Abstract

Abstract. Time profiles of molecular iodine emissions from seven species of seaweed have been measured at high time resolution (7.5 s) by direct spectroscopic quantification of the gas phase I2 using broadband cavity enhanced absorption spectroscopy. Substantial differences were found between species, both in the amounts of I2 emitted when the plants were exposed to air and in the shapes of their emission time profiles. Two species of kelp, Laminaria digitata and Laminaria hyperborea, were found to be the most potent emitters, producing an intense burst of I2 when first exposed to air. I2 was also observed from Saccharina latissima and Ascophyllum nodosum but in lower amounts and with broader time profiles. I2 mixing ratios from two Fucus species and Dictyopteris membranacea were at or below the detection limit of the present instrument (25 pptv). A further set of experiments investigated the time dependence of I2 emissions and aerosol particle formation when fragments of L. digitata were exposed to desiccation in air, to ozone and to oligoguluronate stress factors. Particle formation occurred in all L. digitata stress experiments where ozone and light were present, subject to the I2 mixing ratios being above certain threshold amounts. Moreover, the particle number concentrations closely tracked variations in the I2 mixing ratios, confirming the results of previous studies that the condensable particle-forming gases derive from the photochemical oxidation of the plant's I2 emissions. This work also supports the theory that particle nucleation in the coastal atmosphere occurs in "hot-spot" regions of locally elevated concentrations of condensable gases: the greatest atmospheric concentrations of I2 and hence of condensable iodine oxides are likely to be above plants of the most efficiently emitting kelp species and localised in time to shortly after these seaweeds are uncovered by a receding tide.

Highlights

  • The rapid nucleation of large numbers of ultra-fine aerosol particles has been reported from several field studies conducted at Mace Head on the west coast of Ireland (O’Dowd et al, 2002; O’Dowd and Hoffmann, 2005; Saiz-Lopez et al, 2006)

  • A fraction of these newly nucleated particles may subsequently grow large enough to act as cloud condensation nuclei (CCN) and affect cloud properties and lifetimes, potentially changing the radiative forcing in coastal regions

  • Apart from innate biological variability, the only explanation we offer for the apparently low I2 emission rates seen in our GG stress experiment is that it is possible that the availability of a suitable oxidant was sufficiently limited under the ozone-scrubbed conditions of our GG experiment #3 that only a small fraction of the emitted I−(aq) was oxidised into gas phase molecular iodine

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Summary

Introduction

The rapid nucleation of large numbers of ultra-fine aerosol particles has been reported from several field studies conducted at Mace Head on the west coast of Ireland (O’Dowd et al, 2002; O’Dowd and Hoffmann, 2005; Saiz-Lopez et al, 2006). A similar phenomenon was recently observed during the Reactive Halogens in the Marine Boundary Layer (RHaMBLe) field campaign at Roscoff on the north Brittany coast of France (Whitehead et al, 2009; McFiggans et al, 2010). These nucleation events tend to occur in “bursts” around daytime low tides (but not generally night-time low tides), the most intense events occurring on days with the lowest tides. Parallel studies conducted in laboratory chambers and flow reactors have observed particle formation following the gas phase photo-oxidation of CH2I2 (Jimenez et al, 2003) and the head-space gases sampled from above one particular species of kelp seaweed, Laminaria digitata (McFiggans et al, 2004). Since the McFiggans et al (2004) publication, further flow reactor studies have confirmed that both halocarbons and molecular

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