摘要
该研究建立了一种仪器需求小、技术门槛低、检测效率高的汞形态分析方法应用于食用菌的检测,以偏最小二乘法(PLS)替代常规的色谱分离方法,结合原子荧光光谱(AFS)实现了二价无机汞(Hg^(2+))和甲基汞(MeHg^(+))的准确、便捷、高效检测。以一系列已知浓度的Hg^(2+)和MeHg^(+)混合标准溶液的原子荧光光谱数据作为训练集建立PLS模型。模型对Hg^(2+)和MeHg~+的检测范围分别为0.2~10 ng/m L和0.5~25 ng/m L,当提取的主成分数分别为3和2时,对应最小的预测误差平方和(PRESS)为0.046 6和0.034 8,对训练集中混合标准溶液预测结果的相关系数平方(R^(2) _(cal))为0.999 2和0.998 9,对独立预测集预测结果的相关系数平方(R^(2) _(pre))均为0.998 3,均方根误差(RMSD)为0.127 ng/m L和0.346 ng/m L,预测相对均方根误差(REP)为2.59%和3.21%,上述统计学参数说明模型具有较强的预测能力。模型对Hg^(2+)和MeHg^(+)的检出限可分别达0.021 ng/m L和0.039 ng/m L,低中高浓度平行实验的相对标准偏差分别为1.7%~3.1%和1.8%~3.1%,低中高浓度的加标回收率分别为87.5%~109%和96.0%~111%,模型验证结果表明其灵敏度、精密度、准确度良好。将建立的偏最小二乘法结合原子荧光光谱法应用于多种食用菌的检测,其结果与液相色谱-原子荧光光谱法高度一致,证明采用此法进行食用菌检测切实可行。
A high efficiency analysis method for mercury speciation analysis in edible mushrooms with low instrument requirements and technical threshold was established.Instead of typical separation methods such as liquid chromatography and gas chromatography,the partial least squares(PLS)with atomic fluorescence spectrometry(AFS)can achieve accurate,convenient and efficient detection of divalent inorganic mercury(Hg^(2+))and methyl mercury(MeHg^(+)).A PLS model was built based on the atomic fluorescence spectral data of a series of Hg^(2+)and MeHg^(+)mixed standard solutions with known concentrations as the training set.The detection range for Hg^(2+)and MeHg+were 0.2-10 ng/mL and 0.5-25 ng/mL.The numbers of factors for Hg^(2+)and MeHg^(+)were set at three and two,and the corresponding minimum prediction error sum of squares(PRESS)were 0.0466 and 0.0348.The squared correlation coefficients(R^(2) _(cal))between predicted concentration and actual concentration of Hg^(2+)and MeHg^(+)in the training set calculating by the model were 0.9992 and 0.9989,and the squared correlation coefficient(R^(2) _(pre))in the independent prediction set was 0.9983 both.The root mean square errors of difference(RMSD)were 0.127 ng/mL and 0.346 ng/mL,and the relative errors of prediction(REP)were 2.59% and 3.21%,respectively.All the statistical parameters indicate that the model has strong predictive ability.The detection limits of Hg^(2+)and MeHg^(+)by the model calculating were 0.021 ng/mL and 0.039 ng/mL,respectively.The relative standard deviations of six parallel experiments at low,medium and high Hg^(2+)concentrations was between 1.7% and 3.1%,and that of MeHg^(+)was between 1.8% and 3.1%.The range of spike recovery value for low,medium and high Hg^(2+)concentrations was 87.5%-109%,and that of MeHg^(+)was 96.0%-111%.The model validation results show that the sensitivity,precision and accuracy of the partial least squares model are all excellent.When this method was applied to the mercury speciation analysis in edible mushrooms,the predicting concentrations were highly consistent with results of liquid chromatography-atomic fluorescence spectrometry method.It is proof that the method of partial least squares combined with atomic fluorescence spectrometry is practically feasible for the mercury speciation analysis in Edible Mushrooms.
作者
陈展
罗小娟
吴训
CHEN Zhan;LUO Xiao-juan;WU Xun(Guangxi Zhuang Autonomous Region Center for Disease Control and Prevention,Nanning 530028,China)
出处
《分析测试学报》
北大核心
2025年第12期2564-2572,共9页
Journal of Instrumental Analysis
基金
广西壮族自治区卫生健康委员会课题(Z20200135)
广西壮族自治区疾病预防控制中心科研课题(20201029)。
关键词
偏最小二乘法
原子荧光光谱法
二价无机汞
甲基汞
食用菌
the partial least squares
the atomic fluorescence spectrometry
divalent inorganic mercury
methylmercury
edible mushrooms
