An Ultrahigh Precision, High-Frequency Dissolved Inorganic Carbon Analyzer Based on Dual Isotope Dilution and Cavity Ring-Down Spectroscopy

We present a novel method for continuous and automated shipboard measurements of dissolved inorganic carbon concentration ([DIC]) in surface water. The method is based on dual isotope dilution and cavity ring-down spectroscopy (DID-CRDS). In this method, seawater is continuously sampled and mixed with a flow of NaH(13)CO3 solution that is also enriched in deuterated water (the spike). The isotopic composition of CO2 (δ(13)C(spiked_sample)) derived from the DIC in the mixture, and the D/H ratio of the mixed water (δD(spiked_sample)), are measured by CRDS analyzers. The D/H of the water in the mixture allows accurate estimates of the mixing ratio of the sample and the spike. [DIC] of the sample is then calculated from the mixing ratio, [DI(13)C] of the spike, and δ(13)C(spiked_sample). In the laboratory, the precision of the method is0.02% (±0.4 μmol kg(-1) when [DIC] = 2000 μmol kg(-1)). A shipboard test was conducted in the Delaware Bay and Estuary. For 2 min average [DIC], a precision of0.03% was achieved. Measurements from the DID-CRDS showed good agreement with independent measurements of discrete samples using the well-established coulometric method (mean difference = -1.14 ± 1.68 μmol kg(-1)), and the nondispersive infrared(NDIR)-based methods (mean difference = -0.9 ± 4.73 μmol kg(-1)).