Simple multi-signal calibrations exploiting flow analysis systems

Multi-signal calibrations have been recently exploited in molecular spectrochemical analysis alternatively to traditional calibration methods, improving analytical frequency and accuracy. The application of these strategies is simple and minimizes efficiently matrix effects by analyzing two calibration solutions comprising sample plus standard (S1), and sample plus blank (S2). The plot of the signals obtained with S1 and S2 at multiple settings (e.g. different wavelengths) yield a slope that can be related to the analyte concentration in the sample. Similarly, transient signals could also be related to the analyte concentration exploiting a similar strategy. Thus, in this work, two multi-signal approaches developed in flow-based systems are proposed, based on the responses at multiple wavelengths (online multi-energy calibration, OMEC), and on the dispersion profile of the samples, herein denominated multi-dispersion calibration (MDC). The calibrations were carried out with sample solutions after 2-fold dilution with a standard solution and with water. The feasibility of OMEC and MDC were demonstrated using KMnO₄ solutions (without chemical reactions) under continuous and pulsed flow regimes. The applicability of this strategy was also demonstrated by the spectrophotometric determination of urea in milk and pet potty spray in a multi-pumping flow system, based on the color change of bromothymol blue after catalyzed hydrolysis by urease from jack beans (Canavalia ensiformis). MDC and OMEC were compared with external calibrations (EC) and classical standard addition. The limits of detection for urea were estimated at 13 mg L^-1, 16 mg L^-1, and 10 mg L^-1 using MDC, MEC and EC, respectively. Recoveries from 93 to 101%, and the agreement of sample analyzes with the reference procedure demonstrated the good accuracy achieved by the proposed methods. Therefore, it was demonstrated the feasibility of MDC and OMEC for analytical purposes in a simple and efficient way with the advantages of flow-based manifolds.