Quantitative determination of ametryn in river water using surface-enhanced Raman spectroscopy coupled with an advanced chemometric model

• A novel SERS method for the quantification of ametryn in water was proposed.
• The effects of non-chemical properties on SERS signals were eliminated by MEMSERS.
• The matrix difference between samples has little effect on the predictive results.
• No laborious reference methods are needed to build the MEMSERS calibration model.
• The proposed method can compete with LC-MS/MS in terms of quantitative accuracy.

In this contribution, surface-enhanced Raman spectroscopy (SERS) coupled with an advanced chemometric method-multiplicative effects model (MEMSERS) has been applied to quantitative analysis of ametryn in water samples of the Xiangjiang River (Changsha, China). The adoption of MEMSERS calibration model was to eliminate the detrimental effects caused by variations in the physical properties of enhancing substrates, the intensity and alignment/focusing of laser excitation source. Experimental results showed that the combination of SERS with MEMSERS can provide quite precise concentration predictions for ametryn in water samples of the Xiangjiang River with an average relative prediction error of about 4.8%. The combination of SERS with MEMSERS can compete with LC-MS/MS in terms of precision and accuracy of quantitative results. The limit of quantification was about 0.09 μM. More importantly, no laborious reference methods (e.g., HPLC) were needed to build the MEMSERS calibration model, since the MEMSERS calibration model built on the calibration samples prepared with ultrapure water could provide satisfactory quantification results for the test samples prepared with water collected from the Xiangjiang River. Therefore, it is reasonable to expect that SERS in combination with MEMSERS model would become a competitive alternative in routine quantitative analysis of ametryn in environmental water samples.