Diel variation of TCO2 in the upper layer of oceanic waters reflects microbial composition,variation and possibly methane cycling

Six diel TCO₂ cycles determined by infrared (IR) photometry from five drift stations occupied between 24 February and 16 March 1979 in the mixed layer of the northwestern Caribbean Sea are examined. Comparison of TCO₂ variation with coincident salinity and O₂ variation demonstrated that TCO₂ often co-varied with these independently measured variables. During five diel cycles TCO₂ variation was characterized by nocturnal production and diurnal consumption. The inverse, diurnal production of CO₂, occurred downstream from Misteriosa Bank, whose corals apparently contributed to a water mass having a twofold increase of POC and a sixfold larger population of heterotrophic nanoplankters. For the five diel studies carried out in waters with balanced or nearly blanced heterotrophic and phototrophic components of the nanoplankton, CO₂ consumption at constant salinity always occurred between 06.00 and 09.00 hrs. Net uptake often continued through 15.00 hrs, but not always in the absence of significant salinity changes. At constant salinity net O₂ evolution never exceeded 0.5 mol l^-1 h^-1 while net CO₂ uptake consistently averaged 3 mol l^-1 h^-1 for an apparent net production of 36 mg C m^-3 h^-1, which greatly exceeds the O₂ changes and open ocean ¹⁴C estimates from the literature. Diurnal consumption was apparently balanced by nocturnal production of CO₂ so that no significant net daily change in TCO₂ was observed. Departures from theoretical PQ and RQ and the possibility of nocturnal variations in formaldehyde and carbonate alkalinity imply that chemotrophs, both methane producers and methane oxidizers, play a significant role in CO₂ cycling. This could be through the metabolism of the nonconservative gases CH₄, CO, and H₂, and a link between chemotrophy and phototrophy through these gases is hypothesized. These open system measurements were subject to diffusion and documentable patchiness, but temporal TCO₂ changes appear to indicate the net direction of microbiological activity and join a growing body of literature showing dynamic variation in CO₂ and O₂ that exceeds estimates by ¹⁴C bottle assays of carbon fixation.