摘要
【目的】建立螺螨酯在火龙果全果和果肉中的残留检测方法,并对火龙果果肉中的残留量进行膳食摄入评估。【方法】样品中螺螨酯加乙腈提取,N-丙基乙二胺和石墨化碳黑净化,离心,上清液过滤膜后超高效液相色谱三重四极杆串联质谱检测,外标法定量。【结果】火龙果全果和果肉中螺螨酯平均回收率分别为87%~105%和81%~90%,相对标准偏差分别为4.6%~13%和6.6%~8.1%。火龙果全果和果肉中螺螨酯的最低检测浓度(w,后同)均为0.01 mg·kg^-1。【结论】按本试验设计进行施药,不同采收间隔期火龙果全果和果肉中螺螨酯的残留量分别为<0.71 mg·kg^-1和<0.14 mg·kg^-1。螺螨酯的普通人群国家估计每日摄入量是0.003 1 mg,占日允许摄入量的0.5%左右,认为对一般人群健康不会产生不可接受的风险。
【Objective】The present study developed a method to determine of spirodiclofen based on liquid chromatography triple quadrupole mass spectrometry(LC-MS/MS),which is widely used in analytical labs.We investigated the behavior of terminal residues of spirodiclofen in dragon fruit and flesh under field conditions,risk assessment for dietary intake based on supervised residue trial data,the effects of application frequency and rate and of the interval to harvest on terminal residues.【Methods】The supervised field trials were carried out in six provinces in the year of 2018.Two treatments were included in this study to determine spirodiclofen residues at high and low application rates.Each treatment had 3 replicated plots,and each plot consisted of 2 dragon trees.The low application rate was 80 mg·kg^-1 and the high application rate 120 mg·kg^-1.Both the low and high application rates were used in two or three applications(14 days intervals each).The dragon fruit and flesh were sampled at 7,14 and 21 days after the last spraying.Immediately after collecting,the samples were put into polyethylene bags and transported to the laboratory.The fruit stalk of the dragon samples collected in the field was cut off.The dragon fruit were evenly cut into 4-8 portions along the longitudinal direction.The nonadjacent fruit petals were divided into two groups.The first group was used to prepare the whole fruit samples,and the second group was used to prepare the flesh samples.All the samples were crushed with dry ice and were packed in polyethylene bags,labelled,and stored at-20℃until analyzed.10 g subsample of homogeneous dragon fruit and flesh was put into a 100 mL centrifuge tube,and 5 mL distilled water,20 mL acetonitrile(HPLC grade),and 2.5 g sodium chloride were added in turn.The sample was vortexed for 10 min at high speed on a vortexer.The mixture was centrifuged at 4000 r·min-1 for 5 min,and 2 mL of the supernatant was transferred to a 2 mL centrifuge tube containing 0.05 g PSA and 0.02 g GCB,vortexed for 1 min at 4000 r·min-1 for 5 min,and filtered into a glass autosampler vial through 0.22μm pinhole filtration membrane for LC-MS/MS analysis.The column used for spirodiclofen determination was a Shim-pack GISS(2.1 mm×50 mm,1.9μm),maintained at 40℃.The mobile phases A and B were acetonitrile and water with 0.1 percent formic acid(80∶20,V/V),respectively.Electrospray ionization MS in the positive mode was performed.The flow rate was 0.3 mL·min-1.The cone and fragment voltages were 16 eV and 11 eV,respectively.The temperature and flow rate for drying gas were 400℃and 10 L·min-1,respectively.The ions monitored in MRM were m/z 411.1/71.2 and 411.1/313.05(qualitative ion pair),and 411.1/71.2(quantification ion pair).The retention time of spirodiclofen was 1.3 min at the above conditions.The IEDI was defined according to the formula IEDI=[STMRi(or STMR-Pi)×F]/bw.The ADI%was calculated according to the formula ADI%=(IEDI×100%)/ADI.【Results】A standard calibration curve of spirodiclofen was constructed by plotting the analyzed concentrations against the peak areas.Good linearity(y=28570214.6149x+9992.2046)was achieved in the range of 0.002 to 0.5 mg·L^-1,with a correlation coefficient of r2=0.9900.The recovery study was conducted for dragon fruit at three different fortification levels of 0.01,0.1,and 5 mg·kg^-1.The average recovery from the fortified samples in five replicate experiments ranged from 87%to 105%,with a relative standard deviation(RSD)from 4.6%to 13%.The limits of quantification(LOQ)were 0.01 mg·kg^-1 for dragon fruit.The recovery study was conducted for flesh at three different fortification levels,0.01,0.1,and 1 mg·kg^-1.The average recovery from the fortified samples in five replicate experiments ranged from 81%to 90%,with a relative standard deviation(RSD)from 6.6%to 81%.The limits of quantification(LOQ)were 0.01 mg·kg^-1 for flesh.When the intervals to harvest were 7,14,21 day,the residue levels in dragon fruit were less than 0.71,0.23 and 0.68 mg·kg^-1,respectively and those in the flesh were less than 0.14,0.059 and 0.041 mg·kg^-1,respectively.Under identical application dosage and application frequency,the residue decreased with the increase of interval to harvest,indicating that there was a negative correlation between the residue and interval to harvest.However,under the same application dosage,application frequency and interval to harvest,the residue in the whole fruit was higher than in the flesh.The international estimated daily intake(IEDI)of spirodiclofen was 0.0031 mg,and the ADI%was calculated according to formula and found to be 0.5%,the potential health risk induced by spirodiclofen was not significant based on supervised residue trial data.【Conclusion】A specific,sensitive and simple residue analytical method using LC-MS/MS for the detection and monitoring of spirodiclofen in dragon fruit and flesh was established.When the application of spirodiclofen followed the recommended methods,the potential health risk induced was not significant.
作者
吴绪金
马婧玮
汪红
安莉
乔成奎
马莹
谢汉忠
WU Xujin;MA Jingwei;WANG Hong;AN Li;QIAO Chengkui;MA Ying;XIE Hanzhong(Institute of Quality Standard and Testing Technology for Agro-products,Henan Academy of Agricultural Sciences,Zhengzhou 450002,Henan,China;Zhengzhou Fruit Research Institute,CAAS,Zhengzhou 450009,Henan,China)
出处
《果树学报》
CAS
CSCD
北大核心
2021年第1期90-98,共9页
Journal of Fruit Science
基金
河南省科技创新杰出青年(184100510015)
中国农业科学院科技创新工程(CAAS-ASTIP-2016-ZFRI)。
关键词
火龙果
螺螨酯
残留检测
膳食摄入评估
Dragon fruit
Spirodiclofen
Determination
Risk assessment for dietary residue intake
