A new silicone rubber matrix carbonate-selective membrane and a high-pH buffer diluent are used to enhance the performance of the electrode measurements for serum carbon dioxide. The proposed membrane employs one-component silicone rubber as the matrix and trifluoroacetyl-p-decylbenzene as the neutral ionophore. The optimized membrane formulation incorporates as high as 21.9 wt % plasticizer (e.g., bis(2-ethylhexyl) adipate). The highly plasticized silicone rubber membranes not only function equivalently, in terms of the carbonate response, to the conventional PVC matrix membranes, but they also exhibit substantially reduced interfering response toward salicylate. Furthermore, the silicone rubber membrane exhibits better adhesion to the solid surface than do PVC or PU membranes. The use of higher pH buffers (e.g., 2-amino-2-methyl-1-propanol (AMP)-H(2)SO(4), pH 9.5-10.5) further enhances the selectivity of the carbonate electrode measurement system for total CO(2) species over other anions. It is shown that the combined use of the silicone rubber matrix membrane and the high-pH AMP buffer provides a carbonate sensor system that is substantially less subject to interference from salicylate and chloride than is the conventional measurement system employing the PVC-based electrode with the lower pH (8.4-8.8) buffer diluent.