Feasibility of measuring dissolved carbon dioxide based on head space partial pressures

We describe an instrument prototype that measures dissolved carbon dioxide (DC) without need for standard wetted probe membranes or titration. DC is calculated using Henry's Law, water temperature, and the steady-state partial pressure of carbon dioxide that develops within the instrument's vertical gas-liquid contacting chamber. Gas-phase partial pressures were determined with either an infrared detector (ID) or by measuring voltage developed by a pH electrode immersed in an isolated sodium carbonate solution (SC) sparged with recirculated head space gas. Calculated DC concentrations were compared with those obtained by titration over a range of DC (2, 4, 8, 12, 16, 20, 24, and 28mg/l), total alkalinity (35, 120, and 250mg/l as CaCO3), total dissolved gas pressure (-178 to 120 mmHg), and dissolved oxygen concentrations (7, 14, and 18 mg/l). Statistically significant (P < 0.001) correlations were established between head space (ID) and titrimetrically determined DC concentrations (R2 = 0.987-0.999, N = 96). Millivolt and titrimetric values from the SC solution tests were also correlated (P < 0.001, R 2 = 0.997, N = 16). The absolute and relative error associated with the use of the ID and SC solution averaged 0.9mg/l DC and 7.0% and 0.6 mg/l DC and 9.6%, respectively. The precision of DC estimates established in a second test series was good; coefficients of variation (100(SD/mean)) for the head space (ID) and titration analyses were 0.99% and 1.7%. Precision of the SC solution method was 1.3%. In a third test series, a single ID was coupled with four replicate head space units so as to permit sequential monitoring (15 min intervals) of a common water source. Here, appropriate gas samples were secured using a series of solenoid valves (1.6 mm bore) activated by a time-based controller. This system configuration reduced the capital cost per sample site from US$ 2695 to 876. Absolute error averaged 2.9, 3.1, 3.7, and 2.7 mg/ l for replicates 1-4 (N = 36) during a 21-day test period (DC range, 36-40 mg/l). The ID meter was then modified so as to provide for DO as well as DC measurements across components of an intensive fish production system. ?? 2003 Elsevier B.V. All rights reserved.