Non-Severinghaus Potentiometric Dissolved CO2 Sensor with Improved CharacteristicsClick to copy article linkArticle link copied!
Abstract
A new type of carbon dioxide sensor comprising a pH glass electrode measured against a carbonate-selective membrane electrode based on a tweezer type carbonate ionophore is presented here for the first time. No cumbersome liquid junction based reference element is utilized in this measurement. The sensor shows an expected Nernstian divalent response slope to dissolved CO2 over a wide range covering the routine environmental and physiological PCO2 levels. Unlike the conventional Severinghaus CO2 probe for which the response is substantially delayed to up to 10 min due to diffusion of carbon dioxide into the internal compartment, the ion-selective CO2 sensor proposed here shows a response time (t95%) of 5 s. When used together with a traditional reference electrode, the sensor system is confirmed to also monitor sample pH and carbonate along with carbon dioxide. A selectivity analysis suggests that Cl– does not interfere even at high concentrations, allowing one to explore this type of sensor probe for use in seawater or undiluted blood samples. The CO2 probe has been used in an aquarium to monitor the CO2 levels caused by the diurnal cycles caused by the metabolism of the aquatic plants and shows stable and reproducible results.
Experimental Section
Reagents
Apparatus
Membrane and Measurements
Results and Discussion
Scheme 1


Figure 1
Figure 1. Calibration curves of the sensor responses to CO2 in a 10–4 M hydrogen carbonate solution, the gas phase above 10–4 M hydrogen carbonate solution, and dry CO2 + N2 gas mixture with different levels of PCO2. The term Pθ on the x-axis is the partial pressure under standard conditions (1 atm). Shown structure is that of the tweezer-type carbonate ionophore used in the carbonate-selective membrane.
Figure 2
Figure 2. Comparison of response time between the Severinghaus CO2 probe (SH) and the ion-selective CO2 sensor (PCO2) in 0.1 M, pH 8.0 Tris–H2SO4 buffer solution equilibrated with different CO2 partial pressures: (A) 0.0004 atm; (B) 0.0066 atm; (C) 0.0655 atm.
Figure 3
Figure 3. Response of the ion-selective CO2 sensor as a function of pH at a constant PCO2 of 0.05 atm. Solid lines for CO32– and PCO2 are fitted with the modified Nicolsky-Eisenman equation (20) with a logarithmic selectivity coefficient for CO32– over Cl– of −6.2. The broken line indicates the ideal behavior of the sensor.
Supporting Information
Additional information as noted in text. This material is available free of charge via the Internet at http://pubs.acs.org.
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Acknowledgment
The authors thank the Swiss National Science Foundation for financial support of this research.
References
This article references 36 other publications.
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Abstract
Scheme 1
Scheme 1. Representation of the Ion-Selective CO2 Sensor and Its Working PrincipleFigure 1
Figure 1. Calibration curves of the sensor responses to CO2 in a 10–4 M hydrogen carbonate solution, the gas phase above 10–4 M hydrogen carbonate solution, and dry CO2 + N2 gas mixture with different levels of PCO2. The term Pθ on the x-axis is the partial pressure under standard conditions (1 atm). Shown structure is that of the tweezer-type carbonate ionophore used in the carbonate-selective membrane.
Figure 2
Figure 2. Comparison of response time between the Severinghaus CO2 probe (SH) and the ion-selective CO2 sensor (PCO2) in 0.1 M, pH 8.0 Tris–H2SO4 buffer solution equilibrated with different CO2 partial pressures: (A) 0.0004 atm; (B) 0.0066 atm; (C) 0.0655 atm.
Figure 3
Figure 3. Response of the ion-selective CO2 sensor as a function of pH at a constant PCO2 of 0.05 atm. Solid lines for CO32– and PCO2 are fitted with the modified Nicolsky-Eisenman equation (20) with a logarithmic selectivity coefficient for CO32– over Cl– of −6.2. The broken line indicates the ideal behavior of the sensor.
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