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Measurements of total alkalinity (AT) and pH were made in the Ross Sea in January–February 2008 in order to characterize the carbonate system in the Ross Sea and to evaluate the variability associated with different water masses. The main water masses of the Ross Sea, Antarctic Surface Water, High Salinity Shelf Water (HSSW), Deep Ice Shelf Water, Circumpolar Deep Water (CDW) and Antarctic Bottom Water, were identified on the basis of the physical and chemical data. In particular, the AT ranged between 2275 and 2374 µmol kg−1 with the lowest values in the surface waters (2275–2346 µmol kg−1), where the influence of the sea-ice melting and of the variability of the physical properties was significant. In the deep layers of the water column, the AT maxima were measured in correspondence to the preferential pathways of the spreading HSSW. The pH had variable values in the surface layer (7.890–8.033) with the highest values in Terra Nova Bay and Ross Sea polynyas. A low pH (7.969±0.025) traced the intrusion of the CDW in the Ross Sea shelf area. All samples revealed waters that were oversaturated with respect to both calcite and aragonite, but near corrosive levels of aragonite saturation state (Ω ca. 1.1–1.2) were associated with the entrainment of CDW over the slope. Aragonite undersaturation is of particular concern for the zooplankton species comprising to calcifying organisms such as pteropods. The partial pressure of CO2 at the sea surface was undersaturated with respect to the atmospheric value, particularly in Terra Nova Bay and the Ross Sea polynyas, but a large variability in the sea–air CO2 fluxes was observed associated with different responses in the strength of the biological and physical processes. Keywords: Total alkalinity; pH; saturation state; Terra Nova Bay polynya; Ross Sea.