Application of ATLD-MCR to gas chromatography-mass spectrometric data for the quantification of PAHs in aerosols

In the work, for the first time, alternating trilinear
decomposition-assisted multivariate curve resolution (ATLD-MCR) was
applied to analyse complex gas chromatography–mass spectrometric (GC-MS)
data with severe baseline drifts, serious co-elution peaks and slight
retention time shifts for the simultaneous identification and
quantification of polycyclic aromatic hydrocarbons (PAHs) in aerosols. It
was also compared with the classic multivariate curve
resolution-alternating least-squares (MCR-ALS) and the GC-MS-based
external standard method. In validation samples, average recoveries of
five PAHs were within the range from (96.2 ± 6.8)% to (106.5 ± 4.1)% for
ATLD-MCR, near to the results of MCR-ALS ((98.0 ± 1.5)% to (106.7 ±
4.3)%). In aerosol samples, the concentrations of pyrene provided by
ATLD-MCR were not significantly different from those of MCR-ALS. The other
four PAHs including chrysene, benzo[a]anthracene, fluoranthene and
benzo[b]fluoranthene were not detected by ATLD-MCR and the GC-MS-based
external standard method. The results of figures of merit further
demonstrated that ATLD-MCR achieved high sensitivities (8.9 × 104 to 1.7 ×
106 mAU ml µg−1) and low limits of detection (0.003 to 0.087 µg ml−1),
which were better than or similar to MCR-ALS, presenting a great choice to
deal with complex GC-MS data for the simultaneous determination of
targeted PAHs in aerosols.

本研究首次将交替三线性分解辅助多元曲线分辨（ATLD-MCR）应用于分析存在严重基线漂移、显著共洗脱峰与轻微保留时间偏移的复杂气相色谱-质谱联用（GC-MS）数据，以同时识别并定量气溶胶中的多环芳烃（PAHs）。同时将该方法与经典的多元曲线分辨-交替最小二乘（MCR-ALS）法及基于GC-MS的外标法进行对比。在验证样品中，ATLD-MCR对5种多环芳烃的平均回收率介于(96.2 ± 6.8)%至(106.5 ± 4.1)%之间，与MCR-ALS的结果((98.0 ± 1.5)%至(106.7 ± 4.3)%)相近。在气溶胶样品中，ATLD-MCR测得的芘浓度与MCR-ALS的结果无显著差异；而屈、苯并[a]蒽、荧蒽及苯并[b]荧蒽这其余4种多环芳烃，ATLD-MCR与基于GC-MS的外标法均未检出。性能指标结果进一步表明，ATLD-MCR具备优异的灵敏度（8.9 × 10^4 至 1.7 × 10^6 mAU·mL·μg^-1）与极低的检出限（0.003 至 0.087 μg·mL^-1），其性能优于或接近MCR-ALS，为处理复杂GC-MS数据以同时测定气溶胶中目标多环芳烃提供了一种极佳的解决方案。