Boyacı Ezel, Çağır Ali, Shahwan Talal, Eroğlu Ahmet E
Department of Chemistry, İzmir Institute of Technology, Urla, 35430, İzmir, Türkiye; Department of Chemistry, Middle East Technical University, Ankara, 06800, Türkiye.
Department of Chemistry, İzmir Institute of Technology, Urla, 35430, İzmir, Türkiye.
Talanta. 2025 Dec 1;295:128373. doi: 10.1016/j.talanta.2025.128373. Epub 2025 May 24.
A novel SPME-LC-ICP-MS methodology is described for the simultaneous microextraction/speciation/determination of the metabolically critical inorganic and organoarsenic species, namely, As(III), As(V), dimethylarsinic acid (DMA), and monomethylarsonic acid (MMA) in natural waters such as drinking and geothermal waters, and biological fluids such as urine. The novelty of the study stems also from the use of home-made SPME fibers for the extraction process, and from the proposed methodology needing no derivatization step. SPME fibers were prepared with in-tube capillary template approach through the immobilization of iron nanoparticles into agarose matrix. The fibers demonstrated reproducible extraction (<10 % RSD), good mechanical strength and good solvent resistivity. The separation of the analytes was realized by HPLC with a strong anion exchange column via gradient elution using different concentrations of (NH)CO (pH 8.50), and the on-line detection of eluted analytes was achieved by ICP-MS. The validity of the proposed methodology was verified via the analysis of certified reference materials (SRM 1643e, Natural Water-Trace Elements, and SRM 2669, Arsenic Species in Frozen Human Urine) and through spike recovery tests. The values of percentage recovery for SRM 2669 were 90.7 % for As(III), 99.8 % for As(V), 93.6 % for DMA, and 85.9 % for MMA. A good correlation was also found between the certified (60.45 μgL) and determined (59.00 μgL) values for SRM 1643e. Moreover, the speciation capability of the method was demonstrated on various natural waters and biological fluids.
本文描述了一种新型的固相微萃取-液相色谱-电感耦合等离子体质谱（SPME-LC-ICP-MS）方法，用于同时对饮用水、地热水等天然水体以及尿液等生物流体中具有代谢关键作用的无机和有机砷物种，即三价砷（As(III)）、五价砷（As(V)）、二甲基砷酸（DMA）和一甲基砷酸（MMA）进行微萃取/形态分析/测定。该研究的新颖之处还在于在萃取过程中使用了自制的固相微萃取纤维，以及所提出的方法无需衍生化步骤。通过将铁纳米颗粒固定在琼脂糖基质中，采用管内毛细管模板法制备了固相微萃取纤维。这些纤维表现出可重复的萃取性能（相对标准偏差<10%）、良好的机械强度和耐溶剂性。通过使用强阴离子交换柱的高效液相色谱（HPLC），采用不同浓度的(NH)CO（pH 8.50）进行梯度洗脱实现分析物的分离，并通过电感耦合等离子体质谱（ICP-MS）对洗脱的分析物进行在线检测。通过分析有证标准物质（SRM 1643e，天然水-微量元素，以及SRM 2669，冷冻人尿中的砷物种）和加标回收率试验验证了所提出方法的有效性。SRM 2669中As(III)的回收率为90.7%，As(V)为99.8%，DMA为93.6%，MMA为85.9%。在SRM 1643e的认证值（60.45 μgL）和测定值（59.00 μgL）之间也发现了良好的相关性。此外，该方法的形态分析能力在各种天然水体和生物流体上得到了证明。
