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Contamination and Industrial Systems

                                                            Contamination and Industrial Systems  197

                          0.9

                          0.8

                          0.7                   l min     Sample plus
                         Absorbance (1cm path)  0.5                   l max
                          0.6
                                                          absorbing matrix



                          0.4
                          0.3

                                 Sample in
                          0.2
                                 nonabsorbing solvent
                          0.1

                          0.0
                            250     300     350     400     450     500     550     600     650
                                                       Wavelength (nm)
                       Figure 9.7 Where the known absorption feature is added to a nonuniform absorbing background,
                       three-point measurements can help to recover the true absorbance. Calculate at the peak, or find
                       the area under the feature.


                       absorbance difference will remain fixed. Hence, even if the attenuation due to
                       the contamination changes with time, the dual-wavelength measurement will
                       be well compensated.


           9.3.2 Three-wavelength measurements
                       In many cases with both chemical and biofilm contamination the film attenua-
                       tion is not spectrally flat, and so the two-wavelength procedure breaks down.
                       Now three wavelengths will do a better job of estimating the true species’
                       absorption (Fig. 9.7). A common procedure is to draw a straight line between
                       the absorbance values at the lower and upper reference wavelengths (l min, l max),
                       equally spaced about the peak absorption. Then we can reconstruct the base-
                       line and determine the absorbance at the peak l c from the elevation at the peak,
                       or integrate the area under the absorbance feature between the bounding wave-
                       lengths. In this case the absorption spectrum of the contaminant can change in
                       magnitude and in slope without greatly increasing the error. If a good model or
                       measurement of the contamination alone is available, for example by measur-
                       ing a pure water “blank” in the contaminated cell, then the accuracy of the inte-
                       gration can be further improved. Unfortunately, the spectral absorption of
                       fouling is often neither well characterized nor predictable, so errors will always
                       be present if using a model.


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