Deep-water formation supplies oxygen-rich water to the deep sea, spreading throughout the ocean via the global thermohaline circulation. Models suggest that gases in newly formed deep-water do not come to equilibrium with the atmosphere. However, direct measurements during wintertime convection are scarce, and the controls over the extent of this disequilibria are poorly quantified. Here we show that oxygen is consistently undersaturated at -6.3% to -7.6% in the Labrador Sea at the end of convection, when convection reaches deeper than 800 m. Deeper convection resulted in greater undersaturation while convection lasting later in the year resulted in values closer to equilibrium, from which we produce a predictive relationship. We use dissolved oxygen data from six profiling Argo floats in the Labrador Sea between 2003 to 2016, allowing direct observations of wintertime convection. Four of the six optode oxygen sensors displayed in situ drift of -2.98 μmol O2 kg-1 year-1 on average, which we corrected to stable deep-water oxygen values from repeat hydrography. Observations of low oxygen intrusions during restratification and a simple mixing calculation demonstrate that lateral processes act to lower the oxygen inventory of the central Labrador Sea. This suggests that the Labrador Sea is a net sink for atmospheric oxygen, but uncertainties in parameterizing gas exchange limit our ability to quantify the net uptake. Our results constrain the initial oxygen concentration of Labrador Sea Water and allow more precise estimates of oxygen utilization and nutrient regeneration in this water mass. / Graduate

The major physiological function of hemoglobin (Hb) is to bind, transport and deliver oxygen to tissues; made efficient by endogenous effectors, such as protons and 2,3-diphosphoglycerate. Synthetic allosteric effectors of Hb (AEHs) are also known to modulate Hb oxygen affinity, showing potential for the treatment of sickle cell disease (SCD) and ischemic-related diseases. In this project, AEHs which increase Hb affinity for oxygen, including derivatives of the anti-sickling compounds, 5HMF and benzaldehydes, as well as an AEH that decreases Hb affinity for oxygen, RSR-13, were synthesized for their effects on Hb oxygen binding property and their capability to release NO from substituted nitrate ester moieties. Compounds that were found to increase Hb affinity for oxygen were further tested for their anti-sickling activities. Structural studies were carried out to gain insight into the compound’s mode of action. Development of these agents could be a therapeutic strategy for SCD or ischemic-related diseases.