蔬菜中DEHP含量分析及冬瓜累积DEHP初探
摘要
DEHP(邻苯二甲酸二乙基己酯)为酞酸酯类化合物,是增塑剂的主要品种。由于酞酸酯类化合物与塑料成分之间不是化学键结合,易于从塑料中转移至外环境,造成对空气、水和土壤的污染,甚至可通过塑料桶溶入桶装食用油中,造成对食品的污染。每年有约100吨邻苯二甲酸二乙基己酯(DEHP)以不同的方式进入大气圈、水圈与土壤环境中,部分动植物体内累积较大量的DEHP,可能对人体健康造成危害。本文对蔬菜DEHP进行了分析研究。
首先,建立了一种基于UPLC技术的DEHP快速检测方法,该方法有分离效果好、线性范围宽、速度快、定量准确等优点,可用于实际样品中DEHP分析。其次,测定了冬瓜、黄瓜、长瓜、空心菜、大白菜等30多种蔬菜DEHP的含量,发现冬瓜含DEHP量在560—1580mg/kg;黄瓜含DEHP量在15—120mg/kg;长瓜的DEHP含量在10—16mg/kg;空心菜、大白菜则检测出0.17—3.4mg/kg的DEHP含量。其它蔬菜苦瓜、丝瓜、茄子、西红柿、豇豆、刀豆、四季豆、青椒、菜椒、青菜、茼蒿、菠菜、甘蓝菜(白)、甘蓝菜(紫)、香菜、花椰菜(白)、花椰菜(绿)、奉化芋艿、小芋艿、洋葱、萝卜、胡萝卜、生姜、大蒜、芦笋、茭白、大葱则未检测出DEHP或仅有痕量DEHP存在。然后研究了土壤DEHP浓度对冬瓜累积DEHP的影响,发现冬瓜地上部分各部位累积DEHP的量与土壤中DEHP的含量呈正相关,但土壤无DEHP处理且与其它DEHP处理无隔离的冬瓜植株也累积DEHP,表明冬瓜根系可能没有主动吸收DEHP并输送到地上部分的能力,冬瓜地上部分的DEHP可能主要是吸收累积大气中的DEHP所致。另外,还探讨了地膜覆盖冬瓜植株的不同部位累积DEHP的量,得出叶内累积最多,其次为茎和果中,根和花中累积较少,而地膜覆盖下土壤中并未检出DEHP。从累积分布来看,冬瓜植株各部位能从大气中吸收DEHP,同时可能存在叶茎果实中的运输转移。
本文所取得的研究结果,揭示了我国主要蔬菜受DEHP污染的状况,可为蔬菜食品安全评价提供依据。而土壤DEHP浓度、地膜覆盖致冬瓜累积DEHP的研究结果,可为冬瓜DEHP污染的解决提供科学依据。
DEHP [Di-(2-ethylhexyl) Phthalate] is one of the phthalic ester compounds and is a primary plasticizer. It easily releases to environment and pollutes air, water and soil. Some plants and animals cumulate it with an amount that harms human being. All people have to eat vegetables. So the analysis of DEHP content in vegetables is urgent.
In the present paper, a DEHP determination method based on UPLC was established and DEHP content in 36 vegetables was determined. The results showed waxgourd (the fruit of Benincasa hispida) contain DEHP with an amount of 560-1580mg/kg 10-16mg/kg, cucumber 15-120mg/kg, the fruit of Lagenaria siceraria 10-16mg/kg, Ipomoea aquatica and cabbage 0.17—3.4mg/kg. Balsam pear, towel gourd, auberqine, tomato, cowpea, sword bean, kidney bean, green pepper, green qrocery, chrysanthemum coronarium, spinach, pickled cabbage (white), pickled cabbage (purple), caraway, cauliflower (white), cauliflower (green), murphy, onion, radish, carrot, rhizoma zingiberis recens, garlic, asparaqus, zizania aquatica and scallion did not contain DEHP or only contain a trace amount of DEHP. The study on the effect of DEHP concentration in soil on the cumulation amount of Benincasa hispida showed that the higher the concentration, the higher content in the plant. But Benincasa hispida planted in the soil without DEHP treatment also contained DEHP. A high DEHP content also found in the Benincasa hispida that was planted in the field covered with plastic film. Therefore, the DEHP in Benincasa hispida possibly cumulated from the air DEHP which was released by treated soil or plastic film.
The above results reveal the pollution condition of DEHP in main vegetables in Hangzhou market, which provide us a reference of food safety. And the investigation of the effect of DEHP concentration in soil and plastic film on DEHP cummulation in Benincasa hispida could help us to solve the problem of high DEHP content in waxgourd.
首先,建立了一种基于UPLC技术的DEHP快速检测方法,该方法有分离效果好、线性范围宽、速度快、定量准确等优点,可用于实际样品中DEHP分析。其次,测定了冬瓜、黄瓜、长瓜、空心菜、大白菜等30多种蔬菜DEHP的含量,发现冬瓜含DEHP量在560—1580mg/kg;黄瓜含DEHP量在15—120mg/kg;长瓜的DEHP含量在10—16mg/kg;空心菜、大白菜则检测出0.17—3.4mg/kg的DEHP含量。其它蔬菜苦瓜、丝瓜、茄子、西红柿、豇豆、刀豆、四季豆、青椒、菜椒、青菜、茼蒿、菠菜、甘蓝菜(白)、甘蓝菜(紫)、香菜、花椰菜(白)、花椰菜(绿)、奉化芋艿、小芋艿、洋葱、萝卜、胡萝卜、生姜、大蒜、芦笋、茭白、大葱则未检测出DEHP或仅有痕量DEHP存在。然后研究了土壤DEHP浓度对冬瓜累积DEHP的影响,发现冬瓜地上部分各部位累积DEHP的量与土壤中DEHP的含量呈正相关,但土壤无DEHP处理且与其它DEHP处理无隔离的冬瓜植株也累积DEHP,表明冬瓜根系可能没有主动吸收DEHP并输送到地上部分的能力,冬瓜地上部分的DEHP可能主要是吸收累积大气中的DEHP所致。另外,还探讨了地膜覆盖冬瓜植株的不同部位累积DEHP的量,得出叶内累积最多,其次为茎和果中,根和花中累积较少,而地膜覆盖下土壤中并未检出DEHP。从累积分布来看,冬瓜植株各部位能从大气中吸收DEHP,同时可能存在叶茎果实中的运输转移。
本文所取得的研究结果,揭示了我国主要蔬菜受DEHP污染的状况,可为蔬菜食品安全评价提供依据。而土壤DEHP浓度、地膜覆盖致冬瓜累积DEHP的研究结果,可为冬瓜DEHP污染的解决提供科学依据。
DEHP [Di-(2-ethylhexyl) Phthalate] is one of the phthalic ester compounds and is a primary plasticizer. It easily releases to environment and pollutes air, water and soil. Some plants and animals cumulate it with an amount that harms human being. All people have to eat vegetables. So the analysis of DEHP content in vegetables is urgent.
In the present paper, a DEHP determination method based on UPLC was established and DEHP content in 36 vegetables was determined. The results showed waxgourd (the fruit of Benincasa hispida) contain DEHP with an amount of 560-1580mg/kg 10-16mg/kg, cucumber 15-120mg/kg, the fruit of Lagenaria siceraria 10-16mg/kg, Ipomoea aquatica and cabbage 0.17—3.4mg/kg. Balsam pear, towel gourd, auberqine, tomato, cowpea, sword bean, kidney bean, green pepper, green qrocery, chrysanthemum coronarium, spinach, pickled cabbage (white), pickled cabbage (purple), caraway, cauliflower (white), cauliflower (green), murphy, onion, radish, carrot, rhizoma zingiberis recens, garlic, asparaqus, zizania aquatica and scallion did not contain DEHP or only contain a trace amount of DEHP. The study on the effect of DEHP concentration in soil on the cumulation amount of Benincasa hispida showed that the higher the concentration, the higher content in the plant. But Benincasa hispida planted in the soil without DEHP treatment also contained DEHP. A high DEHP content also found in the Benincasa hispida that was planted in the field covered with plastic film. Therefore, the DEHP in Benincasa hispida possibly cumulated from the air DEHP which was released by treated soil or plastic film.
The above results reveal the pollution condition of DEHP in main vegetables in Hangzhou market, which provide us a reference of food safety. And the investigation of the effect of DEHP concentration in soil and plastic film on DEHP cummulation in Benincasa hispida could help us to solve the problem of high DEHP content in waxgourd.
引文
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[2]杨科峰,厉曙光,蔡智鸣等.食用油及其加热产物中酞酸酯类增塑剂的分析[J].环境与职业医学杂志,2002,19(1):37-39.
[3]赵文红,厉曙光,石红军等.单细胞凝胶电泳检测酞酸酯类对DNA的损伤[J].中国公共卫生,2004,20(10):1164-1165.
[4]吴杰民.聚烯烃类农膜及酞酸酯类(PAEs)在环境中的残留及生物降解前景[J].环境科学,1994,15(2):77-80.
[5]夏凤毅.邻苯二甲酸酯生物降解性研究.浙江大学,1998.
[6]赵振华.我国环境中邻苯二甲酸酷污染的研究[J].环境化学丛刊,1986,7(6):74-76.
[7]石万聪.防雾增塑剂[J].塑料工业,1982,(2):39-40.
[8]蔡玉琪,钱晓睛.植物对酞酸酯的敏感性[J].农村生态环境(学报),1994,10(1):29-32.
[9]吴杰民.聚烯烃类农膜及酞酸脂类(PAES)在环境中的残留及生物降解前景[J].环境科学,1995,15(2):77-80.
[10]Kluwe WM,Carcinogienility testing of phthalate esters and releated compounds by NIP and NCI Environ Health Presp,1982,5:129-133.
[11]Schmitzer JL,Scheunert I,Korte F,Fate of bis(2-ethylhexyl)[14C]phthalate in laboratory and outdoor soil-plant systems[J].J Agric.Food Chem.,1988,36(24):210-215.
[12]曾巧云,莫测辉,蔡全英等.菜心对邻苯二甲酸酯(PAEs)吸收途径的初步研究[J].农业工程学报,2005,21(8):137-141
[13]尹睿,林先贵,王曙光等.土壤中DBP/DEHP污染对几种蔬菜品质的影响[J].农业环境科学学报,2004,23(1):1-5.
[14]Staples CA,Peterson DR,Parkerton TF,The environmental fate of phthalate esters:a literature eview[J].Chemosphere,1997,35(4):667-749.
[15]Ribbons DW,Keyser P,Kunz DA,Microbial degradation of phthalates in Gibson DT,Microbial Degradation of Organ in Compounds[C].New York:Marcel Dekker,1984:371-397.
[16]庞金梅,段亚利,池宝亮等.DEHP在土壤和白菜中的残留及毒性分析[J].环境化学,1995,14(3):184-185.
[17] Lpkke H, Rasmussen L, Phytotoxicological effects of di-(2-ethyl hexyl)-phthalate and di-n-butyl-phthalate on higher plants in laboratory and field experiments.Environ. Poll. (Series A), 1983,32:179-199.
[18] Jaeger RJ, Rubin RJ, Migration of a phthalate ester plasticizer from polyvinyl chloride blood bags into stored human blood and its localization in human tissues[J]. New Eng. J.Med., 1972, 278:1114-1118.
[19] Agarwal D, Eustis S, Lamb J, Effects of di(2-ethylhexyl) phthalate on the gonadal pathophysiology, sperm morphology,and reproductive performance of male rats. Environ Health Perspect,1986, 65:343-350.
[20] Wolf C, Lambright C, Mann P, Administration of potentially antiandrogenic pesticides (procymidone, linuron, iprodione, chlozolinate, p,p'-DDE, and ketoconazole) and toxic substances (dibutyl- and diethylhexyl phthalate, PCB 169, and ethane dimethane sulphonate) during sexual differentiation produces diverse profiles of reproductive malformations in the male rat[J].Toxicol Ind. Health, 1999,15:94-118.
[21] Poon R, Lecavalier P, Mueller R, Subchronic oral toxicity of di-n-octylphthalate and di(2-ethylhexyl)phthalate in the rat.Food Chem.Toxicol, 1997,35:225-239.
[22] Kurata Y, Kidachi F, Yokoyama M, Subchronic toxicity of di(2-ethylhexyl) phthalate in common marmosets:Lack of hepatic peroxisome proliferation,testicular atrophy, or pancreatic acinar cell hyperplasia.Toxicol. Sci, 1998,42:49-56.
[23] Huber WW, Grasl-Kraupp B, Schulte-Hermann R, Hepatocarcinogenic potential of di(2-ethylhexyl)phthalate in rodents and its implications on human risk. Crit. Rev,Toxicol, 1996, 26:365-481.
[24] Eiholzer U, Boltshauser E, Frey D, A common feature in auchenne muscular dystrophy. Eur. J. Pediatr.,1998, 147:41-46.
[25] Ward JM, Peters JM, Perella CM, Gonzalez FJ. Receptor and nonreceptor mediated organ-specific toxicity of DEHP in peroxisome proliferator-activated receptor alpha-null mice.Toxi. Path. 1998, 26:240-246.
[26] Labow R, Nephrotoxic effects of di-(2-ethylhexyl)phthalate (DEHP) hydrolysis products on cultured kidney epithelial cells. Environ Health Perspect, 1990, 89:189-193.
[27] Peters JM, Taubeneck MW, Keen CL, Gonzalez FJ. DEHP induces a functional zinc deficiency during pregnancy and teratogenesis that is independent of peroxisome proliferator-activated receptor-alpha.Teratology,1997,56:311-316.
[28]Moore M,Comins Ftazlewn.Inc,CHV-663-134.Conduste for Eastman Chemical Co,1996.
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