This work presents a novel strategy for simultaneous and rapid quantitative analysis of three pre-emergence herbicides in environmental samples using HPLC-DAD combined with second-order calibration based on the self-weighted alternating trilinear decomposition (SWATLD) algorithm. The sample preparation procedure was simplified only by using water as solvent and methanol as extractant and data were measured in less than 4.2 min by applying an isocratic mode. Although the elution and spectral profiles of the analytes, prometryne (PRO), napropamide (NAP) and alachlor (ALA), are heavily overlapped with each other and with matrix constitutes, the method not only extracts the profiles of the analytes, but also simultaneously determines the concentrations of them in actual complex systems, i.e., river sediment and wastewater samples. In the analysis of river sediment and wastewater samples, the obtained average recoveries were 99 ± 6% and 98 ± 5% for PRO, 108 ± 6% and 100 ± 4% for NAP and 98 ± 5% and 97 ± 4% for ALA, respectively. Furthermore, the accuracy and precision of the proposed method was also evaluated through elliptical joint confidence region tests as well as figures of merit. Such a chemometrics-based protocol may be a very promising tool for more analytical applications in environment monitoring, due to its advantages of easy sample pretreatment, green, sufficient spectral resolution and concentration prediction even in the presence of unknown interferences.
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