Nitrous oxide and methane in Atlantic and Mediterranean waters in the Strait of Gibraltar: Air-sea fluxes and inter-basin exchange

- N2O distribution follows the two layers scheme circulation in the Strait of Gibraltar.
- Mediterranean deep waters are highly undersaturated in CH4.
- Nitrification acts as the main N2O source in the Mediterranean overflow water.
- Temperature controls the seasonal variability of N2O in the upper layer.
- The outflow of Mediterranean waters supplies N2O to the North Atlantic.

The global ocean plays an important role in the overall budget of nitrous oxide (N2O) and methane (CH4), as both gases are produced within the ocean and released to the atmosphere. However, for large parts of the open and coastal oceans there is little or no spatial data coverage for N2O and CH4. Hence, a better assessment of marine emissions estimates is necessary. As a contribution to remedying the scarcity of data on marine regions, N2O and CH4 concentrations have been determined in the Strait of Gibraltar at the ocean Fixed Time series (GIFT). During six cruises performed between July 2011 and November 2014 samples were collected at the surface and various depths in the water column, and subsequently measured using gas chromatography. From this we were able to quantify the temporal variability of the gas air-sea exchange in the area and examine the vertical distribution of N2O and CH4 in Atlantic and Mediterranean waters. Results show that surface Atlantic waters are nearly in equilibrium with the atmosphere whereas deeper Mediterranean waters are oversaturated in N2O, and a gradient that gradually increases with depth was detected in the water column. Temperature was found to be the main factor responsible for the seasonal variability of N2O in the surface layer. Furthermore, although CH4 levels did not reveal any feature clearly associated with the circulation of water masses, vertical distributions showed that higher concentrations are generally observed in the Atlantic layer, and that the deeper Mediterranean waters are considerably undersaturated (by up to 50%). Even though surface waters act as a source of atmospheric N2O during certain periods, on an annual basis the net N2O flux in the Strait of Gibraltar is only 0.35 ± 0.27 μmol m−2 d−1, meaning that these waters are almost in a neutral status with respect to the atmosphere. Seasonally, the region behaves as a slight sink for atmospheric CH4 in winter and as a source in spring and fall. Approximating the circulation pattern in the Strait to a bi-layer scheme, N2O exchange between basins was also calculated, and a net export from the Mediterranean Sea to the Atlantic Ocean equivalent to 39 μmol m−2 d−1 was found.