detected in any yuza samples. Acequinocyl was detected in ve samples in the concentration range of 0.070.15 lg/g (6.3%). Spirodiclofen was found in 38 samples (47.5%) in the concentration range of 0.111.89 lg/g. Carbendazim was detected in 52 samples (65.0%) in the concentration range of 0.035.15 lg/g. Monitoring of pesticide residues in yuza has not been performed, rather research on pesticides in orange samples has been reported several times. Han et al. (2002) reported that chlorpyrifos was detectable in mandarin at concentrations of 0.0040.041 lg/g. In addition, Blasco, Font, and Pic (2006) reported the presence of carbendarzim in some orange samples (range, 0.020.04 lg/g). Dogheim, Gad alla, and El-marsafy (1999) reported that dicofol, dimethoate, and vinclozoline are detectable in orange samples. Detailed pesticide levels detected in yuza tea are shown in Table 3. Three of the seven pesticide residues were found in the yuza tea samples produced in 2009. Chlorpyrifos, prothiofos, phosalone, and deltamethrin were not detected in any sample. The same results were found for the yuza tea samples produced in 2010. The detection frequency and levels of acequinocyl and spirodiclofen in the 2009 samples were higher than those of 2010. Besides, the detection frequency and levels of acequinocyl, spirodiclofen, and carbendazim in yuza samples were higher than those in the yuza tea samples. The number of detected samples, detection frequency, and concentrations of acequinocyl, spirodiclofen and carbendazim was 0.271.05 lg/g in 2009 (seven samples, 14.0%), 0.130.29 lg /g (ve samples, 10.0%) and 0.502.36 lg /g (13 samples, 26.0%), respectively. In contrast, only acequinocyl and carbendazim were detected in the yuza tea samples in 2010. In particular, carbendazim was detected in eight samples in the concentration range of 0.170.45 lg /g. Acequinocyl was detected in one sample (0.18 lg /g). The most frequently detected pesticide in yuza and yuza tea during the 2 years was carbendazim. However, all the pesticide residues of the samples were lower than their respective MRLs. 3.3. Risk assessment An exposure evaluation was conducted based on monitoring the results of the pesticide residue to determine the degree of risk by the detected pesticide residues in samples. Risk assessments were

Table 1 Validation parameters such as linearity, limit of detection (LOD), limit of quantication (LOQ), and recoveries of pesticides used during yuza cultivation. Pesticides Linearity Range (lg/ml) Chlorpyrifos Prothiofos Phosalone Deltamethrin Acequinocyl Spirodiclofen Carbendazim
1 2

LOD Equation y = 16.682x-0.9356 y = 18.722x-2.7729 y = 18.116x-2.9475 y = 22180x-72217 y = 7773x-3737 y = 11818x-7.3200 y = 42955x-560.10 Correlation coefcient (r ) 0.9992 0.9972 0.9974 0.9750 0.9999 0.9999 0.9999
2

LOQ (lg/ml) 0.06 0.10 0.06 0.06 0.33 0.10 0.06

MRL1 (lg/g) 0.5 2.0 0.05 0.5 0.1/3.0a 2.0 7.0

Recovery(%)

Precision2 (%) Intra-day (n = 5) Inter-day (n = 5) 9.4 5.9 11.3 6.5 6.9 7.2 16.9

(lg/ml) 0.02 0.03 0.02 0.02 0.10 0.03 0.02

0.0210 0.0210 0.0210 0.0210 0.0210 0.0210 0.0210

109.9 3.9 99.4 4.2 96.0 3.9 103.2 5.9 93.8 6.9 93.2 2.7 80.4 5.8

10.0 10.3 8.8 6.4 15.9 12.1 14.8

Maximum Residue level. Relative standard deviation (RSD:%) of recovery rates from intra-day (n = 5) and inter-day (n = 5) experiments.

K.-G. Lee, S.-K. Lee / Food Chemistry 135 (2012) 29302933 Table 2 The levels of pesticides in yuza samples (n = 80). Compound Chlorpyrifos Prothiofos Phosalone Deltamethrin Acequinocyl Spirodiclofen Carbendazim ND, not detected. Detection range (lg/g) ND ND ND ND 0.070.15 0.111.89 0.035.15 Frequency (%) 6.3 47.5 65.0 Mean (lg /g) 0.12 0.48 2.92

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Acknowledgements This research was supported by iPET(Korea Institute of Planning and Evaluation for Technology in Food, Agriculture, Forestry and Fisheries), Ministry for Food, Agriculture, Forestry and Fisheries, Republic of Korea. Yuza and yuza tea samples were kindly provided by Hansungfood Company (Goheung, Korea), and we appreciate their donation. References
Blasco, C., Font, G., & Pic, Y. (2002). Comparison of microextraction procedures to determine pesticides in oranges by liquid chromatographymass spectrometry. Journal of Chromatography A, 970, 201212. Blasco, C., Font, G., & Pic, Y. (2006). Evaluation of 10 pesticide residues in oranges and tangerines from Valencia (Spain). Food Control, 17, 841846. Chun, O. K., & Kang, H. G. (2003). Estimation of risks of pesticide exposure, by food intake, to Koreans. Food and Chemical Toxicology, 41, 10631076. Dogheim, S. M., Gad alla, S. A., & El-marsafy, A. M. (1999). Monitoring pesticide residues in Egyptian fruits and vegetables in 1995. Journal of AOAC International, 82, 948955. Fujihara, S., & Shimizu, T. (2003). Growth inhibitory effect of peel extract from Citrus junos. Journal of Plant Growth Regulation, 39, 223233. Goto, T., Ito, Y., Oka, H., Saito, I., Matsumoto, H., & Nakazawa, H. (2003). Simple and rapid determination of N-methylcarbamate pesticides in citrus fruits by electrospray ionization tandem mass spectrometry. Analytica Chimica Acta, 487, 201209. Han, K. T., Park, H. J., Lee, K. S., Kim, I. J., Kim, K. S., & Cho, S. M. (2002). Pesticide residue survey and risk assessment of fruits in Daejeon Korean. Korean Journal of Environmental Agriculture, 21, 279285. Harris, D. C. (2001). Exploring chemical analysis (3rd ed.). New York: W.H. Freeman [Chapter 5]. Kato-Noguchi, H., & Tanaka, Y. (2006). Abscisic acid-glucose ester as an allelopathy agent from citrus fruit. Acta Physiologias Plantrum, 28, 635639. KCPA (Korea Crop Protection Association) (2006). Application for pesticide use guide book. Korea Crop Protection Association. http://koreacpa.org/new/ sub.html?sub=2. KFDA (Korea Food and Drug Administration) (2008). Korean food code. Korea Food and Drug Administration. http://www.foodnara.go.kr/portal/site/kfdaportal/ infotelegram/. Kim, S. H., Choe, W. J., Baik, Y. K., & Kim, W. S. (2008). Monitoring of pesticide residues and risk assessment of agricultural products consumed in South Korea. Journal of the Korean Society of Food Science and Nutrition, 37, 15151522. Kim, W. C., Lee, D. Y., Lee, C. H., & Kim, C. W. (2004). Optimization of narirutin extraction during washing step of the pectin production from citrus peels. Journal of Food Engineering, 63, 191197. Lan-Phi, N. T., Shimamura, T., Ukeda, H., & Sawamura, M. (2009). Chemical and aroma proles of yuza (Citrus junos) peel oils of different cultivars. Food Chemistry, 115, 10421047. Lee, H. J., Choe, W. J., Lee, J. Y., Cho, D. H., Kang, C. S., & Kim, W. S. (2009). Monitoring of ergosterol biosynthesis inhibitor (EBI) pesticide residues in commercial agricultural products and risk assessment. Journal of the Korean Society of Food Science and Nutrition, 37, 17791784. Park, B. J., Son, K. A., Paik, M. K., Kim, J. B., Hong, S. M., Im, G. J., & Hong, M. K. (2010). Monitoring of neonicotinoid pesticide residues in fruit vegetable and human exposure assessment. Korean Journal of Pesticide Science, 14, 104109. Radiic, M., Grujic, S., Vasiljevic, T., & Lauevic, M. (2008). Determination of selected pesticides in fruit juices by matrix solid-phase dispersion and liquid chromatographytandem mass spectrometry. Food Chemistry, 113, 712719. Soler, C., James, K. J., & Pico, Y. (2007). Capabilities of different liquid chromatography tandem mass spectrometry systems in determining pesticide residues in food. Application to estimate their daily intake. Journal of Chromatography A, 1157, 7384. Taylor, M. J., Hunter, K., Hunter, K. B., Lindsay, D., & Le Bouhellec, S. (2002). Multiresidue method for rapid screening and conrmation of pesticides in crude extracts of fruits and vegetables using isocratic liquid chromatography with electro spray tandem mass spectrometry. Journal of Chromatography A, 982, 225236. Yamamoto, M., Nutahara, M., & Taniguchi, H. (1982). Residue of acaricides on fruits of yuzu (Citrus junos Sieb. ex Tanaka) grown in vinyl-houses. Proceedings of the Association for Plant Protection of Shikoku, 17, 2934. Yoo, K. M., Lee, K. W., Park, J. B., Lee, H. J., & Hwang, I. K. (2004). Variation in major antioxidants and total antioxidant activity of yuza (Citrus junos Sieb ex Tanaka) during maturation and between cultivars. Journal of Agricultural Food Chemistry, 52, 59075913.

Table 3 The concentrations of pesticides in yuza tea samples. Compound Detection range (lg /g) 2009 (n = 50) Chlorpyrifos Prothiofos Phosalone Deltamethrin Acequinocyl Spirodiclofen Carbendazim ND, not detected. ND ND ND ND 0.271.05 0.130.29 0.502.36 2010 (n = 25) ND ND ND ND 0.18 ND 0.170.45 Frequency (%) 2009 14 10 26 2010 4 32 Mean (lg /g) 2009 0.69 0.20 0.41 2010 0.18 0.32

Table 4 Exposure assessment parameters of pesticides in yuza tea samples. Pesticide Acequinocyl Spirodiclofen Carbendazim
a b c

ALDa (mg/kg) 0.4271 0.2040 1.1293

EDIb (mg/day) 0.36541 0.17453 0.96592

EDI/ADIc100 24.6 22.7 58.5

average level of detection. estimated daily intake. acceptable daily intake.

performed using the EDI and the ADI. The EDI was calculated from the average consumption per person per day and the pesticide residues data. The percent EDI to ADI ratio was calculated as (EDI/ ADE) 100 and ADE (acceptable dietary exposure) was calculated as ADI (mg/kg) Korean average adult weight (55 kg) Lee et al. 2009; Kim et al., 2008). The results of human exposure to pesticides based on yuza tea intake are shown in Table 4. The EDIs of acequinocyl, spirodiclofen, and carbendazim were 6.6438 103, 3.1733 103, and 1.7562 102 mg/day, respectively. The percent ratios of EDI to ADI for acequinocyl, spirodiclofen and carbendazim were 24.6, 22.7, and 58.5%, respectively. Results exceeding 100% indicate a risk potential (Chun & Kang, 2003). Therefore, the results of this research indicate that the detected pesticides are not harmful to humans. Although the results show a negligible risk associated with exposure via yuza tea consumption, a special precaution should be taken with the possible total exposure to these chemicals from various foods in the future. Monitoring of the pesticide residue data in yuza has not been performed. Therefore, it is necessary to monitor the residues of acequinocyl, spirodiclofen, and carbendazim in yuza continuously because of possible health effects, widespread use, and insufcient residue data. Additionally, further monitoring studies must be performed to improve food safety.