Electrodes, blood gases, luminescence and light scatter
15 min
- Explain why an indirect ion-selective electrode (ISE) can show pseudohyponatremia
- Distinguish measured blood-gas values from calculated values
- Distinguish excitation-driven fluorescence from chemical light production
- Distinguish turbidimetric attenuation from nephelometric scatter
Try first
Get the idea
Direct and indirect electrodes
An ion-selective electrode (ISE) responds to ion activity in the water phase of the specimen.1,2
- A direct ISE measures undiluted plasma or whole blood, so it reads sodium in the water phase alone.
- An indirect ISE dilutes a fixed volume of plasma with buffer and calculates sodium per volume of whole plasma. The calculation assumes plasma is about 93% water.
Severe hyperlipidemia or hyperproteinemia lowers the water fraction. The fixed plasma volume then carries less water and less sodium into the diluent, and the indirect result is falsely low. This artifact is pseudohyponatremia. A direct ISE on the same specimen stays close to the physiologic value.2,3
Measured and calculated blood-gas values
A blood gas analyzer measures pH, pCO2 and pO2 with electrodes. Co-oximetry measures the hemoglobin fractions by absorbance at several wavelengths. Bicarbonate is calculated from pH and pCO2.2,4
A saturation calculated from pO2 and an assumed dissociation curve uses no hemoglobin measurement. It cannot show carboxyhemoglobin or methemoglobin. In carbon monoxide poisoning the pO2 and the calculated saturation can look normal as the measured oxyhemoglobin falls.2,4
Light from a lamp or from a reaction
In fluorescence, a fluorophore absorbs excitation light and emits light of a longer wavelength. The difference is the Stokes shift. The detector sits away from the excitation path, often at 90 degrees.1,2
In chemiluminescence, a chemical reaction makes the excited product, and a photomultiplier tube reads the light it gives off. The analyzer has no excitation lamp. Low or high signal comes from reagent or substrate deterioration, timing error, incomplete washing, carryover or detector saturation.2
Scatter read in line or off axis
Particles in suspension scatter light, and the detector's position decides what is measured.1,2
| Method | Detector position | As concentration rises |
|---|---|---|
| Turbidimetry | In line with the beam | Transmitted light falls |
| Nephelometry | Off axis, commonly 30 to 90 degrees | Scattered light rises from a dark background |
Nephelometry generally detects lower concentrations, because it measures a small signal against a dark background.2
References
- Bishop ML, Fody EP, Van Siclen C, Mistler JM, Moy M. Clinical Chemistry: Principles, Techniques, and Correlations. 9th ed. Jones & Bartlett Learning; 2023.
- Rifai N, Chiu RWK, Young I, Burnham CAD, Wittwer CT, eds. Tietz Textbook of Laboratory Medicine. 7th ed. Elsevier; 2023.
- Fortgens P, Pillay TS. Pseudohyponatremia revisited: a modern-day pitfall. Arch Pathol Lab Med. 2011;135(4):516-519. doi:10.5858/2010-0018-RS.1
- Clinical and Laboratory Standards Institute. Blood Gas and pH Analysis and Related Measurements. 2nd ed. CLSI guideline C46-A2. Clinical and Laboratory Standards Institute; 2009. Archived and retained as technically valid. Accessed September 26, 2026. https://clsi.org/shop/standards/c46/
Watch one
An arterial specimen from a patient brought in from a house fire gives these results on a blood gas analyzer with co-oximetry:
- pH 7.36, pCO2 38 mm Hg and pO2 96 mm Hg
- calculated oxygen saturation 97%
- oxyhemoglobin fraction (FO2Hb) 71%, carboxyhemoglobin 26%, methemoglobin 0.6% and deoxyhemoglobin 2.4%
Which results describe the patient's oxygen-carrying hemoglobin?
- Sort the results: pH, pCO2 and pO2 come from electrodes, the four hemoglobin fractions come from co-oximetry, and the saturation is calculated.
Measured and calculated values rest on different evidence, and the report shows both.
- Read the pO2: 96 mm Hg sits inside the arterial reference interval of 75 to 100 mm Hg.
The partial pressure of oxygen measures dissolved oxygen and says nothing about which hemoglobin species carry it.
- Set the calculated saturation of 97% aside, because no hemoglobin was measured to produce it.
The calculated saturation comes from the partial pressure of oxygen and an assumed curve, so it cannot see carboxyhemoglobin either.
- Read the measured fractions: carboxyhemoglobin is 26%, and oxyhemoglobin is only 71% of total hemoglobin. The four fractions add to 100%.
Co-oximetry resolves every species the instrument supports, carboxyhemoglobin included.
- Report the measured fractions, and follow your laboratory's procedure for notifying a high carboxyhemoglobin.
A high carboxyhemoglobin may need a prompt call under the laboratory's notification list.
Your turn
Use it
- A 44-year-old woman in the emergency department (MRN 0061437) has serum electrolytes and a whole-blood blood gas panel drawn together at 09:40.
- The serum is milky. Her triglycerides, measured after dilution, are 5,200 mg/dL.
- The chemistry analyzer measures electrolytes by indirect ISE.
- The blood gas analyzer measures whole-blood sodium by direct ISE.
- Both analyzers' controls were acceptable this morning.
| Test | Result | Previous | Reference interval | Flag |
|---|---|---|---|---|
| Sodium (serum, indirect ISE) | 128 mmol/L | 138 mmol/LSep 23, 08:15 | 135–145 mmol/L | Low |
| Chloride (serum, indirect ISE) | 95 mmol/L | 103 mmol/LSep 23, 08:15 | 98–107 mmol/L | Low |
| Potassium (serum, indirect ISE) | 3.9 mmol/L | 4.1 mmol/LSep 23, 08:15 | 3.6–5.2 mmol/L | |
| Sodium (whole blood, direct ISE) | 139 mmol/L | 135–145 mmol/L |
Specimen: H 10, L 850, I 2. Serum and heparinized whole blood, both collected 09:40 from the same venipuncture.
The clue that settles this case is the pair of sodium results from one draw. The indirect sodium is 128 mmol/L, and the direct sodium is 139 mmol/L, about 8% apart. The lipemia index is 850 and the triglycerides are 5,200 mg/dL, so lipid takes up enough of the plasma to explain the gap. The direct measurement shows her sodium within the reference interval.
Results
- Explain why an indirect ion-selective electrode (ISE) can show pseudohyponatremia
- Distinguish measured blood-gas values from calculated values
- Distinguish excitation-driven fluorescence from chemical light production
- Distinguish turbidimetric attenuation from nephelometric scatter
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