Conventional pulse oximeters assume that the major absorbers of light within arterial blood are deoxygenated hemoglobin (HHb) and oxygenated hemoglobin (O2Hb) and calculate SpO2 based on the ratio of measured absorbance of only two wavelengths of light (660nm and 940nm).  Methemoglobinemia (MetHb) occurs when the iron in hemoglobin is oxidized, altering its ability to bind and offload oxygen.
The molar extinction coefficient of MetHb at 660 nm red light is approximately 1 and approximately equal to the molar extinction coefficient of HHb (see image below).  The molar extinction coefficient of MetHb at 940 nm infrared light is also approximately 1 and significantly higher than the molar extinction coefficient of O2Hb.  As a result of MetHb absorbing 660 nm and 940 nm light approximately equally, the Modulation Ratio (R-Value) approaches 1, this corresponds to an SpO2 of 80-88%. This can result in either an overestimation or an underestimation of SaO2 levels.
When a patient is cyanotic and methemoglobinemia is suspected, a co-oximeter capable of measuring the absorbance of greater than 2 wavelengths of light is necessary to determine fractional oxygen saturation and MetHb levels.
Figure: Jubran, Critical Care, 2015
Keywords: Dyshemoglobin, Methemoglobin, Methemoglobinemia,
References: Jubran, Critical Care, 2015 Chan et al, Respiratory Medicine 2013