Determination of the CO2 system at sub-zero temperatures in seawater and seawater-derived brines

Lead Research Organisation: University of Southampton
Department Name: School of Ocean and Earth Science


Our understanding of the biogeochemical cycling of carbon in the oceans has been revolutionised through our ability to analyse several of the parameters that describe the carbonate system via gas exchange and the aqueous acid-base thermodynamic equilibria. Thus, the individual, or more commonly, combined measurement of dissolved inorganic carbon (DIC), hydrogen ion concentration (pH), total alkalinity (TA) and the partial pressure of carbon dioxide (pCO2) has provided us with the ability to determine the influence that primary production, respiration, and calcium carbonate precipitation and dissolution have on the chemistry of the oceans.

Although the geographical and temporal data coverage of the CO2 system has increased since the inception of techniques to measure all its directly observable parameters, large gaps still exist in the oceanic data base. Particular black spots are the polar oceans and especially under sea ice cover. This is an important consideration, especially as the polar oceans are experiencing environmental change as a result of ocean acidification, which is particularly rapid in the land-locked Arctic Ocean. In addition, the presence of sea ice adds complexity to the polar environment as it consists of a dynamic environment of numerous inter-connected or isolated micro-habitats that expand and contract during the seasonal cycle of formation and decay of sea ice. The study of the complex, sea ice environment is important as it in now recognized as an active interface in the interaction between the ocean and the atmosphere, through which carbon species, transform and migrate. The biogeochemical information about the polar oceans is limited in part due to its relative inaccessibility, especially when there is ice cover, the complexity of the environment and the difficulty in working in harsh conditions, but also due to a lack of appropriate methods to work at these temperatures and knowledge of the change in the value of equilibrium constants used in determining parameters of the CO2 system under these conditions. Thus, our knowledge of the CO2 system at near-zero polar waters and the sub-zero temperatures in the brine enriched micro-habitats of sea ice is currently rudimentary compared with that in oceanic waters where the temperature is above-zero.As not all of the parameters that can describe the CO2 system fully (TA, DIC, pH, pCO2) can be reliably measured in some of the polar environments, this has meant that the value of the unmeasured or unmeasurable parameters must be calculated, a process that requires extrapolation of physical-chemical equations that really should only be used with above-zero temperatures and salinity less than 50. This type of extrapolation of can lead to large differences in the calculated pCO2 and pH. Thus, the aim of our research is to provide the necessary analytical tools and experimental data so that the CO2 system in polar environments can be investigated with the same degree of sophistication as that currently afforded in temperate and tropical temperature and salinity conditions. To be able to achieve this, we have chosen existing methods of measuring pH and pCO2 in ocean waters, which we can reliable modify to measure the same parameters in brine enriched solutions at sub-zero temperatures. Using our high quality measurements, we will determine the coefficients that are essential for the determination of CO2 system and subsequently test the validity of this approach by measuring any 2 (out of 4) directly observable physical-chemical parameters of the CO2 system to predict the remaining two. In the marine community, the use of these constants, tools, and analytical methodology will aid investigation of ongoing and future changes in the CO2 chemistry, carbon-based fluxes, and saturation with respect to calcium carbonate minerals in high latitude oceans, setting important constraints on model predictions of past, present, and future climate excursions.

Planned Impact

see main proposal
Description Project at early stage. We have established molar extinction coefficients of metal creso purple (MCP) for a range of high (>40) salinities and low temperatures (<0C). The next step will be to establish the acid dissociation constant for MCP at enhanced salinities and low temperatures. This work is currently finalised.
Exploitation Route The data coming from this project will be crucial for calculations of the carbonate system in polar waters. It will consequently influence IPCC projections.
Sectors Environment