油脂脱臭馏出物中多环芳烃含量及检测方法研究
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摘要
植物油精炼的副产物——脱臭馏出物是提取和生产天然维生素E和植物甾醇的原料,针对油脂脱臭馏出物特殊的黏稠性状和复杂组分,对其中多环芳烃(PAHs)含量检测方法和样品前处理条件进行优化研究,建立了液液分配萃取-硅胶SPE柱净化-同位素稀释法-气相色谱串联质谱法(GC-MS)定量检测油脂脱臭馏出物中16种PAHs的方法。结果表明:油脂脱臭馏出物中16种PAHs的检出限和定量限分别为0. 10～0. 28μg/kg和0. 33～0. 92μg/kg,回收率为83. 92%～112. 34%,方法检测灵敏度高、稳定性好、定性及定量准确,能很好地满足对脱臭馏出物中PAHs的检测。利用优化的检测方法分别对6个不同的脱臭馏出物样品中PAHs含量进行检测分析,结果发现脱臭馏出物中BaP、PAH4、PAH16的平均含量分别为11. 89、217. 19、2 268. 85μg/kg,其中LPAHs是主要的PAHs污染物,占PAH16总量的90. 34%～95. 61%。结果提示在利用油脂脱臭馏出物作为维生素E和植物甾醇的提取原料时应充分注意其多环芳烃的安全风险。
Deodorizer distillate,the by-product of vegetable oil refining,is the raw material for extraction and production of natural vitamin E and phytosterol. Based on the special viscous traits and complex components of deodorizer distillate,the detection methods of polycyclic aromatic hydrocarbons( PAHs)and the pretreatment conditions of samples were optimized. The liquid-liquid extraction-silica SPE column purification-isotope dilution-GC-MS method for quantitative detection of 16 PAHs in deodorizer distillate was established. The limits of detection and the limits of quantitation for PAHs were 0. 10-0. 28 μg/kg and 0. 33-0. 92 μg/kg,respectively. The recoveries ranged from 83. 92% to 112. 34%.Therefore,the method had high detection sensitivity,good stability,qualitative and quantitative accuracy,and could meet the detection of PAHs in deodorizer distillate. Through the detection and analysis of PAHs content in six deodorizer distillate samples,the average contents of BaP,PAH4 and PAH16 in deodorizer distillate were 11. 89,217. 19,2 268. 85 μg/kg,respectively. LPAHs were the main PAHs pollutants accounting for 90. 34%-95. 61% of PAH16 in deodorizer distillate. The results suggested that the use of deodorizer distillate as raw material for the extraction of vitamin E and phytosterols should pay full attention to the safety risks of its PAHs.
Deodorizer distillate,the by-product of vegetable oil refining,is the raw material for extraction and production of natural vitamin E and phytosterol. Based on the special viscous traits and complex components of deodorizer distillate,the detection methods of polycyclic aromatic hydrocarbons( PAHs)and the pretreatment conditions of samples were optimized. The liquid-liquid extraction-silica SPE column purification-isotope dilution-GC-MS method for quantitative detection of 16 PAHs in deodorizer distillate was established. The limits of detection and the limits of quantitation for PAHs were 0. 10-0. 28 μg/kg and 0. 33-0. 92 μg/kg,respectively. The recoveries ranged from 83. 92% to 112. 34%.Therefore,the method had high detection sensitivity,good stability,qualitative and quantitative accuracy,and could meet the detection of PAHs in deodorizer distillate. Through the detection and analysis of PAHs content in six deodorizer distillate samples,the average contents of BaP,PAH4 and PAH16 in deodorizer distillate were 11. 89,217. 19,2 268. 85 μg/kg,respectively. LPAHs were the main PAHs pollutants accounting for 90. 34%-95. 61% of PAH16 in deodorizer distillate. The results suggested that the use of deodorizer distillate as raw material for the extraction of vitamin E and phytosterols should pay full attention to the safety risks of its PAHs.
引文
[1]刘玉兰,温运启,许利丽,等.不同植物油制取工艺对毛油中多环芳烃含量的影响[J].中国油脂,2018,43(2):41-45.
[2]WEN Y Q,LIU Y L,XU L L,et al.Occurrence of polycyclic aromatic hydrocarbons in various types of raw oilseeds from different regions of China[J].Food Add Contam B Surveill,2017,29:1-9.
[3]王建华.不同加工过程花生油中16种多环芳烃(PAHs)的含量变化[J].食品科技,2013(5):183-187.
[4]MA Y X,SHI L K,LIU Y L,et al.Effects of neutralization,decoloration,and deodorization on polycyclic aromatic hydrocarbons during laboratory-scale oil refining process[J].J Chem,2017,2017:1-9.
[5]刘玉兰,温运启,马宇翔,等.大豆油精炼过程多环芳烃迁移规律研究[J].食品科学,2018(22):263-268.
[6]刘玉兰,石龙凯,刘畅.吸附法脱除油脂中多环芳烃的效果研究[J].中国油脂,2015,40(9):70-76.
[7]刘玉兰,石龙凯,胡爱鹏.碱炼脱酸对油脂中16种多环芳烃脱除效果的研究[J].中国粮油学报,2016,31(2):75-80.
[8]温运启.植物油料及其加工产物中多环芳烃的研究[D].郑州:河南工业大学,2017.
[9]温运启,刘玉兰,王璐阳,等.不同食用植物油中维生素E组分及其含量研究[J].中国油脂,2017,42(3):35-39.
[10]刘玉兰.油脂制取与加工工艺学[M].北京:科学出版社,2009.
[11]石龙凯,刘玉兰,张东东.水蒸气蒸馏脱臭对食用油中多环芳烃脱除效果的研究[J].中国粮油学报,2016,31(4):57-60.
[12]刘玉兰,张明明,杨金强.水蒸汽蒸馏法对油脂中DBP和DEHP脱除效果的研究[J].现代食品科技,2017,33(5):176-182.
[13]丁新杰.精炼对大豆油和菜籽油中有益微量组分的影响[D].郑州:河南工业大学,2015.
[14]刘玉兰,彭团儿,马宇翔.米糠油及其脱臭馏出物中生育酚和生育三烯酚的分析检测[J].中国油脂,2010,35(3):70-74.
[15]李奇.大豆油脱臭馏出物中生育酚、甾醇和脂肪酸的提取工艺研究[D].天津:天津大学,2008.
[16]张莉华,许新德,邵斌,等.油脂加工副产物---脱臭馏出物的综合利用[J].中国食品添加剂,2015(1):157-164.
[17]SHIMADA Y,NAKAI S,SUENAGA M,et al.Facile purification of tocopherols from soybean oil deodorizer distillate in high yield using lipase[J].J Am Oil Chem Soc,2000,77(10):1009-1013.
[18]QIN L,ZENG Q,ZHANG J J,et al.Integrated process for extracting vitamin E with high purity from the methylated oil deodorizer distillate[J].Sep Purif Technol,2018,196:229-239.
[19]万建春.大豆脱臭馏出物中生育酚及甾醇单体的分离纯化[D].武汉:武汉工业学院,2008.
[20]刘存存,方学智,李宝才,等.茶油脱臭馏出物中甾醇精制的研究[J].食品工业科技,2012(2):250-253.
[21]刘玉兰,胡爱鹏,马宇翔,等.植物油料和食用油脂加工质量安全控制[J].中国粮油学报,2017,32(11):177-185.
[22]张东东.炒香型油脂生产中多环芳烃的控制[D].郑州:河南工业大学,2016.
[23]石龙凯,刘玉兰,崔瑞福,等.油籽炒籽条件对油脂中PAHs含量影响的研究[J].中国粮油学报,2016,31(3):79-83.
[24]ROJO CAMARGO M C,ANTONIOLLI P R,VICENTEE.Evaluation of polycyclic aromatic hydrocarbons content in different stages of soybean oils processing[J].Food Chem,2012,135(3):937-942.
[25]曹小丽,杨晓倩,刘素华.高效液相色谱-荧光检测法测定植物油中15种多环芳烃[J].中国卫生检验杂志,2013(12):2580-2582.
[26]SHI L K,ZHANG D D,LIU Y L.Survey of polycyclic aromatic hydrocarbons of vegetable oils and oilseeds by GC-MS in China[J].Food Addit Contam,2016,33(4):603-611.
[27]石龙凯,刘玉兰.液相色谱-串联质谱法检测食用油脂中多环芳烃[J].中国粮油学报,2015,30(12):114-119.
[28]张东东,刘玉兰,马宇翔,等.SPE净化-同位素稀释-GC-MS法检测食用油脂中16种多环芳烃[J].粮食与油脂,2016(1):53-59.
[29]WANG J H,GUO C.Ultrasonication extraction and gel permeation chromatography clean-up for the determination of polycyclic aromatic hydrocarbons in edible oil by an isotope dilution gas chromatography-mass spectrometry[J].J Chromatogr A,2010,1217(28):4732-4737.
[30]DRABOVA L,TOMANIOVA M,KALACHOVA K,et al.Application of solid phase extraction and two-dimensional gas chromatography coupled with time-of-flight mass spectrometry for fast analysis of polycyclic aromatic hydrocarbons in vegetable oils[J].Food Control,2013,33(2):489-497.
[2]WEN Y Q,LIU Y L,XU L L,et al.Occurrence of polycyclic aromatic hydrocarbons in various types of raw oilseeds from different regions of China[J].Food Add Contam B Surveill,2017,29:1-9.
[3]王建华.不同加工过程花生油中16种多环芳烃(PAHs)的含量变化[J].食品科技,2013(5):183-187.
[4]MA Y X,SHI L K,LIU Y L,et al.Effects of neutralization,decoloration,and deodorization on polycyclic aromatic hydrocarbons during laboratory-scale oil refining process[J].J Chem,2017,2017:1-9.
[5]刘玉兰,温运启,马宇翔,等.大豆油精炼过程多环芳烃迁移规律研究[J].食品科学,2018(22):263-268.
[6]刘玉兰,石龙凯,刘畅.吸附法脱除油脂中多环芳烃的效果研究[J].中国油脂,2015,40(9):70-76.
[7]刘玉兰,石龙凯,胡爱鹏.碱炼脱酸对油脂中16种多环芳烃脱除效果的研究[J].中国粮油学报,2016,31(2):75-80.
[8]温运启.植物油料及其加工产物中多环芳烃的研究[D].郑州:河南工业大学,2017.
[9]温运启,刘玉兰,王璐阳,等.不同食用植物油中维生素E组分及其含量研究[J].中国油脂,2017,42(3):35-39.
[10]刘玉兰.油脂制取与加工工艺学[M].北京:科学出版社,2009.
[11]石龙凯,刘玉兰,张东东.水蒸气蒸馏脱臭对食用油中多环芳烃脱除效果的研究[J].中国粮油学报,2016,31(4):57-60.
[12]刘玉兰,张明明,杨金强.水蒸汽蒸馏法对油脂中DBP和DEHP脱除效果的研究[J].现代食品科技,2017,33(5):176-182.
[13]丁新杰.精炼对大豆油和菜籽油中有益微量组分的影响[D].郑州:河南工业大学,2015.
[14]刘玉兰,彭团儿,马宇翔.米糠油及其脱臭馏出物中生育酚和生育三烯酚的分析检测[J].中国油脂,2010,35(3):70-74.
[15]李奇.大豆油脱臭馏出物中生育酚、甾醇和脂肪酸的提取工艺研究[D].天津:天津大学,2008.
[16]张莉华,许新德,邵斌,等.油脂加工副产物---脱臭馏出物的综合利用[J].中国食品添加剂,2015(1):157-164.
[17]SHIMADA Y,NAKAI S,SUENAGA M,et al.Facile purification of tocopherols from soybean oil deodorizer distillate in high yield using lipase[J].J Am Oil Chem Soc,2000,77(10):1009-1013.
[18]QIN L,ZENG Q,ZHANG J J,et al.Integrated process for extracting vitamin E with high purity from the methylated oil deodorizer distillate[J].Sep Purif Technol,2018,196:229-239.
[19]万建春.大豆脱臭馏出物中生育酚及甾醇单体的分离纯化[D].武汉:武汉工业学院,2008.
[20]刘存存,方学智,李宝才,等.茶油脱臭馏出物中甾醇精制的研究[J].食品工业科技,2012(2):250-253.
[21]刘玉兰,胡爱鹏,马宇翔,等.植物油料和食用油脂加工质量安全控制[J].中国粮油学报,2017,32(11):177-185.
[22]张东东.炒香型油脂生产中多环芳烃的控制[D].郑州:河南工业大学,2016.
[23]石龙凯,刘玉兰,崔瑞福,等.油籽炒籽条件对油脂中PAHs含量影响的研究[J].中国粮油学报,2016,31(3):79-83.
[24]ROJO CAMARGO M C,ANTONIOLLI P R,VICENTEE.Evaluation of polycyclic aromatic hydrocarbons content in different stages of soybean oils processing[J].Food Chem,2012,135(3):937-942.
[25]曹小丽,杨晓倩,刘素华.高效液相色谱-荧光检测法测定植物油中15种多环芳烃[J].中国卫生检验杂志,2013(12):2580-2582.
[26]SHI L K,ZHANG D D,LIU Y L.Survey of polycyclic aromatic hydrocarbons of vegetable oils and oilseeds by GC-MS in China[J].Food Addit Contam,2016,33(4):603-611.
[27]石龙凯,刘玉兰.液相色谱-串联质谱法检测食用油脂中多环芳烃[J].中国粮油学报,2015,30(12):114-119.
[28]张东东,刘玉兰,马宇翔,等.SPE净化-同位素稀释-GC-MS法检测食用油脂中16种多环芳烃[J].粮食与油脂,2016(1):53-59.
[29]WANG J H,GUO C.Ultrasonication extraction and gel permeation chromatography clean-up for the determination of polycyclic aromatic hydrocarbons in edible oil by an isotope dilution gas chromatography-mass spectrometry[J].J Chromatogr A,2010,1217(28):4732-4737.
[30]DRABOVA L,TOMANIOVA M,KALACHOVA K,et al.Application of solid phase extraction and two-dimensional gas chromatography coupled with time-of-flight mass spectrometry for fast analysis of polycyclic aromatic hydrocarbons in vegetable oils[J].Food Control,2013,33(2):489-497.