Calibration Transfer Between a Bench Scanning and a Submersible Diode Array Spectrophotometer for In Situ Wastewater Quality Monitoring in Sewer Systems

Abstract

Online monitoring programs based on spectroscopy have a high application potential for the detection of hazardous wastewater discharges in sewer systems. Wastewater hydraulics poses a challenge for in situ spectroscopy, especially when the system includes storm water connections leading to rapid changes in water depth, velocity, and in the water quality matrix. Thus, there is a need to optimize and fix the location of in situ instruments, limiting their availability for calibration. In this context, the development of calibration models on bench spectrophotometers to estimate wastewater quality parameters from spectra acquired with in situ instruments could be very useful. However, spectra contain information not only from the samples, but also from the spectrophotometer generally invalidating this approach. The use of calibration transfer methods is a promising solution to this problem. In this study, calibration models were developed using interval partial least squares (iPLS), for the estimation of total suspended solids (TSS) and chemical oxygen demand (COD) in sewage from Ultraviolet-visible spectra acquired in a bench scanning spectrophotometer. The feasibility of calibration transfer to a submersible, diode array equipment, to be subsequently operated in situ, was assessed using three procedures: slope and bias correction (SBC); single wavelength standardization (SWS) on mean spectra; and local centering (LC). The results showed that SBC was the most adequate for the available data, adding insignificant error to the base model estimates. Single wavelength standardization was a close second best, potentially more robust, and independent of the base iPLS model. Local centering was shown to be inadequate for the samples and instruments used.