The feasibility of determining low levels of organic solvents in water by near-infrared (near-IR) spectroscopy is investigated. Mixture samples of tributyl phosphate (TBP) and methyl iso-butyl ketone (MIBK) are determined in aqueous solutions over the concentration range of 1-160 ppm. Through the use of C-H combination bands in the region of 5000-4000 cm<sup>-1</sup>, sufficient selectivity is obtained to determine each compound in the presence of the other. Separate multivariate calibration models are computed for each compound by use of a combination of bandpass Fourier digital filtering and partial least-squares (PLS) regression with both analysis of absorbance and single-beam spectra. A genetic algorithm is used to implement a joint optimization of the parameters governing the filtering and PLS calculations. Through the use of this procedure, a calibration model based on absorbance spectra is computed for MIBK with a standard error of prediction (SEP) of 3.82 ppm over the 1-160 ppm range. This five-term model utilizes the spectral range of 4495-4335 cm<sup>-1</sup>. A similar nine-term model based on absorbance spectra is computed for TBP over the 4620-4320 cm<sup>-1</sup> range. For the range of 1-100 ppm, an SEP of 4.84 ppm is achieved. The results obtained from the analysis of single-beam spectra are comparable with those obtained in the analysis of absorbance data. Calibration models computed with samples prepared in natural water are also found to have a similar level of performance. These results establish the feasibility of using near-IR spectroscopy to screen water samples for solvent contamination.
Qing Ding, Brian L. Boyd, and Gary W. Small, "Determination of Organic Contaminants in Aqueous Samples by Near-Infrared Spectroscopy," Appl. Spectrosc. 54, 1047-1054 (2000)