Abstract. Automated in situ gas chromatograph/mass spectrometer (GC/MS) measurements of a range of predominantly biogenic alkyl halides in air, including CHBr3, CHBr2C1, CH3Br, C2HsBr, CH3I, C2HsI, CH2IC1, CH212, and the hitherto unreported CH2IBr were made at Mace Head during a 3-week period in May 1997. C3H7I and CH3CHICH3 were monitored but not detected. Positive correlations were observed between the polyhalomethane pairs CHBr3/C•r2C1 and CHBr3/CH2IBr and between the monohalomethane pair CH3I/C2HsI, which are interpreted in terms of common or linked marine sources. During periods when air masses were affected by emissions from local seaweed beds, the concentrations of CHBr3, CH2IC1, and CH2IBr not only showed remarkable correlation but also maximized at low water. These are the first field observations to provide evidence for a link between the tidal cycle, polyhalomethanes in air, and potential marine production. The calculated total flux of iodine atoms into the boundary layer at Mace Head from organic gaseous precursors was dominated by photolytic destruction of CH212. Photolysis of CH3I contributed less than 3%. The calculated peak flux of iodine atoms during the campaign coincided with the highest measured levels of iodine oxide radicals, as determined using Differential Optical Absorption Spectrometry (DOAS).

Abstract. Current estimates of annual bromoform production by temperate marine algae underestimate, by at least an order of magnitude, the flux required to sustain atmospheric concentrations. In the light of recent evidence of the potential of bromoform to deplete uppertropospheric/lower-stratospheric ozone, such a substantial discrepancy in global emission rateq iq of considerable concern. Here we present new information on air and seawater CHBr3, CH2Br2, and CHBr2C1 concentrations in the coastal east Atlantic and review previous data from widespread locations which suggest that concentrations and ratios of reactive organobromines are consistent with marine macroalgal emissions. Detailed reviews of algal halocarbon emissions and biomass estimates imply that macroalgae produce around 70% of the world's bromoform, rather than only -20% as previously thought, and that the underestimation was most likely caused by over conservative biomass estimates. Our total global source strength estimate of 2.2 x 1011 g CHBr3 yr'agrees well with recent calculations derived from atmospheric data. Given the dominant role of macroalgae in producing bromoform, the effect of changing climate and environment on seaweed populations and consequent effect on biogenic bromine emissions should be investigated.

[1] Reactive halogen species (RHS) such as the halogen oxide radicals IO and BrO influence tropospheric oxidation processes in both polar and temperate regions. Oceanic photolabile halocarbons have been shown to be strong sources of RHS in midlatitudes. However, the global source strengths of these halocarbon precursors and the relative importance of the coastal and pelagic oceans on their concentrations are highly uncertain. Here we present atmospheric measurements of the reactive organic halogens CH 3 I, CH 2 I 2 , CH 2 ClI, CH 2 IBr, CHIBr 2 , CHBr 3 , CH 2 Br 2 , and CHBr 2 Cl made at Mace Head, Ireland, during the Particle Formation and Fate in the Coastal Environment campaign in September 1998 and at Cape Grim, Tasmania, during the Southern Ocean Atmospheric Photochemistry Experiment 2 campaign in January/February 1999. Mace Head is strongly influenced by local macroalgae, whereas Cape Grim, owing to its cliff-top location, suffers much less impact from seaweeds. The very reactive halocarbons CH 2 I 2 , CH 2 IBr, and CHIBr 2 observed at Mace Head were below detection limits at Cape Grim, although CH 2 ClI was detected at both locations. Mixing ratios of CH 3 I, CH 2 ClI, CHBr 3 , CHBr 2 Cl, and CH 2 Br 2 at Cape Grim were on average 25-50% of those at Mace Head. Concentrations of the polybromomethanes correlated well at both sites. Using these correlations, we estimate molar source strengths of CHBr 2 Cl and CH 2 Br 2 to be between 3 and 6% and between 15 and 25% of the global CHBr 3 flux, respectively. These values fall within ranges estimated independently from concentration and lifetime data.

Abstract. This paper presents a summary of the measurements made during the heavily-instrumented Reactive Halogens in the Marine Boundary Layer (RHaMBLe) coastal study in Roscoff on the North West coast of France throughout September 2006. It was clearly demonstrated that iodinemediated coastal particle formation occurs, driven by daytime low tide emission of molecular iodine, I 2 , by macroalgal species fully or partially exposed by the receding waterline. Ultrafine particle concentrations strongly correlate with the rapidly recycled reactive iodine species, IO, produced at high concentrations following photolysis of I 2 . The heterogeneous macroalgal I 2 sources lead to variable relative concentrations of iodine species observed by path-integrated and in situ measurement techniques.

Abstract. We present a global simulation of tropospheric iodine chemistry within the GEOS-Chem chemical transport model. This includes organic and inorganic iodine sources, standard gas-phase iodine chemistry and simplified higher iodine oxide (I2OX, X = 2, 3, 4) chemistry, photolysis, deposition and parametrised heterogeneous reactions. In comparisons with recent Iodine Oxide (IO) observations the iodine simulation shows an average bias of ~+66 % available surface observations in the marine boundary layer (outside of polar regions), and of ~+73 % within the free troposphere (350 < hPa < 900) over the eastern Pacific. Iodine emissions (3.8 Tg yr−1) are overwhelmingly dominated by the inorganic ocean source, with 76 % of this emission from Hypoiodous acid (HOI). HOI is also found to be the dominant iodine species in terms of global tropospheric IY burden (contributing up to 70 %). The iodine chemistry leads to a significant global tropospheric O3 burden decrease (9.0 %) compared to standard GEOS-Chem (v9-2). The iodine-driven OX loss rate (748 Tg OX yr−1) is by photolysis of HOI (78 %), photolysis of OIO (21 %), and reaction of IO and BrO (1 %). Increases in global mean OH concentrations (1.8 %) by increased conversion of hydroperoxy radicals exceeds the decrease in OH primary production from the reduced O3 concentration. We perform sensitivity studies on a range parameters and conclude that the simulation is sensitive to choices in parameterisation of heterogeneous uptake, ocean surface iodide, and I2OX (X = 2, 3, 4) photolysis. The new iodine chemistry combines with previously implemented bromine chemistry to yield a total bromine and iodine driven tropospheric O3 burden decrease of 14.4 % compared to a simulation without iodine and bromine chemistry in the model. This is a significant impact and so halogen chemistry needs to be considered in climate and air quality models.