固相微萃取（SPME）测定生物样品中挥发性有机物的应用研究
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摘要
目的
固相微萃取(SPME)是利用涂有吸附剂的熔融石英纤维吸附样品中的有机物质而达到萃取浓缩的目的,具有无溶剂、可直接进样、操作简便快捷、灵敏的特点,克服了传统的样品前处理技术的缺点。SPME集取样、萃取、富集和进样于一体,操作简便、分析周期短、样品用量少、重现性好、易于自动化,特别适合现场分析,且不用或少量使用有机溶剂,既有利于分析人员的健康又免除了对环境的二次污染。本实验将最新的SPME技术应用到职业卫生生物监测工作中,根据SPME技术的原理,自主研制SPME装置,着重研究固相微萃取技术中固相涂层的制作方法,筛选出适合于测定尿中丙酮、血中苯乙烯的固相涂层,研究制定测定尿中丙酮、血中苯乙烯的SPME检测方法。拟将研究的方法申报为职业卫生生物监测标准方法,在全国职业卫生技术服务部门应用。
方法
1.SPME装置的研制:根据SPME技术的基本原理自主研制了SPME装置,SPME技术中固相涂层材料的选择及制作工艺探讨:根据有机物与溶剂间相似相容原理,选择适用于尿中丙酮、血中苯乙烯的固相涂层材料。通过改变涂层溶液浓度、涂布时间、涂布次数来改变涂层厚度,确定一个最适合上述代谢产物测定的涂层厚度及涂层涂布方法。
2.尿中丙酮、血中苯乙烯的SPME方法学研究:试样量、容器体积、萃取时间、萃取温度、搅拌方式及速率的选择。
3.SPME与气相色谱(GC)连用条件的选择:包括柱类型、柱温、进样口温度、检测器温度的选择、解吸温度、解吸时间的确定。
4.现场应用研究:选择接触丙酮、苯乙烯等毒物的接毒工人进行方法学验证,同时取空白样品作对照。
结果
1.自制SPME萃取装置制作简单、使用方便。适合尿中丙酮、血中苯乙烯的萃取涂层为PDMS涂层,涂层涂布3次,涂层溶液浓度50g/L,加入6%固化剂时,萃取效果较好,萃取时间适宜。用显微镜测得制成的PDMS涂层厚度为120μm。
2.尿中丙酮测定最优SPME条件为无水硫酸钠用量4克,萃取温度为30℃,萃取时间为20min,转速选择为低速,尿样体积与顶空空间比例为1:3,解吸温度为250℃,解吸时间为5min。尿中丙酮在0.0～150.0μg/mL范围内线性关系良好,方程式为Y=3.55X+3.05,相关系数r=0.9990,检出限为0.0008μg/mL,方法精密度良好,回收率90.7%以上,尿样可在室温下和4℃冰箱中保存14天,环境可能存在的丙酮共存物二氯甲烷、2-丁酮、甲醇、乙酸乙酯及尿样中基体均不干扰丙酮的测定。应用本方法测定了30名丙酮接触者和10名丙酮非接触者尿中丙酮的含量。丙酮接触者尿样中丙酮含量范围为0.04～62.97μg/mL,丙酮非接触者尿样中丙酮含量均小于检出限。实验结果表明SPME-GC法适用于尿中丙酮的测定。
3.血中苯乙烯测定最优SPME条件为浓磷酸15μl/2毫升血样,萃取温度为20℃,萃取时间为10min,转速选择为中速,血样体积/项空空间比例为1:4,解吸温度为250℃,解吸时间为5min。血中苯乙烯在0.00～1.65μg/mL范围内线性关系良好,方程式为Y=187.24X-2.10,相关系数r=0.9994,检出限为0.0006μg/mL,方法精密度良好,回收率77.0%以上,血样可在4℃冰箱和冷冻条件下-8℃下均可保存14天,环境可能存在的苯乙烯共存物苯、甲苯、乙苯、二甲苯、四氯乙烯和血样基体均不干扰苯乙烯的测定。应用本方法测定了30名苯乙烯接触者和10名非接触者血中苯乙烯的含量。苯乙烯接触者血样中苯乙烯含量范围为0.024～0.58μg/mL,苯乙烯非接触者血中苯乙烯含量均小于检出限。实验表明SPME-GC法适用于血中苯乙烯的测定。
结论
1.本文根据SPME技术的基本原理研制了SPME装置及纤维涂层,与商品化SPME装置及涂层相比,具有富集能力相当、价格低廉,制备工艺简单等特点。
2.利用自制SPME装置对尿中丙酮、血中苯乙烯的检测方法进行规范化研究,并对该方法进行了方法学评价及各项实验验证,该方法各项实验指标均符合《生物材料分析方法的研制准则(尿样及血样)》(WS/T 68-1996)的要求,可以申报为职业卫生生物监测标准方法,并在全国职业卫生技术服务部门应用。
Objectives
The solid-phase microextraction(SPME)utilizes the fused quartz fiber which is coated on adsorbing material to absorb the organics in the samples to achieve the purpose of extraction and concentration.It haves the characteristic of no-solvent, direct sample introduction,convenient and shortcut to manipulate and sensitive and it overcomes the weakness of the orthodox sample pre-processing technical.SPME integrates the sampling,extraction,enriching and injection in one step,it is convenient to manipulate,analysis cycle is short,few dosage of sample is used,the reproducibility is good,and it is easy to be automatic so it is fit for analysis on the spot particularly,little organic solvent used is profit for the healthy of analytical personnel,and the secondary pollution to environment is to exempt.In this experiment,the newest SPME technology was applied to biological monitoring in occupational health.Based on the development,principle and type of the solid-phase microextraction,the SPME installation was developed and the developing methods of the fiber coating was researched emphasizily.The coatings fit for the determination of acetone in urine and styrene in blood were screened.The SPME detection methods of the determination for acetone in urine and styrene in blood were institute.Then the methods researched will be reported as biological monitoring standard methods in occupational health for utilizing in the occupational health technical service departments in the whole country.
Methods
1.The manufacture of the SPME installation:according to the principle of the SPME,design the SPME installation.The selection of the coating materials and the approach for manufacture technology:select the coating materials referring to acetone in the urine and styrene in the blood according to the principle that the organics and solvents similar were compatible.The coating thickness and the coating methods fit for the metabolic product above mentioned by changing the concentration of the coating solution,coating time,coating number of times to alter the coating thickness.
2.The technology research of solid-phase microextraction for determining acetone in the urine and styrene in the blood:the selection of sample size, container volume,extraction time,extraction temperature,stirring style and velocity.
3.The selection of GC condition connecting with SPME:including the selection of the type of the chromatographic column,the column temperature,the inject opening temperature,the detector temperature,and the definition of the adsorption temperature,adsorption time,adsorption solvent.
4.Technology validation by selecting the workers contacting with the poisons such as acetone,styrene and so on,at the same time comparison by determining the blank sample.
Results
1.The self-made SPME extraction installation was made easily and used conveniently.The extraction coating PDMS was effective to extract acetone in urine and styrene in blood,the coating was coated for thrice,the concentration of the coating solution was 50g/L,and 6%curing agent was added in,at that time,the effect was good,and the extraction time was suitable.The PDMS coating thickness was 120μm measured by the microscope.
2.The optimal condition of SPME for determining acetone in urine was as follows: 4gNa_2SO_4,the extraction temperature was 30℃,the extraction time was 5min,the rotation speed was brachytely,the ratio of sample volume and headspace vacuity was 1:3,the desorption temperature was 250℃,the desorption time was 5min.The linear correlation for acetone in urine was good in 0.0～150.0μg/ml,and the equation was Y =3.55X+3.05,r=0.9990,the detection limit 0.0008μg/ml,the precision was good,the recovery was greater than 90.7%.The urine sample can be kept for 14 days at 4℃.The common possible coexistence agent of the acetone in the environment dichloromethane, 2-butanone,methanol,acetic ether and the basal body in urine all didn't interfere with the determination of the acetone in urine.The acetone contents of the 30 contact persons and 10 non-contact persons were determined by this method.The acetone contents of the contact persons were form 0.04μg/ml to 62.97μg/ml,the acetone contents of the non-contact persons were all lower than the detection limit.The experiment indicated SPME-GC refers to the determination of the acetone in urine.
3.The optimal condition of SPME for determining styrene in blood was as follows: 15 H_3PO_4μL/2ml blood,the extraction temperature was 20℃,the extraction time was 10min,the rotation speed was the middle speed,the ratio of sample volume and headspace vacuity was 1:4.The desorption temperature was 250℃,the desorption time was 5min.The linear correlation for acetone in urine was good in 0.00～1.65μg/ml, and the equation was Y=187.24X-2.1059,r=0.9994,the detection limit 0.0006μg/ml, the precision was good,the recovery was greater than 77.0%.The urine sample can be kept for 14 days at 4℃and-8℃.The common possible coexistence agent of the styrene in the environment styrene benzene,toluene,ethyl benzene,xylene,ethylene tetrachloride and the basal body in blood all didn't interfere with the determination of the styrene in blood.The styrene contents of the 30 contact persons and 10 non-contact persons were determined by this method.The styrene contents of the contact persons were form 0.024μg/ml to 0.58μg/ml,the styrene contents of the non-contact persons were all lower than the detection limit.The experiment indicated SPME-GC refers to the determination of the styrene in blood.
Conclusions
1.The article mainly manufactured SPME installation and fiber coating,based on the principle of the SPME technology,which have the characteristic of the similar enriching capability,cheap and simple preparation technology compared with SPME installation and fiber coating in commerce.
2.The determination methods of acetone,benzene,toluene in urine and styrene in blood were researched to standardize by using the self-made SPME installation. According to WS/T 68-1996 the development norm of the biomaterial analytical method(urine and blood),The results indicated that the indexs of the methods researched were all coincidence with the development norm,so they can be reported as biological monitoring standard methods in occupational health for utilizing in the occupational health technical service departments in the whole country.
固相微萃取(SPME)是利用涂有吸附剂的熔融石英纤维吸附样品中的有机物质而达到萃取浓缩的目的,具有无溶剂、可直接进样、操作简便快捷、灵敏的特点,克服了传统的样品前处理技术的缺点。SPME集取样、萃取、富集和进样于一体,操作简便、分析周期短、样品用量少、重现性好、易于自动化,特别适合现场分析,且不用或少量使用有机溶剂,既有利于分析人员的健康又免除了对环境的二次污染。本实验将最新的SPME技术应用到职业卫生生物监测工作中,根据SPME技术的原理,自主研制SPME装置,着重研究固相微萃取技术中固相涂层的制作方法,筛选出适合于测定尿中丙酮、血中苯乙烯的固相涂层,研究制定测定尿中丙酮、血中苯乙烯的SPME检测方法。拟将研究的方法申报为职业卫生生物监测标准方法,在全国职业卫生技术服务部门应用。
方法
1.SPME装置的研制:根据SPME技术的基本原理自主研制了SPME装置,SPME技术中固相涂层材料的选择及制作工艺探讨:根据有机物与溶剂间相似相容原理,选择适用于尿中丙酮、血中苯乙烯的固相涂层材料。通过改变涂层溶液浓度、涂布时间、涂布次数来改变涂层厚度,确定一个最适合上述代谢产物测定的涂层厚度及涂层涂布方法。
2.尿中丙酮、血中苯乙烯的SPME方法学研究:试样量、容器体积、萃取时间、萃取温度、搅拌方式及速率的选择。
3.SPME与气相色谱(GC)连用条件的选择:包括柱类型、柱温、进样口温度、检测器温度的选择、解吸温度、解吸时间的确定。
4.现场应用研究:选择接触丙酮、苯乙烯等毒物的接毒工人进行方法学验证,同时取空白样品作对照。
结果
1.自制SPME萃取装置制作简单、使用方便。适合尿中丙酮、血中苯乙烯的萃取涂层为PDMS涂层,涂层涂布3次,涂层溶液浓度50g/L,加入6%固化剂时,萃取效果较好,萃取时间适宜。用显微镜测得制成的PDMS涂层厚度为120μm。
2.尿中丙酮测定最优SPME条件为无水硫酸钠用量4克,萃取温度为30℃,萃取时间为20min,转速选择为低速,尿样体积与顶空空间比例为1:3,解吸温度为250℃,解吸时间为5min。尿中丙酮在0.0～150.0μg/mL范围内线性关系良好,方程式为Y=3.55X+3.05,相关系数r=0.9990,检出限为0.0008μg/mL,方法精密度良好,回收率90.7%以上,尿样可在室温下和4℃冰箱中保存14天,环境可能存在的丙酮共存物二氯甲烷、2-丁酮、甲醇、乙酸乙酯及尿样中基体均不干扰丙酮的测定。应用本方法测定了30名丙酮接触者和10名丙酮非接触者尿中丙酮的含量。丙酮接触者尿样中丙酮含量范围为0.04～62.97μg/mL,丙酮非接触者尿样中丙酮含量均小于检出限。实验结果表明SPME-GC法适用于尿中丙酮的测定。
3.血中苯乙烯测定最优SPME条件为浓磷酸15μl/2毫升血样,萃取温度为20℃,萃取时间为10min,转速选择为中速,血样体积/项空空间比例为1:4,解吸温度为250℃,解吸时间为5min。血中苯乙烯在0.00～1.65μg/mL范围内线性关系良好,方程式为Y=187.24X-2.10,相关系数r=0.9994,检出限为0.0006μg/mL,方法精密度良好,回收率77.0%以上,血样可在4℃冰箱和冷冻条件下-8℃下均可保存14天,环境可能存在的苯乙烯共存物苯、甲苯、乙苯、二甲苯、四氯乙烯和血样基体均不干扰苯乙烯的测定。应用本方法测定了30名苯乙烯接触者和10名非接触者血中苯乙烯的含量。苯乙烯接触者血样中苯乙烯含量范围为0.024～0.58μg/mL,苯乙烯非接触者血中苯乙烯含量均小于检出限。实验表明SPME-GC法适用于血中苯乙烯的测定。
结论
1.本文根据SPME技术的基本原理研制了SPME装置及纤维涂层,与商品化SPME装置及涂层相比,具有富集能力相当、价格低廉,制备工艺简单等特点。
2.利用自制SPME装置对尿中丙酮、血中苯乙烯的检测方法进行规范化研究,并对该方法进行了方法学评价及各项实验验证,该方法各项实验指标均符合《生物材料分析方法的研制准则(尿样及血样)》(WS/T 68-1996)的要求,可以申报为职业卫生生物监测标准方法,并在全国职业卫生技术服务部门应用。
Objectives
The solid-phase microextraction(SPME)utilizes the fused quartz fiber which is coated on adsorbing material to absorb the organics in the samples to achieve the purpose of extraction and concentration.It haves the characteristic of no-solvent, direct sample introduction,convenient and shortcut to manipulate and sensitive and it overcomes the weakness of the orthodox sample pre-processing technical.SPME integrates the sampling,extraction,enriching and injection in one step,it is convenient to manipulate,analysis cycle is short,few dosage of sample is used,the reproducibility is good,and it is easy to be automatic so it is fit for analysis on the spot particularly,little organic solvent used is profit for the healthy of analytical personnel,and the secondary pollution to environment is to exempt.In this experiment,the newest SPME technology was applied to biological monitoring in occupational health.Based on the development,principle and type of the solid-phase microextraction,the SPME installation was developed and the developing methods of the fiber coating was researched emphasizily.The coatings fit for the determination of acetone in urine and styrene in blood were screened.The SPME detection methods of the determination for acetone in urine and styrene in blood were institute.Then the methods researched will be reported as biological monitoring standard methods in occupational health for utilizing in the occupational health technical service departments in the whole country.
Methods
1.The manufacture of the SPME installation:according to the principle of the SPME,design the SPME installation.The selection of the coating materials and the approach for manufacture technology:select the coating materials referring to acetone in the urine and styrene in the blood according to the principle that the organics and solvents similar were compatible.The coating thickness and the coating methods fit for the metabolic product above mentioned by changing the concentration of the coating solution,coating time,coating number of times to alter the coating thickness.
2.The technology research of solid-phase microextraction for determining acetone in the urine and styrene in the blood:the selection of sample size, container volume,extraction time,extraction temperature,stirring style and velocity.
3.The selection of GC condition connecting with SPME:including the selection of the type of the chromatographic column,the column temperature,the inject opening temperature,the detector temperature,and the definition of the adsorption temperature,adsorption time,adsorption solvent.
4.Technology validation by selecting the workers contacting with the poisons such as acetone,styrene and so on,at the same time comparison by determining the blank sample.
Results
1.The self-made SPME extraction installation was made easily and used conveniently.The extraction coating PDMS was effective to extract acetone in urine and styrene in blood,the coating was coated for thrice,the concentration of the coating solution was 50g/L,and 6%curing agent was added in,at that time,the effect was good,and the extraction time was suitable.The PDMS coating thickness was 120μm measured by the microscope.
2.The optimal condition of SPME for determining acetone in urine was as follows: 4gNa_2SO_4,the extraction temperature was 30℃,the extraction time was 5min,the rotation speed was brachytely,the ratio of sample volume and headspace vacuity was 1:3,the desorption temperature was 250℃,the desorption time was 5min.The linear correlation for acetone in urine was good in 0.0～150.0μg/ml,and the equation was Y =3.55X+3.05,r=0.9990,the detection limit 0.0008μg/ml,the precision was good,the recovery was greater than 90.7%.The urine sample can be kept for 14 days at 4℃.The common possible coexistence agent of the acetone in the environment dichloromethane, 2-butanone,methanol,acetic ether and the basal body in urine all didn't interfere with the determination of the acetone in urine.The acetone contents of the 30 contact persons and 10 non-contact persons were determined by this method.The acetone contents of the contact persons were form 0.04μg/ml to 62.97μg/ml,the acetone contents of the non-contact persons were all lower than the detection limit.The experiment indicated SPME-GC refers to the determination of the acetone in urine.
3.The optimal condition of SPME for determining styrene in blood was as follows: 15 H_3PO_4μL/2ml blood,the extraction temperature was 20℃,the extraction time was 10min,the rotation speed was the middle speed,the ratio of sample volume and headspace vacuity was 1:4.The desorption temperature was 250℃,the desorption time was 5min.The linear correlation for acetone in urine was good in 0.00～1.65μg/ml, and the equation was Y=187.24X-2.1059,r=0.9994,the detection limit 0.0006μg/ml, the precision was good,the recovery was greater than 77.0%.The urine sample can be kept for 14 days at 4℃and-8℃.The common possible coexistence agent of the styrene in the environment styrene benzene,toluene,ethyl benzene,xylene,ethylene tetrachloride and the basal body in blood all didn't interfere with the determination of the styrene in blood.The styrene contents of the 30 contact persons and 10 non-contact persons were determined by this method.The styrene contents of the contact persons were form 0.024μg/ml to 0.58μg/ml,the styrene contents of the non-contact persons were all lower than the detection limit.The experiment indicated SPME-GC refers to the determination of the styrene in blood.
Conclusions
1.The article mainly manufactured SPME installation and fiber coating,based on the principle of the SPME technology,which have the characteristic of the similar enriching capability,cheap and simple preparation technology compared with SPME installation and fiber coating in commerce.
2.The determination methods of acetone,benzene,toluene in urine and styrene in blood were researched to standardize by using the self-made SPME installation. According to WS/T 68-1996 the development norm of the biomaterial analytical method(urine and blood),The results indicated that the indexs of the methods researched were all coincidence with the development norm,so they can be reported as biological monitoring standard methods in occupational health for utilizing in the occupational health technical service departments in the whole country.
引文
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[25]K.Watanabe-Suzuki,A.Ishii,O.Suzuki.Cryogenic oven-trapping gas chromatography for analysis of volatile organic compounds in body fluids[J].Anal Bioanal Chem,2002,373:75-80.