Robust sensor for extended autonomous measurements of surface ocean dissolved inorganic carbon.

Ocean carbon monitoring efforts have increased dramatically in the past few decades in response to the need for better marine carbon cycle characterization. Autonomous pH and carbon dioxide (CO2) sensors capable of yearlong deployments are now commercially available; however, due to their strong covariance, this is the least desirable pair of carbonate system parameters to measure for high-quality, in situ, carbon-cycle studies. To expand the number of tools available for autonomous carbonate system observations, we have developed a robust surface ocean dissolved inorganic carbon (DIC) sensor capable of extended (>year) field deployments with a laboratory determined uncertainty of ±5 µmol kg(-1). Results from the first two field tests of this prototype sensor indicate that measurements of DIC are ∼90% more accurate than estimates of DIC calculated from contemporaneous and collocated measurements of pH and CO2. The improved accuracy from directly measuring DIC gives rise to new opportunities for quantitative, autonomous carbon-cycle studies.

Autonomous in situ measurements of seawater alkalinity.

Total alkalinity (AT) is an important parameter for describing the marine inorganic carbon system and understanding the effects of atmospheric CO2 on the oceans. Measurements of AT are limited, however, because of the laborious process of collecting and analyzing samples. In this work we evaluate the performance of an autonomous instrument for high temporal resolution measurements of seawater AT. The Submersible Autonomous Moored Instrument for alkalinity (SAMI-alk) uses a novel tracer monitored titration method where a colorimetric pH indicator quantifies both pH and relative volumes of sample and titrant, circumventing the need for gravimetric or volumetric measurements. The SAMI-alk performance was validated in the laboratory and in situ during two field studies. Overall in situ accuracy was -2.2 ± 13.1 µmol kg(-1) (n = 86), on the basis of comparison to discrete samples. Precision on duplicate analyses of a carbonate standard was ±4.7 µmol kg(-1) (n = 22). This prototype instrument can measure in situ AT hourly for one month, limited by consumption of reagent and standard solutions.