茶葉高氯酸鹽污染及分析技術

鄧家軍，潘華，張富生，張莉，曹芳，張志芳，陳俊松

茶葉高氯酸鹽污染及分析技術

鄧家軍1,2，潘華1,2，張富生1,2，張莉1,2，曹芳1,2，張志芳1,2，陳俊松3

1. 江西省農(nóng)產(chǎn)品質(zhì)量安全檢測中心，江西 南昌 330046；2. 農(nóng)業(yè)部農(nóng)產(chǎn)品質(zhì)量安全風險評估實驗室（南昌），江西 南昌 330046；3. 九江市農(nóng)產(chǎn)品質(zhì)量安全監(jiān)測中心，江西 九江 332000

高氯酸鹽是茶葉中的一種新型污染物，對茶葉產(chǎn)品質(zhì)量安全、人體健康和對外貿(mào)易構成了潛在風險，已引起了國內(nèi)外越來越多的關注。本文綜述了茶葉中高氯酸鹽的來源及污染現(xiàn)狀，介紹了茶葉中高氯酸鹽的分析技術，以期為開展高氯酸鹽環(huán)境化學行為、農(nóng)產(chǎn)品質(zhì)量安全、人體健康風險及其相關安全標準等方面的研制提供借鑒。

茶葉；高氯酸鹽；污染；分析技術

1.1 環(huán)境中污染來源

1.1.1 自然來源

1.1.2 人為生產(chǎn)

1.2 環(huán)境中污染狀況

2 茶葉中的污染

2.1 茶葉中污染現(xiàn)狀

2.2 茶葉中污染來源

3.1 IC法

3.2 IC-MS/MS法

表1 文獻報道過的方法比較

注：NR：未見報道

Note: NR: not reported

3.3 LC-MS/MS法

4 結語

[1] 梅宇. 2014年中國茶葉產(chǎn)銷報告及2015年形勢預測[J]. 茶世界, 2015(6): 50-59.

[2] 梅宇, 王智超. 2016全國春茶產(chǎn)銷形勢分析報告[J]. 茶世界, 2016(6): 40-49.

[3] 梅宇. 2016年中國茶業(yè)經(jīng)濟形勢簡報[J]. 茶世界, 2017(2): 14-18.

[4] 梅宇, 王智超, 林璇. 2017年全國春茶產(chǎn)銷形勢分析報告[J]. 茶世界, 2017(5): 14-22.

[5] 陳宗懋. 我國茶產(chǎn)業(yè)質(zhì)量安全和環(huán)境安全問題研究[J]. 農(nóng)產(chǎn)品質(zhì)量與安全, 2011(3): 5-7.

[6] 韓文炎, 魯成銀, 劉新. 我國茶葉在種植環(huán)節(jié)的質(zhì)量安全問題及對策[J]. 食品科學技術學報, 2014, 32(2): 12-15.

[7] 劉新, 張穎彬, 潘蓉, 等. 我國茶葉加工過程的質(zhì)量安全問題及對策[J]. 食品科學技術學報, 2014, 32(2): 16-19.

[8] European Commission. Statement as regards the presence ofperchlorate in food endorsed by the Standing Committee on Plants, Animals, Food and Feed on 10 March 2015, updated on 23 June 2015 [EB/OL]. (2015-06-23)[2018-09-10]. https://ec.europa.eu/food/sites/food/files/safety/docs/cs_con taminants_catalogue_perchlorate_statement_food_update_en.pdf .

[9] Leung A M, Pearce E N, Braverman L E. Perchlorate, iodine and the thyroid [J]. Best Practice & Research Clinical Endocrinology & Metabolism, 2010, 24(1): 133-141.

[10] Blount B C, Pirkle J L, Osterloh J D, et al.Urinary perchlorate and thyroid hormone levels in adolescent and adult men and women living in the United States [J]. Environmental Health Perspectives, 2006, 114(12): 1865-1871.

[11] EFSA Panel on Contaminants in the Food Chain (CONTAM). Scientific opinion on the risks to public health related to the presence of perchlorate in food, in particular fruits and vegetables [J]. EFSA Journal, 2014, 12(10), 3869. https://doi.org/10.2903/j.efsa.2014.3869.

[12] Acevedo-Barrios R, Sabater-Marco C, Olivero-Verbel J. Ecotoxicological assessment of perchlorate usingandassays [J]. Environmental Science & Pollution Research International, 2018, 25(14): 13697-13708.

[13] USEPA. Announcement of the Drinking Water Contaminant Candidate List. Notice [J]. Federal Regist, 1998, 63(40): 10273-10287.

[14] Kannan K, Praamsma M L, Oldi J F, et al. Occurrence of perchlorate in drinking water, groundwater, surface water and human saliva from India [J]. Chemosphere, 2009, 76(1): 22-26.

[15] Kumarathilaka P, Oze C, Vithanage M. Perchlorate mobilization of metals in serpentine soils [J]. Applied Geochemistry, 2016, 74: 203-209

[16] Kumarathilaka P, Oze C, Indraratne S P, et al. Perchlorate as an emerging contaminant in soil, water and food[J]. Chemosphere, 2016, 150: 667-677.

[17] Calderón R, Godoy F, Escudey M, et al. A review of perchlorate (ClO4－) occurrence in fruits and vegetables [J]. Environmental Monitoring & Assessment, 2017, 189(2): 82. https://doi.org/10.1007/s10661-017-5793-x.

[18] Lee S Y, Mccarthy A M, Stohl H E, et al. Urinary iodine, perchlorate, and thiocyanate concentrations in U.S. lactating women [J]. Thyroid, 2017, 27(12): 1574-1581.

[19] Zhang T, Wu Q, Sun H W, et al. Perchlorate and iodide in whole blood samples from infants, children, and adults in Nanchang, China [J]. Environmental Science & Technology, 2010, 44(18): 6947-6953.

[20] Qin X, Zhang T, Gan Z, et al. Spatial distribution of perchlorate, iodide and thiocyanate in the aquatic environment of Tianjin, China [J]. Environmental source analysis, Chemosphere, 2014, 111: 201-208.

[21] Wan Y, Wu Q, Abualnaja K O, et al. Occurrence of perchlorate in indoor dust from the United States and eleven other countries: Implications for human exposure [J]. Environment International, 2015, 75: 166-171.

[22] Jackson W A, B?hlke J K, Gu B, et al. Isotopic composition and origin of indigenous natural perchlorate an co-occurring nitrate in the Southwestern United States [J]. Environmental Science & Technology, 2010, 44(13): 4869-4876.

[23] Rao B, Anderson T A, Redder A, et al. Perchlorate formation by ozone oxidation of aqueous chlorine/oxy-chlorine species: Role of ClxOyradicals [J]. Environmental Science & Technology, 2010, 44(8): 2961-2967.

[24] Rao B, Estrada N, McGee S, et al. Perchlorate production by photodecomposition of aqueous chlorine solutions [J]. Environmental Science & Technology, 2012, 46(21): 11635-11643

[25] Kang N, Jackson W A, Dasgupta P K, et al. Perchlorate production by ozone oxidation of chloride in aqueous and dry systems [J]. Science of the Total Environment, 2008, 405(1/3): 301-309.

[26] Jiang S, Li, Y S, Sun B. Determination of trace level of perchlorate in Antarctic snow and ice by ion chromatography coupled with tandem mass spectrometry using an automated sample on-line preconcentration method [J]. Chinese Chemical Letters, 2013, 24(4): 311-314.

[27] Duncan P B, Morrison R D, Vavricka E. Forensic identification of anthropogenic and naturally occurring sources of perchlorate [J]. Environmental Forensics, 2005, 6(2): 205-215.

[28] Michalski J, B?hlke J K, Thiemens M. Long-term atmospheric deposition as the source of nitrate and other salts in the Atacama Desert, Chile: New evidence from mass-independent oxygen isotopic compositions [J]. Geochimica et Cosmochimica Acta, 2004, 68(20): 4023-4038.

[29] Wu C, Sullivan K, Chowdhury S, et al. Encapsulation of perchlorate salts within metal oxides for application as nanoenergetic oxidizers [J]. Advanced Functional Materials, 2012, 22(1): 78-85.

[30] Wilkin R T, Fine D D, Burnett N G. Perchlorate behavior in a municipal lake following fireworks displays [J]. Environmental Science & Technology, 2007, 41(11): 3966-3971.

[31] Shi Y L, Zhang N, Gao J M, et al. Effect of fireworks display on perchlorate in air aerosols during the Spring Festival [J]. Atmospheric Environment, 2011, 45(6): 1323-1327.

[32] Isobe T, Ogawa S P, Sugimoto R, et al. Perchlorate contamination of groundwater from fireworks manufacturing area in South India [J]. Environmental Monitoring and Assessment, 2013, 185(7): 5627-5637.

[33] Urbansky E T, Brown S K, Magnuson M L, et al. Perchlorate levels in samples of sodium nitrate fertilizer derived from Chilean caliche [J]. Environ Pollut, 2001, 112(3): 299-302

[34] Susarla S, Collette T W, Garrison A W, et al. Perchlorate identification in fertilizers [J]. Environmental Science & Technology, 1999, 33(19): 3469-3472.

[35] Massachusetts Department of Environmental Protection. The occurrence and sources of perchlorate in Massachusetts—Draft report [EB/OL]. (2006-04)[2018-09-10].http://www.mass.gov/eea/docs/dep/cleanup/sites/percsour.pdf.

[36] Barron L, Nesterenko P N, Paull B. Rapid on-line preconcentration and suppressed micro-bore ion chromatography of part per trillion levels of perchlorate in rainwater [J]. Anal Chim Acta, 2006, 567(1): 127-134.

[37] Furdui V, Tomassini F. Trends and sources of perchlorate in Arctic snow [J]. Environmental Science & Technology, 2010, 44(2): 588-592.

[38] Parker D R, Seyfferth A L, Reese B K. Perchlorate in groundwater: a synoptic survey of “pristine” sites in the coterminous United States [J]. Environmental Science & Technology, 2008, 42(5): 1465-1471.

[39] Ji G L, Kong X L. Adsorption of chloride, nitrate and perchlorate by variable charge soils [J]. Pedosphere. 1992, 2(4): 317-326.

[40] Urbansky E T, Brown S K. Perchlorate retention and mobility in soils [J]. Journal of Environmental Monitoring, 2003, 5(3): 455-462.

[41] Tipton D K, Rolston D E, Scow K M. Transport and biodegradation of perchlorate in soils [J]. Journal of Environmental Quality 2003, 32(1): 40-46.

[42] Gan Z, Sun H, Wang R, et al. Occurrence and exposure evaluation of perchlorate in outdoor dust and soil in mainland China [J]. Science of the Total Environment, 2014, 470/471: 99-106.

[43] Ye L, You H, Yao J, et al. Seasonal variation and factors influencing perchlorate in water, snow, soil and corns in Northeastern China [J]. Chemosphere, 2013, 90(10): 2493-2498.

[44] Qin X, Zhang T, Gan Z, et al. Spatial distribution of perchlorate, iodide and thiocyanate in the aquatic environment of Tianjin, China: Environmental source analysis [J]. Chemosphere, 2014, 111: 201-208.

[45] Wu Q, Zhang T, Sun H, et al. Perchlorate in tap water, groundwater, surface waters, and bottled water from China and its association with other inorganic anions and with disinfection byproducts [J]. Archives of Environmental Contamination and Toxicology, 2010, 58(3): 543-550.

[46] Smith P N, Yu L, McMurry S T et al. Perchlorate in water, soil, vegetation, and rodents collected from the Las Vegas Wash, Nevada, USA [J]. Environmental Pollution, 2004, 132(1): 121-127.

[47] Kim D H, Yoon Y, Baek K, et al. Occurrence of perchlorate in rice from different areas in the Republic of Korea [J]. Environmental Science and Pollution Research, 2014, 21(2): 1251-1257.

[48] Seyfferth A L, Sturchio N C, Parker D R. Is perchlorate metabolized or re-translocated within lettuce leaves? A stable isotope approach [J]. Environmental Science & Technology, 2008, 42(24): 9437-9442.

[49] Seyfferth A L, Henderson M K, Parker D R. Effects of common soil anions and pH on the uptake and accumulation of perchlorate in lettuce [J]. Plant Soil, 2008, 302(1/2): 139-148.

[50] Yu L, Canas J E, Cobb G P, et al. Uptake of perchlorate in terrestrial plants [J]. Ecotoxicology and Environmental Safety, 2004, 58(1): 44-49.

[51] Yifru D D, Nzengung V A. Uptake of perchlorate by vegetation growing at field sites in arid and subhumid climates [J]. Remediation Journal, 2007, 17(4): 53-68.

[52] Sanchez C A, Crump K S, Krieger R I, et al. Perchlorate and nitrate in leafy vegetables of North America [J]. Environmental Science & Technology, 2005, 39(24): 9391-9397.

[53] Yang M, Her N. Perchlorate in soybean sprouts (L. Merr.), water dropwort (DC), and lotus (Gaertn.) root in South Korea [J]. Journal of Agricultural and Food Chemistry, 2011, 59(13): 7490-7495.

[54] 陳桂葵, 駱世明, 杜寧寧, 等. 高氯酸鹽對水稻生理生態(tài)的影響及其在稻田系統(tǒng)中的分布規(guī)律[J]. 農(nóng)業(yè)環(huán)境科學學報, 2011, 30(11): 2137-2144.

[55] Jackson W A, Joseph P, Laxman P, et al. Perchlorate accumulation in forage and edible vegetation [J]. Journal of Agricultural and Food Chemistry, 2005, 53(2): 369-373.

[56] Seyfferth A L, Parker D R. Effects of genotype and transpiration rate on the uptake and accumulation of perchlorate (ClO4-) in lettuce [J]. Environmental Science & Technology, 2007, 41(9): 3361-3367.

[57] Seyfferth A L, Sturchio N C, Parker D R. Is perchlorate metabolized or re-translocated within lettuce leaves? A stable isotope approach [J]. Environmental Science & Technology, 2008, 42(24): 9437-9442.

[58] 陳東, 范賽, 沙博郁, 等. 同位素標記－超高效液相色譜－串聯(lián)質(zhì)譜法測定茶葉中的高氯酸鹽[J]. 中國衛(wèi)生檢驗雜, 2017, 27(16): 2298-2300.

[59] 華永有, 李宇翔, 林宏琳, 等. 茶葉中高氯酸鹽檢測與污染情況分析[J]. 海峽預防醫(yī)學雜志, 2018, 24(1): 4-6, 12.

[60] Liu Y, Sun H Z, Zhou L, et al. Quantitative determination and contamination pattern of perchlorate in tea by ultra performance liquid chromatography and tandem mass spectrometry [J]. Food Chemistry. 2019, 274: 180-186.

[61] 鄧家軍, 張莉, 廖健, 等. 茶葉中高氯酸鹽健康風險研究[J]. 鄉(xiāng)村科技, 2016(36): 42.

[62] S?b? A, Popek R , Nawrot B, et al. Plant species differences in particulate matter accumulation on leaf surfaces [J]. Science of the Total Environment, 2012, 427/428: 347-354.

[63] 郭夢媚, 郭勝利, 周佳雯, 等. 江西省植被NDVI變化及其對氣候變化的響應[J]. 江蘇農(nóng)業(yè)科學, 2015, 43(11): 421-426.

[64] Collette T W, Williams T L, Urbansky E T., et al. Analysis of hydroponic fertilizer matrixes for perchlorate: comparison of analytical techniques [J]. Analyst, 2003, 128(1): 88-97.

[65] 中華人民共和國國家質(zhì)量監(jiān)督檢驗檢疫總局. SN/T 4089—2015出口食品中高氯酸鹽的測定[S]. 北京: 中國標準出版社, 2015.

[66] 孟維偉. 茶葉中高氯酸鹽的檢測——離子色譜法[J]. 輕工科技, 2016, 32(11): 12-13.

[67] U.S. Food and Drug Administration (FDA). Rapid determination of perchlorate anion in foods by ion chromatography-tandem mass spectrometry. Version 2[EB/OL]. (2005-04-12)[2018-09-10]. https://www.fda.gov/Food/FoodborneIllnessContaminants/ChemicalContaminants/ucm077793.html.

[68] 劉小芳, 方從容, 劉慧, 等. 離子色譜-串聯(lián)質(zhì)譜法檢測茶葉中的高氯酸鹽[J]. 色譜, 2016, 34(10): 986-988.

[69] 赫優(yōu)訊. 賽默飛發(fā)布茶葉中高氯酸鹽的檢測方案[J]. 中國儀器儀表, 2016(2): 18.

[70] Hepperle J, Wolheim A, Kohlberg D, et al. Analysis of perchlorate in food samples of plant origin applying the QuPPe-method and LC-MS/MS [J]. Aspects of Food Control and Animal Health, 2013(2): 1-16.

[71] 馮德建, 鄒燕, 史謝飛, 等. 茶葉中高氯酸鹽的液相色譜-串聯(lián)質(zhì)譜測定方法研究[J]. 中國測試, 2016, 42(4): 1-4.

[72] 李雨哲, 楊杰, 王雨昕, 等. 同位素稀釋-超高效液相色譜-串聯(lián)質(zhì)譜法測定茶葉中的高氯酸鹽[J]. 中國食品衛(wèi)生雜志, 2016, 28(5): 616-619.

[73] 陳東, 范賽, 沙博郁, 等. 超高效液相色譜-串聯(lián)質(zhì)譜法測定茶葉中高氯酸鹽[J]. 食品安全質(zhì)量檢測學報, 2018, 9(4): 925-929.

[74] 宋正規(guī), 張書芬, 周子焱, 等. 超高效液相色譜-串聯(lián)質(zhì)譜同時測定茶葉中高氯酸鹽和氯酸鹽[J]. 茶葉科學, 2017, 37(6): 597-604.

Perchlorate Contamination in Tea andIts Analytical Techniques

DENG Jiajun1,2, PAN Hua1,2, ZHANG Fusheng1,2, ZHANG Li1,2,CAO Fang1,2, ZHANG Zhifang1,2, CHEN Junsong3

1.Testing Center of Agro-Product Quality and Safety of Jiangxi Province, Nanchang 330046, China;2. Laboratory of Quality and Safety Risk Assessment for Agro-products (Nanchang), Ministry of Agriculture, Nanchang 330046, China;3. Monitoring Center of Agro-Product Quality and Safety of Jiujiang City, Jiujiang 332000, China

Perchlorate in tea, as an emerging contaminant, poses a potential risk for food safety, human health and foreign trade, which has raised increasing concerns over the contamination of tea with perchlorate. In this paper, pollution sources, status and the main causes of pollution in tea of perchlorate were described. The analytical techniques of perchloratein tea samples were also summarized. These data would provide references for studies of environmental transport behaviors, agri-food safety, human health risk and relevant standards of security in China.

tea, perchlorate, contamination, analytical techniques

S571.1；TS201.6

A

1000-369X(2019)04-372-10

2018-09-10

2018-12-12

農(nóng)業(yè)部農(nóng)產(chǎn)品質(zhì)量安全風險評估項目（GJFP201700503、GJFP201800503）

鄧家軍，男，博士，主要從事農(nóng)產(chǎn)品質(zhì)量安全風險評價、污染生態(tài)修復等方面的研究，E-mail: dengjj2118@163.com