Polycyclic aromatic hydrocarbons (PAHs) are a group of organic compounds that are both toxic and hazardous to human health and ecological systems. In recent work, a novel analytical strategy based on the chemometric-assisted HPLC-DAD method was proposed for the quantification and source apportionment of eight PAHs in PM10 samples. Compared to traditional chromatographic methods, this approach does not require the purification of complex PM10 samples. Instead, it utilizes a mathematical separation method to extract analytes’ profiles from overlapping chromatographic peaks, enabling precise quantification of PAHs in PM10. Firstly, 40 PM10 samples collected in Loudi city during two sampling periods were used for analysis. Subsequently, the second-order calibration method based on alternating trilinear decomposition (ATLD) was employed to handle the three-way HPLC-DAD data. Finally, the pollution sources of PAHs were analyzed by the feature component analysis method according to the obtained relative concentration matrix. For the validation model, the average recoveries of eight PAHs were between (88.8 ± 7.6)% and (105.6 ± 7.5)%, and the root-mean-square errors of prediction ranged from 0.03 μg mL−1to 0.47 μg mL−1. The obtained limits of quantification for eight PAHs were in the range of 0.0050 μg mL−1to 0.079 μg mL−1. For actual PM10 samples, results of the feature component analysis indicated that the main source of PAHs in PM10 may be traffic emissions and coal combustion. In summary, the proposed method provided a new and rapid analysis method for the accurate determination and source apportionment of PAHs in atmospheric aerosols.
Xuan Luo,Xiang-Dong Qing,Xu-Chang Miao,Sen Xiang,Hong-Jun Chen,Xiao-Hua Zhang,Min He
In this study, PM10 samples at four locations of Loudi, China were collected from January 2017 to March 2017 and December 2017 to February 2018 at first. Then, a new analytical strategy of second-order calibration based on the alternating trilinear decomposition (ATLD) coupled with gas chromatography-mass spectrometry (GC-MS) was firstly developed for quantitative analysis of seven polycyclic aromatic hydrocarbons (PAHs) in these samples. This strategy is more sensitive and efficient than traditional chromatography not only, but also it can resolve the problems of baseline drift and peaks overlapping in chromatographic analysis. Without the need for intricate pretreatment process and any derivation reactions, useful qualitative and quantitative information of seven PAHs was quickly extracted from the GC-MS-Sample data array by replacing chemical or physical separation with mathematical separation. In validation samples, the average recoveries of seven PAHs ranged from (96.7 ± 4.8) % to (107.9 ± 4.2) %, and the root-mean-square errors of prediction (RMSEPs) were within the range of 0.03–0.35 μg mL−1. The highest concentrations of individual PAHs in these samples were for phenanthrene (1.34 μg mL−1 in monitoring station), acenaphthylene (0.79 μg mL−1 in municipal government) and chrysene (0.53 μg mL−1 in monitoring station). Identified by component analysis, coal combustion and vehicle exhaust were the most possible sources of Loudi, China. These results demonstrated that the proposed method is characterised as a more precise, simple and promising analytical strategy to identify and quantify PAHs in actual aerosol.
The application of calibration transfer methods has been successful in combination with near-infrared spectroscopy or other tools for prediction of chemical composition. One of the developed methods that can provide accurate performances is the piecewise direct standardization (PDS) method, which in this paper is firstly applied to transfer from one day to another the second-order calibration model based on alternating trilinear decomposition (ATLD) method built for the interference-free resolution and determination of multi-analytes in complex systems by liquid chromatography–mass spectrometry (LC–MS) in full scan mode. This is an example of LC–MS analysis in which interferences have been found, making necessary the use of second-order calibration because of its capacity for modeling this phenomenon, which implies analytes of interest can be resolved and quantified even in the presence of overlapped peaks and unknown interferences. Once the second-order calibration model based on ATLD method was built, the calibration transfer was conducted to compensate for the signal instability of LC–MS instrument over time. This allows one to reduce the volume of the heavy works for complete recalibration which is necessary for later accurate determinations. The root-mean-square error of prediction (RMSEP) and average recovery were used to evaluate the performances of the proposed strategy. Results showed that the number of calibration samples used on the real LC–MS data was reduced by using the PDS method from 11 to 3 while producing comparable RMSEP values and recovery values that were statistically the same ( F -test, 95% confidence level) to those obtained with 11 calibration samples. This methodology is in accordance with the highly recommended green analytical chemistry principles, since it can reduce the experimental efforts and cost with regard to the use of a new calibration model built in modified conditions.
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