Stevens Harrison, Sanz Rodriguez Estrella, Lai Mingxia, Vance Tessa R, Curran Mark, Ritchie Harald, Bowie Andrew R, Paull Brett
ARC Training Centre for Hyphenated Analytical Separation Technologies (HyTECH), Chemistry School of Natural Sciences, University of Tasmania, Hobart, Tasmania, Australia.
ARC Training Centre for Hyphenated Analytical Separation Technologies (HyTECH), Chemistry School of Natural Sciences, University of Tasmania, Hobart, Tasmania, Australia; Australian Centre for Research on Separation Science (ACROSS), Chemistry School of Natural Sciences, University of Tasmania, Hobart, Tasmania, Australia.
J Chromatogr A. 2025 May 10;1748:465878. doi: 10.1016/j.chroma.2025.465878. Epub 2025 Mar 14.
Levoglucosan (LEV) and two of its isomers, mannosan (MAN) and galactosan (GAL), are commonly used as biomass burning tracers, however 1,6-anhydro-β-D-glucofuranose (AGF), another isomer derived from biomass burning, is rarely identified or quantified in existing literature. When present in environmental samples, AGF may be unknowingly co-eluting with another isomer, thus potentially compromising the accuracy of previously reported results. We present a novel hydrophilic interaction liquid chromatography (HILIC)-based separation method, coupled with tandem triple quadrupole mass spectrometry (MS/MS), capable of separating and quantifying all four fire-marker monosaccharide anhydrides (MAs). This separation relies on the hydrophilic penta‑hydroxy ligand functionality of HALO Penta-HILIC columns. Parameters such as mobile phase composition, column temperature, spray voltage, and selected reaction monitoring transitions were optimised to achieve a baseline separation to both confirm and improve detection of each isomer. Under optimal conditions, the limits of detection for LEV, MAN, GAL, and AGF were 0.39, 0.62, 0.52, and 0.04 µg/L, respectively. The accuracy of the method was validated via the analysis of the NIST Urban Dust 1649b certified reference material, with LEV, MAN, GAL concentrations in good agreement with previously determined results, and the concentration of AGF reported for the first time. The method was applied to a range of environmental samples (aerosols, sediments, and ice cores) to prove its applicability for different matrices. Due to its speed (< 10 min), selectivity, and sensitivity, this HILIC-MS/MS based method can be utilised in future studies to quantify all four fire-marker isomers, allowing the calculation of additional isomer ratios, which may assist with biomass burning source identification.
左旋葡聚糖（LEV）及其两种异构体甘露聚糖（MAN）和半乳聚糖（GAL）通常用作生物质燃烧示踪剂，然而，另一种源自生物质燃烧的异构体1,6-脱水-β-D-葡萄糖呋喃糖（AGF）在现有文献中很少被鉴定或定量。当AGF存在于环境样品中时，它可能会在不知不觉中与另一种异构体共洗脱，从而可能影响先前报道结果的准确性。我们提出了一种基于亲水相互作用液相色谱（HILIC）的新型分离方法，并结合串联三重四极杆质谱（MS/MS），能够分离和定量所有四种火灾标记单糖酐（MA）。这种分离依赖于HALO Penta-HILIC柱的亲水性五羟基配体功能。对流动相组成、柱温、喷雾电压和选择反应监测跃迁等参数进行了优化，以实现基线分离，从而确认并改进每种异构体的检测。在最佳条件下，LEV、MAN、GAL和AGF的检测限分别为0.39、0.62、0.52和0.04μg/L。通过对NIST城市灰尘1649b认证参考物质的分析验证了该方法的准确性，LEV、MAN、GAL的浓度与先前测定的结果高度一致，并且首次报道了AGF的浓度。该方法应用于一系列环境样品（气溶胶、沉积物和冰芯），以证明其对不同基质的适用性。由于其速度快（<10分钟）、选择性高和灵敏度高，这种基于HILIC-MS/MS的方法可用于未来的研究中，以定量所有四种火灾标记异构体，从而计算额外的异构体比率，这可能有助于生物质燃烧源的识别。
