Mississippi River affects the carbon dynamics in the northern Gulf of Mexico (N-GoM) significantly. Hence, total alkalinity (TA) algorithms developed for major ocean basins produce inaccurate estimations for this region. A TA algorithm was developed, which addresses the local effects of coastal processes and complex spatial influences. In-situ data collected during numerous previous research cruises in the N-GoM were compiled and used to calculate the efficiency of an existing TA algorithm that uses Sea-Surface-Temperature (SST) and Sea-Surface-Salinity (SSS) as explanatory variables. To improve this algorithm, statistical analyses were performed to improve the coefficients and functional form of this algorithm. Then, chlorophyll-a (Chla) was included as an additional explanatory variable. Chla worked as a proxy for addressing the organic carbon pump’s pronounced effects on coastal waters. Finally, a Geographically Weighted Regression (GWR) algorithm was developed to address spatial non-stationarity, which apparently could not be addressed in the previously developed global algorithm.

Ocean uptake of anthropogenic CO2 causes ocean acidification, a secular, global-scale decline in the pH of seawater. In order to better understand the implications of contemporary acidification for marine organisms and ecosystems, there is a need to better characterise natural variability in carbonate chemistry. In this thesis, climatological seasonal variability of sea surface pH and aragonite saturation state (OmegaA) in the open ocean is indirectly derived from other parameters of the marine CO2 system, namely total alkalinity (TA) and seawater pCO2/fCO2 (pCO2sw/fCO2sw). New monthly sea surface TA, fCO2sw and temperature climatologies are developed for this purpose, utilising newly-released observational synthesis products (PACIFICA for TA and SOCAT v2 for fCO2sw). Two versions of the new SST climatology are developed, referred to as upper and lower SST (USST and LSST), to test sensitivity to the depth range of the input observations. Annual ranges are generally found to be larger for the USST climatology, derived using observations from the upper 2 m, compared to LSST (which is based on deeper observations). Further, a seasonal cycle is found in the monthly average of the differences between these climatologies north of 30 degN, perhaps partly due to seasonal variation in near-surface stratification. The USST seasonal ranges are also found to be generally larger than in two previous SST climatologies, however, difference in the depth distribution of the input measurements is unlikely the main cause. The new monthly sea surface TA climatology extends coverage into the Nordic seas, excluded from previous climatologies. TA seasonality is found to be small outside of regions with large seasonal ranges in salinity. Large seasonal ranges in salinity and TA are found beneath the Intertropical Convergence Zone, in the Antarctic seasonal sea ice zone and in the western Greenland Sea. Non-salinity driven TA seasonality is found to be large in the Gulf of Alaska, eastern equatorial Pacific and western Greenland Sea. Compared to the Lee et al. (2006) TA climatology, substantially lower annual means and seasonal ranges are found for the subarctic Pacific, a region with greatly improved coverage courtesy of PACIFICA. The pH/OmegaA climatologies derived in the final chapter suggest pH seasonality is predominantly temperature driven in the subtropics and mainly driven by variation in salinity normalised dissolved inorganic carbon (sDIC) in the subpolar north Atlantic, western subarctic Pacific and Southern Ocean. Salinity variation is found to only exert a strong influence on pH seasonality in the western Greenland Sea. Climatological seasonal pH ranges are found to be mostly small in the tropics (<0.05), moderate in the subtropics (0.05-0.10) but very large (>0.1) in parts of the Ross, Weddell, Irminger and Iceland Seas and western subarctic Pacific gyre. OmegaA seasonality is found to be predominantly sDIC-driven everywhere except in the western Greenland Sea, with temperature variation generally being of modest influence. Seasonal cycles of pH and OmegaA are found to be in anti-phase where pH is mainly thermally driven and in-phase where pH is mainly sDIC-forced (both pH and OmegaA vary inversely with DIC). Comparison is made between the primary new pH/OmegaA climatology and various open ocean carbonate chemistry time-series. The climatology captures the general form of the climatological seasonal cycles of pH and OmegaA from the time-series, although with some differences in phasing and seasonal range. Analysing the time-series for long-term trends, I find that inter-decadal anthropogenic CO2 uptake driven pH and OmegaA declines can be modulated by trends in temperature, salinity or sTA. Investigation is also conducted into how the amplitude of pH and OmegaA seasonal cycles might change by 2100 for a subpolar and subtropical time-series. Under a high CO2 emissions scenario, the seasonal range of pH is found to be strongly enhanced for the subpolar time-series and moderately reduced for the subtropical time-series, with both being due to changes in seawater buffer capacity. / Graduate / 0425 / 0415 / robdj87@hotmail.com