The Arctic marine system is currently undergoing transition as a result of climate change. This study examines the effects of this transition on rates of air-sea CO2 exchange within the eastern Canadian Arctic. Continuous seawater pCO2 measurements revealed this area to be a strong summertime sink of atmospheric CO2. Total alkalinity and stable oxygen isotopes were utilized as freshwater tracers, revealing areas of significant sea ice melt and riverine inputs. Eastern Baffin Bay and Barrow Strait were found to be strongly influenced by sea ice melt, lowering seawater pCO2; whereas Kennedy Channel contained significant river discharge, raising seawater pCO2. Primary production in surface waters was low throughout the region, with the exception of Petermann Fjord where glacial ice melt likely transports nutrients to the surface. This region is anticipated to represent a weaker CO2 sink in the future, due mainly to predicted decreases in sea ice thickness and extent. / February 2016

With rising atmospheric CO2 concentrations, a detailed understanding of processes that impact atmospheric CO2 fluxes is required. While a sink of atmospheric carbon from the continents to the ocean from carbonate mineral weathering is, to some degree, offset by carbonate mineral precipitation in the oceans, efforts are underway to make direct measurements of these fluxes. Measurement of the continental sink has two parts: 1) measurement of the dissolved inorganic carbon (DIC) flux leaving a river basin, and 2) partitioning the inorganic carbon flux between the amount removed from the atmosphere and the portion from the bedrock. This study attempted to improve methods to measure the DIC flux using existing data to estimate the DIC flux from carbonate weathering within the limestone karst region of south central Kentucky. The DIC flux from the Barren River drainage basin upstream from Bowling Green in southern Kentucky and northern Tennessee, and the upper Green River drainage basin, upstream from Greensburg, Kentucky, was measured, each for a year, using U.S.G.S. discharge data and water-chemistry data from municipal water plants. A value of the (DIC) flux, normalized by time and area of carbonate rock, of 4.29 g km-3 day-1 was obtained for the Barren River, and 4.95 kg km-3 for the Green. These compared favorably with data obtained by Osterhoudt (2014) from two nested basins in the upper Green River with values of 5.66 kg km-3 day-1 and 5.82 kg km-3 day-1 upstream from Greensburg and Munfordville, respectively. Additional normalization of the values obtained in this study by average precipitation minus evapotranspiration over the area of carbonate rock, or water available for carbonate dissolution, resulted in values of 5.61x107 g C (km3 H20)- 1 day-1 (grams of carbon per cubic kilometer of water, per day) for the Barren, and 7.43x107g C (km3 H20)-1 day-1 for the Green River. Furthermore, a statistical relationship between the total DIC flux and time-volume of water available for dissolution has been observed, yielding an r2 value of 0.9478. This relationship indicates that the primary variables affecting DIC flux for these drainage basins are time and the volume of water available for dissolution.

Estuaries are dynamic environments that are strongly affected by natural variability, as well as direct and indirect anthropogenic impacts. A better understanding of the drivers of carbon fluxes and biogeochemical variability in estuarine systems is needed, particularly with the increasing threat of ocean acidification. Morro Bay in Central California is a small nationally protected estuary, with seasonally low freshwater inputs. Since 2007, the bay has experienced a significant loss of native seagrass, Zostera marina, which is an important component of the marine ecosystem. Because seagrass photosynthesis decreases carbon dioxide and increases oxygen in the water column, the loss of seagrass has the potential to substantially change short-term carbonate chemistry and long-term carbon fluxes of an estuary. The spatial variability of carbonate chemistry was measured in Morro Bay using ship-board surveys during the low-inflow summer season and measured the temporal variability by collecting samples close to the shore from July to November. Discrete samples show an increase in total alkalinity and dissolved inorganic carbon in the mid and back bay regions, historically dominated by seagrass. Slightly lower total alkalinity and dissolved inorganic carbon were observed in the Fall season compared to the low-inflow Summer season. Analysis of the relative modification of alkalinity and dissolved inorganic carbon, paired with salinity and temperature data, contributes to an understanding of the drivers of the observed carbonate variability. This understanding may provide clues to the causes and effects of observed changes to the bay with seagrass loss. More broadly, it will inform the vulnerability of other low-inflow estuaries to future acidification and highlight the role seagrasses play in mitigating local acidification.

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