Tidally exposed macroalgae emit large amounts of I(2) and iodocarbons that produce hotspots of iodine chemistry and intense particle nucleation events in the coastal marine boundary layer. Current emission rates are poorly characterized, however, with reported emission rates varying by 3 orders of magnitude. In this study, I(2) emissions from 25 Laminaria digitata samples were investigated in a simulation chamber using incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS). The chamber design allowed gradual extraction of seawater to simulate tidal emersion of algae. Samples were exposed to air with or without O(3) and to varying irradiances. Emission of I(2) occurred in four distinct stages: (1) moderate emissions from partially submerged samples; (2) a strong release by fully emerged samples; (3) slowing or stopping of I(2) release; and (4) later pulses of I(2) evident in some samples. Emission rates were highly variable and ranged from 7 to 616 pmol min(-1) gFW(-1) in ozone-free air, with a median value of 55 pmol min(-1) gFW(-1) for 20 samples.
Laboratory studies into particle formation from Laminaria digitata macroalgae were undertaken to elucidate aerosol formation for a range of I(2) (0.3-76 ppb(v)) and O(3) (<3-96 ppb(v)) mixing ratios and light levels (E(PAR) = 15, 100, and 235 μmol photons m(-2) s(-1)). No clear pattern was observed for I(2) or aerosol parameters as a function of light levels. Aerosol mass fluxes and particle number concentrations, were, however, correlated with I(2) mixing ratios for low O(3) mixing ratios of <3 ppb(v) (R(2) = 0.7 and 0.83, respectively for low light levels, and R(2) = 0.95 and 0.98, respectively for medium light levels). Additional experiments into particle production as a function of laboratory-generated I(2), over a mixing ratio range of 1-8 ppb(v), were conducted under moderate O(3) mixing ratios (∼24 ppb(v)) where a clear, 100-fold or greater, increase in the aerosol number concentrations and mass fluxes was observed compared to the low O(3) experiments. A linear relationship between particle concentration and I(2) was found, in reasonable agreement with previous studies. Scaling the laboratory relationship to aerosol concentrations typical of the coastal boundary layer suggests a I(2) mixing ratio range of 6-93 ppt(v) can account for the observed particle production events. Aerosol number concentration produced from I(2) is more than a factor of 10 higher than that produced from CH(2)I(2) for the same mixing ratios.
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