Principles of measuring PCO₂ with the Severinghaus electrode

This chapter is most relevant to Section F12(iii) from the 2017 CICM Primary Syllabus, which expects the exam candidates to be able to "describe the methods of measurement of oxygen and carbon dioxide tension in blood". By some weird cruelty of the CICM examiners, it had come up once in Question 9.1 from the second Fellowship Exam paper of 2009. One can be reasonably confident that it will never appear again.

In summary:

  •  The Severinghaus electrode is a modified glass electrode;
  • The electrode contains some sodium bicarbonate, which reacts with the CO2;
  • The reaction changes the pH in the electrode, which corresponds to a change in potential difference, and this is measured.
  • The CO2 is then inferred from the change in pH.

The recollections of John Severinghaus are not available to most people, as they are locked behind paywalls. This is unfortunate, because he has co-authored some awesomely wacky articles. Thankfully, John W Severinghaus and A. Freeman Bradley's 1958 paper detailing the design and performance characteristics of their first ABG analyser can still be seen at the Journal of Applied Physiology.

The Severinghaus Electrode

This thing is essentially a slightly modified glass electrode. Observe:

severinghaus CO2 electrode

The CO2 dissolved in the sample diffuses into the middle compartment of the electrode via a thin membrane. After experimenting with several thin films of different polymers, Severinghaus settled on Teflon; however subsequent generations have changed over to silicon polymer.

Once inside, the CO2 finds itself in an aqueous solution. For convenience, there may or may not be a bicarbonate solution added to this chamber. The reaction which takes place is an old familiar carbonic acid dissociation equilibrium:

CO2 + H2O ⇌ H2CO3 ⇌ H+ + HCO3-

Thus, the pH of the solution in the middle chamber changes. The change in pH is completely dependent on the pCO2, provided the temperature and pressure remain constant:

relationship of pH to the CO2 of the sample in a severinghaus electrode

This results in a change in potential difference in the glass electrode; and the function of this item has already been discussed at some length in another chapter. Thus, from the change in pH, one can calculate the pCO2.

References

Device-specific information in all these ABG pages refers to the ABG machine used in my home unit.

Other machines may have different reference ranges and different symbols.

For my ABG analyser, one can examine this handy operations manual.

There is also an even more handy reference manual, but one needs to be an owner of this equipment before one can get hold of it. Its called the "989-963I ABL800 Reference Manual"

Nastuk, William L., ed. Special Methods: Physical Techniques in Biological Research. Elsevier, 1962.

Severinghaus, John W. "First electrodes for blood PO2 and PCO2 determination." Journal of Applied Physiology 97.5 (2004): 1599-1600.

Severmghaus, J. W., and A. E. Bradley. "Electrodes for blood PO2 and PC02 determination." J Appl Physzol 13 (1958): 515-520.