Quantification of Lanthanides on a PMMA Microfluidic Device with Three Optical Pathlengths Using PCR of UV-Visible, NIR, and Raman Spectroscopy.

Microfluidic devices (MFDs) offer customizable, low-cost, and low-waste platforms for performing chemical analyses. Optical spectroscopy techniques provide nondestructive monitoring of small sample volumes within microfluidic channels. Optical spectroscopy can probe speciation, oxidation state, and concentration of analytes as well as detect counterions and provide information about matrix composition. Here, ultraviolet-visible (UV-vis) absorbance, near-infrared (NIR) absorbance, and Raman spectroscopy are utilized on a custom poly(methyl methacrylate) (PMMA) MFD for the detection of three lanthanide nitrates in solution. Absorbance spectroscopies are conducted across three pathlengths using three portions of a contiguous channel within the MFD. Univariate and chemometric multivariate modeling, specifically Beer's law regression and principal component regression (PCR), respectively, are utilized to quantify the three lanthanides and the nitrate counterion. Models are composed of spectra from one or multiple pathlengths. Models are also constructed from multiblock spectra composed of UV-vis, NIR, and Raman spectra at one or multiple pathlengths. Root-mean-square errors (RMSE), limit of detection (LOD), and residual predictive deviation (RPD) values are compared for univariate, multivariate, multi-pathlength, and multiblock models. Univariate modeling produces acceptable results for analytes with a simple signal, such as samarium cations, producing an LOD of 5.49 mM. Multivariate and multiblock models produce enhanced quantification for analytes that experience spectral overlap and interfering nonanalyte signals, such as holmium, which had an LOD reduction from 7.21 mM for the univariate model down to 3.96 mM for the multiblock model. Multi-pathlength models are developed that maintain model errors in line with single-pathlength models. Multi-pathlength models have RPDs from 9.18 to 46.4, while incorporating absorbance spectra collected at optical paths of up to 10-fold difference in length.