An in-tube solid phase microextraction, coupled with high-performance liquid chromatography with diode array detection (IT-SPME-HPLC-DAD) method, has been developed for the simultaneous determination of 13 diesters (from dimethyl to dioctylphthalate plus diisobutyl, benzylbutyl, di-2-ethylhexyl, diisononyl and diisodecylphthalate) and 2 monoesters of phthalic acid (mono-butyl and mono-(2-ethylhexyl) phthalate) in particulate matter (PM₁₀). Triethylamine at pH = 3 was used as an ion-pair reagent with a double function, of regulating the chromatographic retention of the monoesters and the most hydrophilic diesters on a monolithic silica column, and of improving their extraction on a porous polymer with divinylbenzene-4-vinylpyridine capillary. The chromatographic separation was achieved in 13 min. A previous ultrasound-assisted extraction from PM₁₀filters was also optimized using methanol as solvent. The method detection limits were 0.09–0.52 ng m⁻³, the inter-day precision at concentration of 20 ng mL⁻¹ was between 4.2% and 12.7% (n = 15), and the average recovery was 87.3%. The average absolute IT-SPME recovery was 26.2% and the linear range reached up to 109 ng m⁻³ for most analytes. The method was applied to PM₁₀ samples from different environments collected in Galicia (Spain). DiBP was the major phthalate, followed by its isomer DnBP in urban sites and by DEP in the suburban area. In all samples, DEHP quantified correlates with the isomers of dibutylphthalate. Total PAE concentration was between 14.5 and 245.5 ng m⁻³. To the best of our knowledge, this is the first time that a method allows the simultaneous determination of 13 phthalates and their degradation products in particulate matter.

已开发出一种管内固相微萃取结合高效液相色谱和二极管阵列检测（IT-SPME-HPLC-DAD）方法，用于同时测定13种二酯（从邻苯二甲酸二甲酯到邻苯二甲酸二辛酯加二异丁基，苄基丁基酯，颗粒物中的邻苯二甲酸二-2-乙基己酯，邻苯二甲酸二异壬基酯和邻苯二甲酸二异癸酯）和2种邻苯二甲酸单酯（邻苯二甲酸单丁酯和邻苯二甲酸单（2-乙基己基）酯）（PM ₁₀）。pH = 3的三乙胺用作具有双重功能的离子对试剂，可调节单酯和最亲水的二酯在整体硅胶柱上的色谱保留率，并改善在二乙烯基苯-4多孔聚合物上的萃取率-乙烯基吡啶毛细管。色谱分离在13分钟内完成。还使用甲醇作为溶剂优化了先前从PM ₁₀过滤器中进行的超声辅助提取。该方法的检出限为0.09–0.52 ng m ^-3，浓度为20 ng mL ^-1时，日间精密度在4.2％和12.7％之间（n = 15），平均回收率是87.3％。IT-SPME的平均绝对回收率为26.2％，线性范围达到109 ng m ^-3适用于大多数分析物。该方法应用于从加利西亚（西班牙）收集的不同环境中的PM ₁₀样品。DiBP是主要的邻苯二甲酸酯，其次是城市地区的异构体DnBP和郊区的DEP。在所有样品中，定量的DEHP与邻苯二甲酸二丁酯的异构体相关。PAE的总浓度在14.5至245.5 ng m ^-3之间。据我们所知，这是首次允许同时测定13种邻苯二甲酸酯及其在颗粒物中的降解产物的方法。