González-Sálamo Javier, Socas-Rodríguez Bárbara, Hernández-Borges Javier, Rodríguez-Delgado Miguel Ángel
Departamento de Química, Unidad Departamental de Química Analítica, Facultad de Ciencias, Universidad de La Laguna (ULL), Avda. Astrofísico Fco. Sánchez, s/n(o), 38206 San Cristóbal de La Laguna, Spain.
Departamento de Química, Unidad Departamental de Química Analítica, Facultad de Ciencias, Universidad de La Laguna (ULL), Avda. Astrofísico Fco. Sánchez, s/n(o), 38206 San Cristóbal de La Laguna, Spain.
J Chromatogr A. 2017 Dec 29;1530:35-44. doi: 10.1016/j.chroma.2017.11.013. Epub 2017 Nov 8.
In this work, the first application of core-shell poly(dopamine) magnetic nanoparticles as sorbent for the extraction of a group of eleven phthalic acid esters of interest (i.e. diethyl phthalate (DEP), dipropyl phthalate (DPP), dibutyl phthalate (DBP), bis-isopentyl phthalate (DIPP), bis-n-pentyl phthalate (DNPP), benzylbutyl phthalate (BBP), dicyclohexyl phthalate (DCHP), di-(2-ethylhexyl) phthalate (DEHP), di-n-octyl phthalate (DNOP), diisononyl phthalate (DINP) and diisodecyl phthalate (DIDP)) and one adipate (bis (2-ethylhexyl) adipate, DEHA) from different water samples (Milli-Q, mineral, tap, pond and waste water) is proposed. Analysis were carried out by gas chromatography triple quadrupole tandem mass spectrometry. Parameters that affect the extraction performance were optimized following a step by step approach, being the optimum conditions the extraction of water at pH 6, with 60mg of sorbent and the elution with 6mL of dichloromethane. The methodology was validated for the five selected water samples using DBP-d as internal standard. Determination coefficients of matrix-matched calibration curves were above 0.9904 in all cases while relative recovery values ranged between 71 and 120%, with relative standard deviation values below 19%. The limits of quantification of the method ranged between 9 and 20ng/L. Matrix effects were found for most analytes and water samples. Real water samples were also analyzed, finding DEP and DBP at concentrations below 4.20 and 1.23μg/L, respectively, in mineral, tap and waste water. DCHP, DEHP and BBP were also found in some of the samples at concentrations below the LOQs of the method.
在本研究中，首次提出将核壳聚多巴胺磁性纳米颗粒用作吸附剂，从不同水样（超纯水、矿泉水、自来水、池塘水和废水）中萃取一组11种目标邻苯二甲酸酯（即邻苯二甲酸二乙酯（DEP）、邻苯二甲酸二丙酯（DPP）、邻苯二甲酸二丁酯（DBP）、邻苯二甲酸双异戊酯（DIPP）、邻苯二甲酸双正戊酯（DNPP）、邻苯二甲酸苄基丁酯（BBP）、邻苯二甲酸二环己酯（DCHP）、邻苯二甲酸二（2-乙基己基）酯（DEHP）、邻苯二甲酸二正辛酯（DNOP）、邻苯二甲酸二异壬酯（DINP）和邻苯二甲酸二异癸酯（DIDP））以及一种己二酸酯（己二酸双（2-乙基己基）酯，DEHA）。采用气相色谱三重四极杆串联质谱法进行分析。采用逐步方法对影响萃取性能的参数进行了优化，最佳条件为在pH 6的水中，使用60mg吸附剂进行萃取，并用6mL二氯甲烷进行洗脱。以DBP-d为内标，对所选的五种水样进行了方法验证。在所有情况下，基质匹配校准曲线的测定系数均高于0.9904，相对回收率在71%至120%之间，相对标准偏差值低于19%。该方法的定量限在9至20ng/L之间。大多数分析物和水样均存在基质效应。还对实际水样进行了分析，在矿泉水、自来水和废水中分别检测到浓度低于4.20和1.23μg/L的DEP和DBP。在一些样品中还检测到浓度低于该方法定量限的DCHP、DEHP和BBP。
