气相色谱法在血清邻苯二甲酸酯类化合物检测中的应用

Application of Gas Chromatography in the Detection of DEHP and DBP in Human Serum

目的:建立一种有效的检测血清邻苯二甲酸二丁酯(DBP)、邻苯二甲酸酯(DEHP)的气相色谱法,并分析人体受其污染的现状。方法:选择健康志愿者及性早熟女童为研究对象,采用液-液萃取法对其血清中DBP、DEHP进行分离、纯化,气相色谱法进行检测。结果:DBP、DEHP含量在0.10-10.0mg/L范围内呈良好的线性关系,相关系数分别为r=0.999 6和r=0.999 3,检出限为0.10mg/L和0.08mg/L。平均加标回收率分别为96.76%-104.99%和94.78%-99.91%。日内与日间精密度的相对标准偏差范围,DBP为3.05%-4.81%和3.23%-6.50%,DEHP为2.40%-3.63%和2.93%-8.67%。血清DBP、DEHP检出率,健康成人志愿者分别为70.61%、67.91%,女性和男性无显著性差异(P>0.05),性早熟女童显著高于正常对照女童(DBP为95%比72.50%,P<0.05;DEHP为96.25%比73.75%,P<0.05);健康成人志愿者血清DBP水平,女性高于男性[(0.598±0.124)比(0.246±0.043)mg/L,P<0.05],性早熟女童血清DBP[(1.801±0.052)比[(1.376±0.135)DEHP(0.253±0.044)比(0.488±0.236)mg/L],P<0.05]水平显著高于同龄健康对照女童。结论:本方法灵敏度高、重现性好,可用于血清邻苯二甲酸酯类化合物的检测;人体受邻苯二甲酸酯类化合物的污染严重,DBP和DEHP可能是导致女童性早熟的重要致病因素之一。

Objective： To establish an efficient method to detect Dibutyl phthalate （DBP） and Bis （2-eth- ylhexyl） phthalate （DEHP） in human serum by gas chromatography. Methods： Healthy subjects and sexually precocious girls were involved in this study, their serum samples were separated and purified by liquid-liquid extraction, gas chromatograph method with FID detector was adopted to measure DBP and DEHP concentration. Results： Good linearity was observed within the range from 0.10 mg/L to 10.00 mg/L （r=0. 999 6 and r=0. 999 3）, and the lowest detectable concen- tration was 0. 10 mg/L and 0. 08 mg/L. The average recoveries were 96. 76%-104. 99% and 94.78%-99.91% respectively for DBP and DEHP. The relative standard deviation （RSD） for in- ter- and intra-day was 3. 05%-4. 81% and 3. 23%-6. 50% respectively for DBP, and 2. 40%- 3.63% and 2.93%-8.67% respectively for DEHP. The relevance ratios of the DBP and DEHP were 70.61% and 67.91% respectively, there was no significant difference between women and men （P〉0.05）. The relevance ratios of precocious puberty girls were significantly higher than in normal girls （DBP： 95% vs 72.50%, P%0.05; DEHP. 96.25% vs 73.75%, P〈0.05）. The levels of DBP and DEHP in precocious puberty girls were significantly higher than that in normal girls （DBP： [1. 801±0. 052] vs [0. 253±0. 044] mg/L, P〈0.05; DEHP： [1. 376±0. 135] vs [0. 488±0. 236] mg/L, P〈0.05）. Conclusion： This method for DEHP and DBP detection is sen- sitive, economic and convenient, so it is suitable for biological monitoring. The phthalate esters pollution in serum of the human is serious,and DBP and DEHP are important factors of the girls＇ precocious puberty.