Abstract. Mercury is a contaminant of global concern. It is transported in the atmosphere primarily as gaseous elemental mercury, but its reactivity and deposition to the surface environment, through which it enters the aquatic food chain, is greatly enhanced following oxidation. Measurements and modelling studies of oxidised mercury in the polar to sub-tropical marine boundary layer (MBL) have suggested that photolytically produced bromine atoms are the primary oxidant of mercury. We report year-round measurements of elemental and oxidised mercury, along with ozone, halogen oxides (IO and BrO) and nitrogen oxides (NO2), in the MBL over the Galápagos Islands in the equatorial Pacific. Elemental mercury concentration remained low throughout the year, while higher than expected levels of oxidised mercury occurred around midday. Our results show that the production of oxidised mercury in the tropical MBL cannot be accounted for by bromine oxidation only, or by the inclusion of ozone and hydroxyl. As a two-step oxidation mechanism, where the HgBr intermediate is further oxidised to Hg(II), depends critically on the stability of HgBr, an additional oxidant is needed to react with HgBr to explain more than 50% of the observed oxidised mercury. Based on best available thermodynamic data, we show that atomic iodine, NO2, or HO2 could all play the potential role of the missing oxidant, though their relative importance cannot be determined explicitly at this time due to the uncertainties associated with mercury oxidation kinetics. We conclude that the key pathway that significantly enhances atmospheric mercury oxidation and deposition to the tropical oceans is missing from the current understanding of atmospheric mercury oxidation.

Abstract. Emitted mainly by the oceans, iodine is a halogen compound important for atmospheric chemistry due to its high ozone depletion potential and effect on the oxidizing capacity of the atmosphere. Here we present a comprehensive data set of iodine oxide (IO) measurements in the open marine boundary layer (MBL) made during the Malaspina 2010 circumnavigation. Results show IO mixing ratios ranging from 0.4 to 1 pmol mol−1 (30% uncertainty) and, complemented with additional field campaigns, this data set confirms through observations the ubiquitous presence of reactive iodine chemistry in the global marine environment. We use a global model with organic (CH3I, CH2ICl, CH2I2 and CH2IBr) and inorganic (HOI and I2) iodine ocean emissions to investigate the contribution of the different iodine source gases to the budget of IO in the global MBL. In agreement with previous estimates, our results indicate that, globally averaged, the abiotic precursors contribute about 75 % to the IO budget. However, this work reveals a strong geographical pattern in the contribution of organic vs. inorganic precursors to reactive iodine in the global MBL.

Ship-based Multi-Axis Differential Optical Absorption Spectroscopy measurements of iodine monoxide (IO) and atmospheric and seawater Gas Chromatography-Mass Spectrometer observations of methyl iodide (CH₃I) were made in the Eastern Pacific marine boundary layer during April 2010 as a part of the HaloCarbon Air Sea Transect-Pacific (HaloCAST-P) scientific cruise. The presence of IO in the open ocean environment was confirmed, with a maximum differential slant column density of 5 × 10¹³ molecules cm⁻² along the 1° elevation angle (corresponding to approximately 1 pptv) measured in the oligotrophic region of the Southeastern Pacific. Such low IO mixing ratios and their observed geographical distribution are inconsistent with satellite estimates and with previous understanding of oceanic sources of iodine. A strong correlation was observed between reactive iodine (defined as IO + I) and CH₃I, suggesting common sources. In situ measurements of meteorological parameters and physical ocean variables, along with satellite-based observations of Chlorophyll <i>a</i> (Chl <i>a</i>) and Chromophoric Dissolved Organic Matter (CDOM) were used to gain insight into the possible sources of iodine in this remote environment. Surprisingly, reactive iodine showed a negative correlation (> 99% confidence) to Chl <i>a</i> and CDOM across the cruise transect. However, a significant positive correlation (> 99% confidence) with sea surface temperature (SST) and salinity instead suggests a widespread abiotic source related to the availability of aqueous iodine and to temperature

[1] Observations of gas-phase iodine species were made during a field campaign in the eastern Pacific marine boundary layer (MBL). The Climate and Halogen Reactivity Tropical Experiment (CHARLEX) in the Galápagos Islands, running from September 2010 to present, is the first long-term ground-based study of trace gases in this region. Observations of gas-phase iodine species were made using long-path differential optical absorption spectroscopy (LP-DOAS), multi-axis DOAS (MAX-DOAS), and resonance and off-resonance fluorescence by lamp excitation (ROFLEX). These measurements were supported by ancillary measurements of ozone, nitrogen oxides, and meteorological variables. Selective halocarbon and ultrafine aerosol concentration measurements were also made. MAX-DOAS observations of iodine monoxide (IO) display a weak seasonal variation. The maximum differential slant column density was 3.8 Â 10 13 molecule cm À2 (detection limit~7 Â 10 12 molecule cm À2 ). The seasonal variation of reactive iodine IO x (= I + IO) is stronger, peaking at 1.6 pptv during the warm season (February-April). This suggests a dependence of the iodine sources on the annual cycle in sea surface temperature, although perturbations by changes in ocean surface iodide concentration and solar radiation are also possible. An observed negative correlation of IO x with chlorophyll-a indicates a predominance of abiotic sources. The low IO mixing ratios measured (below the LP-DOAS detection limit of 0.9 pptv) are not consistent with satellite observations if IO is confined to the MBL. The IO x loading is consistent with the observed absence of strong ozone depletion and nucleation events, indicating a small impact of iodine chemistry on these climatically relevant factors in the eastern Pacific MBL.

Abstract. Iodine monoxide (IO) differential slant column densities (DSCD) have been retrieved from a new multi-axis differential optical absorption spectroscopy (MAX-DOAS) instrument deployed at the Izaña subtropical observatory as part of the Network for the Detection of Atmospheric Composition Change (NDACC) programme. The station is located at 2370 m a.s.l., well above the trade wind inversion that limits the top of the marine boundary layer, and hence is representative of the free troposphere. We report daily observations from May to August 2010 at different viewing angles. During this period, the spectral signature of IO was unequivocally detected on every day of measurement. A mean IO DSCD of 1.52×10 13 molecules cm −2 was observed at the 5 • instrument elevation angle (IEA) on clear days using a single zenith reference for the reported period, with a day-to-day variability of 33 % at one standard deviation. Based on the simulation of the DSCDs using radiative transfer calculations with five different hypothesized IO profiles, the IO mixing ratio is estimated to range between 0.2 and 0.4 pptv in the free troposphere. Episodes of Saharan dust outbreaks were also observed, with large increases in the DSCDs at higher IEA, suggesting an enhancement of IO inside the dust cloud.

Glyoxal is an important intermediate species formed by the oxidation of common biogenic and anthropogenic volatile organic compounds such as isoprene, toluene, and acetylene. Although glyoxal has been shown to play an important role in urban and forested environments, its role in the open ocean environment is still not well understood, with only a few observations showing evidence for its presence in the open ocean marine boundary layer (MBL). In this study, we report observations of glyoxal from 10 field campaigns in different parts of the world's oceans. These observations together represent the largest database of glyoxal in the MBL. The measurements are made with similar instruments that have been used in the past, although the open ocean values reported here, average of about 25 parts per trillion by volume (pptv) with an upper limit of 40 pptv, are much lower than previously reported observations that were consistently higher than 40 pptv and had an upper limit of 140 pptv, highlighting the uncertainties in the differential optical absorption spectroscopy method for the retrieval of glyoxal. Despite retrieval uncertainties, the results reported in this work support previous suggestions that the currently known sources of glyoxal are insufficient to explain the average MBL concentrations. This suggests that there is an additional missing source, more than a magnitude larger than currently known sources, which is necessary to account for the observed atmospheric levels of glyoxal. Therefore, it could play a more important role in the MBL than previously considered.

Ship-based Multi-Axis Differential Optical Absorption Spectroscopy measurements of iodine monoxide (IO) and atmospheric and seawater Gas Chromatography – Mass Spectrometer observations of methyl iodide (CH₃I) were made in the Eastern Pacific marine boundary layer during April 2010 as a part of the HaloCarbon Air Sea Transect-Pacific (HaloCAST-P) scientific cruise. The presence of IO in the open ocean environment was confirmed, with a maximum differential slant column density of 5 &times; 10¹³ molecules cm^&minus;2 (corresponding to approximately 1 pptv) measured in the oligotrophic region of the Southeastern Pacific. Such low IO mixing ratios and their observed geographical distribution are inconsistent with satellite estimates and with previous understanding of oceanic sources of iodine. A strong correlation was observed between reactive iodine (defined as IO + I) and CH₃I, suggesting common sources. In situ measurements of meteorological parameters and physical ocean variables, along with satellite-based observations of Chlorophyll <i>a</i> (Chl <i>a</i>) and Chromophoric Dissolved Organic Matter (CDOM) were used to gain insight into the possible sources of iodine in this remote environment. Surprisingly, reactive iodine showed a negative correlation (>99% confidence) to Chl <i>a</i> and CDOM across the cruise transect. However, a significant positive correlation (>99% confidence) with sea surface temperature (SST) and salinity instead suggests a widespread abiotic source related to the availability of aqueous iodine and to temperature

Current chemistry climate models do not include polar emissions and chemistry of halogens.This work presents the first implementation of an interactive polar module into the very short-lived (VSL) halogen version of the Community Atmosphere Model with Chemistry (CAM-Chem) model. The polar module includes photochemical release of molecular bromine, chlorine, and interhalogens from the sea-ice surface, and brine diffusion of iodine biologically produced underneath and within porous sea-ice. It also includes heterogeneous recycling of inorganic halogen reservoirs deposited over fresh sea-ice surfaces and snow-covered regions. The polar emission of chlorine, bromine, and iodine reach approximately 32, 250, and 39 Gg/year for Antarctica and 33, 271, and 4 Gg/year for the Arctic, respectively, with a marked seasonal cycle mainly driven by sunlight and sea-ice coverage. Model results are validated against polar boundary layer measurements of ClO, BrO, and IO, and satellite BrO and IO columns. This validation includes satellite observations of IO over inner Antarctica for which an iodine "leapfrog" mechanism is proposed to transport active iodine from coastal source regions to the interior of the continent. The modeled chlorine and bromine polar sources represent up to 45% and 80% of the global biogenic VSL Cl and VSL Br emissions, respectively, while the Antarctic sea-ice iodine flux is~10 times larger than that from the Southern Ocean. We present the first estimate of the contribution of polar halogen emissions to the global tropospheric halogen budget. CAM-Chem includes now a complete representation of halogen sources and chemistry from pole-to-pole and from the Earth's surface up to the stratopause. Key Points:• The contribution of polar sea-ice sources to the global tropospheric halogen budget has been computed using the CAM-Chem model • The annual halogen flux from the sea-ice surface represents between 45% and 80% of the global chloro-and bromo-carbon oceanic VSL emissions • In Antarctica, the annual iodine sea-ice flux is~10 times larger than the oceanic inorganic iodine sourceSupporting Information:• Supporting Information S1