Using Noble Gases to Assess the Ocean's Carbon Pumps.

Natural mechanisms in the ocean, both physical and biological, concentrate carbon in the deep ocean, resulting in lower atmospheric carbon dioxide. The signals of these carbon pumps overlap to create the observed carbon distribution in the ocean, making the individual impact of each pump difficult to disentangle. Noble gases have the potential to directly quantify the physical carbon solubility pump and to indirectly improve estimates of the biological organic carbon pump. Noble gases are biologically inert, can be precisely measured, and span a range of physical properties. We present dissolved neon, argon, and krypton data spanning the Atlantic, Southern, Pacific, and Arctic Oceans. Comparisons between deep-ocean observations and models of varying complexity enable the rates of processes that control the carbon solubility pump to be quantified and thus provide an important metric for ocean model skill. Noble gases also provide a powerful means of assessing air-sea gas exchange parameterizations.

Risks of hypoxia and acidification in the high energy coastal environment near Victoria, Canada's untreated municipal sewage outfalls.

Wastewater disposal often has deleterious impacts on the receiving environment. Low dissolved oxygen levels are particularly concerning. Here, we investigate the impacts on dissolved oxygen and carbon chemistry of screened municipal wastewater in the marine waters off Victoria, Canada. We analyzed data from undersea moorings, ship-based monitoring, and remotely-operated vehicle video. We used these observations to construct a two-layer model of the nearfield receiving environment. Despite the lack of advanced treatment, dissolved oxygen levels near the outfalls were well above a 62 µmol kg-1 hypoxic threshold. Furthermore, the impact on water column oxygen at the outfall is likely <2 µmol kg-1. Dissolved inorganic carbon is not elevated and pH not depressed compared to the surrounding region. Strong tidal currents and cold, well-ventilated waters give Victoria's marine environment a high assimilative capacity for organic waste. However, declining oxygen levels offshore put water near the outfall at risk of future hypoxia.

Continuous high-frequency dissolved O2/Ar measurements by equilibrator inlet mass spectrometry.

The oxygen (O(2)) concentration in the surface ocean is influenced by biological and physical processes. With concurrent measurements of argon (Ar), which has similar solubility properties as oxygen, we can remove the physical contribution to O(2) supersaturation and determine the biological oxygen supersaturation. Biological O(2) supersaturation in the surface ocean reflects the net metabolic balance between photosynthesis and respiration, i.e., the net community productivity (NCP). We present a new method for continuous shipboard measurements of O(2)/Ar by equilibrator inlet mass spectrometry (EIMS). From these measurements and an appropriate gas exchange parametrization, NCP can be estimated at high spatial and temporal resolution. In the EIMS configuration, seawater from the ship's continuous intake flows through a cartridge enclosing a gas-permeable microporous membrane contactor. Gases in the headspace of the cartridge equilibrate with dissolved gases in the flowing seawater. A fused-silica capillary continuously samples headspace gases, and the O(2)/Ar ratio is measured by mass spectrometry. The ion current measurements on the mass spectrometer reflect the partial pressures of dissolved gases in the water flowing through the equilibrator. Calibration of the O(2)/Ar ion current ratio (32/40) is performed automatically every 2 h by sampling ambient air through a second capillary. A conceptual model demonstrates that the ratio of gases reaching the mass spectrometer is dependent on several parameters, such as the differences in molecular diffusivities and solubilities of the gases. Laboratory experiments and field observations performed by EIMS are discussed. We also present preliminary evidence that other gas measurements, such as N(2)/Ar and pCO(2) measurements, may potentially be performed with EIMS. Finally, we compare the characteristics of the EIMS with the previously described membrane inlet mass spectrometry (MIMS) approach.