Dynamics of halocarbons in coastal surface waters during short term mesocosm experiments

The aim of the present study was to evaluate the influence of different light quality, especially ultraviolet radiation (UVR), on the dynamics of volatile halogenated organic compounds (VHOCs) at the sea surface. Short term experiments were conducted with floating gas-tight mesocosms of different optical qualities. Six halocarbons (CH3I, CHCl3, CH2Br2, CH2ClI, CHBr3 and CH2I2), known to be produced by phytoplankton, together with a variety of biological and environmental variables were measured in the coastal southern Baltic Sea and in the Raunefjord (North Sea). These experiments showed that ambient levels of UVR have no significant influence on VHOC dynamics in the natural systems. We attribute it to the low radiation doses that phytoplankton cells receive in a normal turbulent surface mixed layer. The VHOC concentrations were influenced by their production and removal processes, but they were not correlated with biological or environmental parameters investigated. Diatoms were most likely the dominant biogenic source of VHOCs in the Baltic Sea experiment, whereas in the Raunefjord experiment macroalgae probably contributed strongly to the production of VHOCs. The variable stable carbon isotope signatures (d13C values) of bromoform (CHBr3) also indicate that different autotrophic organisms were responsible for CHBr3 production in the two coastal environments. In the Raunefjord, despite strong daily variations in CHBr3 concentration, the carbon isotopic ratio was fairly stable with a mean value of -26 per mil. During the declining spring phytoplankton bloom in the Baltic Sea, the d13C values of CHBr3 were enriched in 13C and showed noticeable diurnal changes (-12 per mil ± 4). These results show that isotope signature analysis is a useful tool to study both the origin and dynamics of VHOCs in natural systems.

Upwelling and associated heat flux in the equatorial Atlantic inferred from helium isotope disequilibrium

Sea-to-air and diapycnal fluxes of nitrous oxide (N2O) into the mixed layer were determined during three cruises to the upwelling region off Mauritania. Sea-to-air fluxes as well as diapycnal fluxes were elevated close to the shelf break, but elevated sea-to-air fluxes reached further offshore as a result of the offshore transport of upwelled water masses. To calculate a mixed layer budget for N2O we compared the regionally averaged sea-to-air and diapycnal fluxes and estimated the potential contribution of other processes, such as vertical advection and biological N2O production in the mixed layer. Using common parameterizations for the gas transfer velocity, the comparison of the average sea-toair and diapycnal N2O fluxes indicated that the mean sea-toair flux is about three to four times larger than the diapycnal flux. Neither vertical and horizontal advection nor biological production were found sufficient to close the mixed layer budget. Instead, the sea-to-air flux, calculated using a parameterization that takes into account the attenuating effect of surfactants on gas exchange, is in the same range as the diapycnal flux. From our observations we conclude that common parameterizations for the gas transfer velocity likely overestimate the air-sea gas exchange within highly productive upwelling zones.