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We collected mercury observations as part of the Nitrogen, Oxidants, Mercury, and Aerosol Distributions, Sources, and Sinks (NOMADSS) aircraft campaign over the southeastern US between 1 June and 15 July 2013. We use the GEOS-Chem chemical transport model to interpret these observations and place new constraints on bromine radical initiated mercury oxidation chemistry in the free troposphere. We find that the model reproduces the observed mean concentration of total atmospheric mercury (THg) (observations: 1:49±0:16 ngm-3, model: 1:51± 0:08 ngm-3), as well as the vertical profile of THg. The majority (65 %) of observations of oxidized mercury (Hg(II)) were below the instrument's detection limit (detection limit per flight: 58-228 pgm-3), consistent with model-calculated Hg(II) concentrations of 0-196 pgm-3. However, for observations above the detection limit we find that modeled Hg(II) concentrations are a factor of 3 too low (observations: 212±112 pgm-3, model: 67±44 pgm-3). The highest Hg(II) concentrations, 300-680 pgm-3, were observed in dry (RH<35 %) and clean air masses during two flights over Texas at 5-7 km altitude and off the North Carolina coast at 1-3 km. The GEOS-Chem model, back trajectories and observed chemical tracers for these air masses indicate subsidence and transport from the upper and middle troposphere of the subtropical anticyclones, where fast oxidation of elemental mercury (Hg(0)) to Hg(II) and lack of Hg(II) removal lead to efficient accumulation of Hg(II). We hypothesize that the most likely explanation for the model bias is a systematic underestimate of the Hg.(0)+Br reaction rate. We find that sensitivity simulations with tripled bromine radical concentrations or a faster oxidation rate constant for Hg.0/CBr, result in 1.5-2 times higher modeled Hg(II) concentrations and improved agreement with the observations. The modeled tropospheric lifetime of Hg(0) against oxidation to Hg(II) decreases from 5 months in the base simulation to 2.8-1.2 months in our sensitivity simulations. In order to maintain the modeled global burden of THg, we need to increase the in-cloud reduction of Hg(II), thus leading to faster chemical cycling between Hg(0) and Hg(II). Observations and model results for the NOMADSS campaign suggest that the subtropical anticyclones are significant global sources of Hg(II). [ABSTRACT FROM AUTHOR]

High wintertime ozone levels have been observed in the Uintah Basin, Utah, a sparsely populated rural region with intensive oil and gas operations. The reactive nitrogen budget plays an important role in tropospheric ozone formation. Measurements were taken during three field campaigns in the winters of 2012, 2013 and 2014, which experienced varying climatic conditions. Average concentrations of ozone and total reactive nitrogen were observed to be 2.5 times higher in 2013 than 2012, with 2014 an intermediate year in most respects. However, photochemically active NOx (NO + NO2) remained remarkably similar all three years. Nitric acid comprised roughly half of NOz (≡NOy – NOx) in 2013, with nighttime nitric acid formation through heterogeneous uptake of N2O5 contributing approximately 6 times more than daytime formation. In 2012, N2O5 and ClNO2 were larger components of NOz relative to HNO3. The nighttime N2O5 lifetime between the high-ozone year 2013 and the low-ozone year 2012 is lower by a factor of 2.6, and much of this is due to higher aerosol surface area in the high-ozone year of 2013. A box-model simulation supports the importance of nighttime chemistry on the reactive nitrogen budget, showing a large sensitivity of NOx and ozone concentrations to nighttime processes. [ABSTRACT FROM AUTHOR]

We collected mercury observations as part of the Nitrogen, Oxidants, Mercury, and Aerosol Distributions, Sources, and Sinks (NOMADSS) aircraft campaign over the southeastern US between 1 June and 15 July 2013. We use the GEOS-Chem chemical transport model to interpret these observations and place new constraints on bromine radical initiated mercury oxidation chemistry in the free troposphere. We find that the model reproduces the observed mean concentration of total atmospheric mercury (THg) (observations: 1.49±0.16 ngm-3, model: 1.51±0.08 ngm-3), as well as the vertical profile of THg. The majority (65 %) of observations of oxidized mercury (Hg(II)) are below the instrument's detection limit (detection limit per flight: 58-228 pgm-3), consistent with model-calculated Hg(II) concentrations of 0-196 pgm-3. However, for observations above the detection limit we find that modeled Hg(II) concentrations are a factor of 3 too low (observations: 212±112 pgm-3, model: 67±44 pgm-3). The highest Hg(II) concentrations, 300-680 pgm-3, were observed in dry (RH<35 %) and clean air masses during two flights over Texas at 5-7 km altitude and off the North Carolina coast at 1-3 km. The GEOS-Chem model, back trajectories and observed chemical tracers for these air masses indicate subsidence and transport from the upper and middle troposphere of the subtropical anticyclones, where fast oxidation of elemental mercury (Hg(0)) to Hg(II) and lack of Hg(II) removal lead to efficient accumulation of Hg(II). We hypothesize that the most likely explanation for the model bias is a systematic underestimate of the Hg(0)+Br reaction rate. We find that sensitivity simulations with tripled bromine radical concentrations or a faster oxidation rate constant for Hg(0)+Br, result in 1.5-2 times higher modeled Hg(II) concentrations and improved agreement with the observations. The modeled tropospheric lifetime of Hg(0) against oxidation to Hg(II) decreases from 5 months in the base simulation to 2.8-1.2 months in our sensitivity simulations. In order to maintain the modeled global burden of THg, we need to increase the in-cloud reduction of Hg(II), thus leading to faster chemical cycling between Hg(0) and Hg(II). Observations and model results for the NOMADSS campaign suggest that the subtropical anticyclones are significant global sources of Hg(II). [ABSTRACT FROM AUTHOR]

Nitrous acid (HONO) acts as a major precursor of the hydroxyl radical (OH) in the urban atmospheric boundary layer in the morning and throughout the day. Despite its importance, HONO formation mechanisms are not yet completely understood. It is generally accepted that conversion of NO2 on surfaces in the presence of water is responsible for the formation of HONO in the nocturnal boundary layer, although the type of surface on which the mechanism occurs is still under debate. Recent observations of higher than expected daytime HONO concentrations in both urban and rural areas indicate the presence of unknown daytime HONO source(s). Various formation pathways in the gas phase, and on aerosol and ground surfaces have been proposed to explain the presence of daytime HONO. However, it is unclear which mechanism dominates and, in the cases of heterogeneous mechanisms, on which surfaces they occur. Vertical concentration profiles of HONO and its precursors can help in identifying the dominant HONO formation pathways. In this study, daytime HONO and NO2 vertical profiles, measured in three different height intervals (20-70, 70-130, and 130-300m) in Houston, TX, during the 2009 Study of Houston Atmospheric Radical Precursors (SHARP) are analyzed using a one-dimensional (1-D) chemistry and transport model. Model results with various HONO formation pathways suggested in the literature are compared to the the daytime HONO and HONO/NO2 ratios observed during SHARP. The best agreement of HONO and HONO/NO2 ratios between model and observations is achieved by including both a photolytic source of HONO at the ground and on the aerosol. Model sensitivity studies show that the observed diurnal variations of the HONO/NO2 ratio are not reproduced by the model if there is only a photolytic HONO source on aerosol or in the gas phase from NO2 +H2O. Further analysis of the formation and loss pathways of HONO shows a vertical dependence of HONO chemistry during the day. Photolytic HONO formation at the ground is the major formation pathway in the lowest 20 m, while a combination of gas-phase, photolytic formation on aerosol, and vertical transport is responsible for daytime HONO between 200- 300ma.g.l. HONO removal is dominated by vertical transport below 20m and photolysis between 200-300ma.g.l. [ABSTRACT FROM AUTHOR]

From 10 May through 17 June 2007 and 6 June through 9 July 2008 intensive sampling campaigns at Summit, Greenland confirmed that active bromine chemistry is occurring in and above the snow pack at the highest part of the Greenland ice sheet (72° 36' N, 38° 25' W and 3.2 km above sea level). Direct measurements found BrO and soluble gas phase Br mixing ratios in the low pptv range on many days (maxima < 10 pptv). Conversion of up to 200 pgm of gaseous elemental mercury (GEM) to reactive gaseous mercury (RGM) and enhanced OH relative to HO2 plus RO2 confirm that active bromine chemistry is impacting chemical cycles even at such low abundances of reactive bromine species. However, it does not appear that Bry chemistry can fully account for observed perturbations to HOx partitioning, suggesting unknown additional chemical processes may be important in this unique environment, or that our understanding of coupled NO x-HO x-Bry chemistry above sunlit polar snow is incomplete. Rapid transport from the north Atlanticmarine boundary layer occasionally caused enhanced BrO at Summit (just two such events observed during the 12 weeks of sampling over the two seasons). In general observed reactive bromine was linked to activation of bromide (Br-) in, and release of reactive bromine from, the snowpack. A coupled snow-atmosphere model simulated observed NO and BrO at Summit during a three day interval when winds were weak. The source of Br- in surface and near surface snow at Summit is not entirely clear, but concentrations were observed to increase when stronger vertical mixing brought free tropospheric air to the surface. Reactive Bry mixing ratios above the snow often increased in the day or two following increases in snow concentration, but this response was not consistent. On seasonal time scales concentrations of Br- in snow and reactive bromine in the air were directly related. [ABSTRACT FROM AUTHOR]

The chemical composition of the boundary layer in snow covered regions is impacted by chemistry in the snowpack via uptake, processing, and emission of atmospheric trace gases. We use the coupled one-dimensional (1-D) snow chemistry and atmospheric boundary layer model MISTRA-SNOW to study the impact of snowpack chemistry on the oxidation capacity of the boundary layer. The model includes gas phase photochemistry and chemical reactions both in the interstitial air and the atmosphere. While it is acknowledged that the chemistry occurring at ice surfaces may consist of a true quasi-liquid layer and/or a concentrated brine layer, lack of additional knowledge requires that this chemistry be modeled as primarily aqueous chemistry occurring in a liquid-like layer (LLL) on snow grains. The model has been recently compared with BrO and NO data taken on 10 June-13 June 2008 as part of the Greenland Summit Halogen-HOx experiment (GSHOX). In the present study, we use the same focus period to investigate the influence of snowpack derived chemistry on OH and HOx + RO2 in the boundary layer. We compare model results with chemical ionization mass spectrometry (CIMS) measurements of the hydroxyl radical (OH) and of the hydroperoxyl radical (HO2) plus the sum of all organic peroxy radicals (RO2) taken at Summit during summer 2008. Using sensitivity runs we show that snowpack influenced nitrogen cycling and bromine chemistry both increase the oxidation capacity of the boundary layer and that together they increase the midday OH concentrations. Bromine chemistry increases the OH concentration by 10-18% (10% at noon LT), while snow sourced NOx increases OH concentrations by 20-50%(27% at noon LT). We show for the first time, using a coupled one-dimensional snowpack-boundary layer model, that air-snow interactions impact the oxidation capacity of the boundary layer and that it is not possible to match measured OH levels without snowpack NOx and halogen emissions. Model predicted HONO compared with mistchamber measurements suggests there may be an unknown HONO source at Summit. Other model predicted HOx precursors, H2O2 and HCHO, compare well with measurements taken in summer 2000, which had lower levels than other years. Over 3 days, snow sourced NOx contributes an additional 2 ppb to boundary layer ozone production, while snow sourced bromine has the opposite effect and contributes 1 ppb to boundary layer ozone loss. [ABSTRACT FROM AUTHOR]

Nitrous Acid (HONO) plays an important role in tropospheric chemistry as a precursor of the hydroxyl radical (OH), the most important oxidizing agent in the atmosphere. Nevertheless, the formation mechanisms of HONO are still not completely understood. Recent field observations found unexpectedly high daytime HONO concentrations in both urban and rural areas, which point to unrecognized, most likely photolytically enhanced HONO sources. Several gas-phase, aerosol, and ground surface chemistry mechanisms have been proposed to explain elevated daytime HONO, but atmospheric evidence to favor one over the others is still weak. New information on whether HONO formation occurs in the gas-phase, on aerosol, or at the ground may be derived from observations of the vertical distribution of HONO and its precursor nitrogen dioxide, NO2, as well as from its dependence on solar irradiance or actinic flux. Here we present field observations of HONO, NO2 and other trace gases in three altitude intervals (30-70 m, 70-130m and 130-300 m) using UCLA's long path DOAS instrument, as well as in situ measurements of OH, NO, photolysis frequencies and solar irradiance, made in Houston, TX, during the Study of Houston Atmospheric Radical Precursor (SHARP) experiment from 20 April to 30 May 2009. The observed HONO mixing ratios were often ten times larger than the expected photostationary state with OH and NO. Larger HONO mixing ratios observed near the ground than aloft imply, but do not clearly prove, that the daytime source of HONO was located at or near the ground. Using a pseudo steady-state (PSS) approach, we calculated the missing daytime HONO formation rates, Punknown, on four sunny days. The NO2-normalized Punknown, Pnorm, showed a clear symmetrical diurnal variation with a maximum around noontime, which was well correlated with actinic flux (NO2 photolysis frequency) and solar irradiance. This behavior, which was found on all clear days in Houston, is a strong indication of a photolytic HONO source. [HONO]/[NO2] ratios also showed a clear diurnal profile, with maxima of 2-3% around noon. PSS calculations show that this behavior cannot be explained by the proposed gas-phase reaction of photoexcited NO2 (NO2*) or any other gas-phase or aerosol photolytic process occurring at similar or longer wavelengths than that of HONO photolysis. HONO formation by aerosol nitrate photolysis in the UV also seems to be unlikely. Pnorm correlated better with solar irradiance (average R² = 0.85/0.87 for visible/UV) than with actinic flux (R² = 0.76) on the four sunny days, clearly pointing to HONO being formed at the ground rather than on the aerosol or in the gas-phase. In addition, the observed [HONO]/[NO2] diurnal variation can be explained if the formation of HONO depends on solar irradiance, but not if it depends on the actinic flux. The vertical mixing ratio profiles, together with the stronger correlation with solar irradiance, support the idea that photolytically enhanced NO2 to HONO conversion on the ground was the dominant source of HONO in Houston. [ABSTRACT FROM AUTHOR]

Reactive halogens, and in particular bromine oxide (BrO), have frequently been observed in regions with large halide reservoirs, for example during bromine catalyzed coastal polar ozone depletion events. Much less is known about the presence and impact of reactive halogens in areas without obvious halide reservoirs, such as the polar ice sheets or continental snow. We report the first LP-DOAS measurements of BrO at Summit research station in the center of the Greenland ice sheet at an altitude of 3200 m. BrO mixing ratios in May 2007 and June 2008 were typically between 1-3 pmol mol-1, with maxima of up to 3 pmol mol-1. These measurements unequivocally show that halogen chemistry is occurring in the remote Arctic, far from known bromine reservoirs, such as the ocean. During periods when FLEXPART retroplumes show that airmasses resided on the Greenland ice sheet for 3 or more days, BrO exhibits a clear diurnal variation, with peak mixing ratios of up to 3 pmol mol -1 in the morning and at night. The diurnal cycle of BrO can be explained by a changing boundary layer height combined with photochemical formation of reactive bromine driven by solar radiation at the snow surface. The shallow stable boundary layer in the morning and night leads to an accumulation of BrO at the surface, leading to elevated BrO despite the expected smaller release from the snowpack during these times of low solar radiation. During the day when photolytic formation of reactive bromine is expected to be highest, efficient mixing into a deeper neutral boundary layer leads to lower BrO mixing ratios than during mornings and nights. The extended period of contact with the Greenland snow-pack combined with the diurnal profile of BrO, modulated by boundary layer height, suggests that photochemistry in the snow is a significant source of BrO measured at Summit during the 2008 experiment. In addition, a rapid transport event on 4 July 2008, during which marine air from the Greenland east coast was rapidly transported to Summit, led to enhanced mixing ratios of BrO and a number of marine tracers. However, rapid transport of marine air from the Greenland east coast is rare and most likely not the main source of bromide in surface snow at Summit. The observed levels of BrO are predicted to influence NOx chemistry as well as impact HOx partitioning. However, impact of local snow photochemistry on HOx is smaller than previously suggested for Summit. [ABSTRACT FROM AUTHOR]

The Greenland Summit Halogen-HOx (GSHOX) Campaign was performed in spring 2007 and summer 2008 to investigate the impact of halogens on HOx (=OH+HO2) cycling above the Greenland Ice Sheet. Chemical species including hydroxyl and peroxy radicals (OH and HO2+ RO2), ozone (O 3), nitrogen oxide (NO), nitric acid (HO3), nitrous acid (HONO), reactive gaseous mercury (RGM), and bromine oxide (BrO) were measured during the campaign. The median midday values of HO2+ RO2 and OH concentrations observed by chemical ionization mass spectrometry (CIMS) were 2.7x108 molec cm-3 and 3.0x106 molec cm-3 in spring 2007, and 4.2x108 molec cm-3 and 4.1x106 molec cm-3 in summer 2008. A basic photochemical 0-D box model highly constrained by observations of H2O, O3, CO, CH4, NO, and J values predicted HO2+ RO2 (R = 0.90, slope = 0.87 in 2007; R = 0.79, slope = 0.96 in 2008) reasonably well and under predicted OH (R = 0.83, slope = 0.72 in 2007; R = 0.76, slope = 0.54 in 2008). Constraining the model to HONO observations did not signi?cantly improve the ratio of OH to HO2+ RO2 and the correlation between predictions and observations. Including bromine chemistry in the model constrained by observations of BrO improved the correlation between observed and predicted HO2+ RO2 and OH, and brought the average hourly OH and HO2+ RO2 predictions closer to the observations. These model comparisons confirmed our understanding of the dominant HOx sources and sinks in this environment and indicated that BrO impacted the OH levels at Summit. Although, significant discrepancies between observed and predicted OH could not be explained by the measured BrO. Finally, observations of enhanced RGM were found to be coincident with under prediction of OH. [ABSTRACT FROM AUTHOR]

Sun-lit snow is increasingly recognized as a chemical reactor that plays an active role in uptake, transformation, and release of atmospheric trace gases. Snow is known to influence boundary layer air on a local scale, and given the large global surface coverage of snow may also be significant on regional and global scales. We present a new detailed one-dimensional snow chemistry module that has been coupled to the I-D atmospheric boundary layer model MISTRA. The new I-D snow module, which is dynamically coupled to the overlaying atmospheric model, includes heat transport in the snowpack, molecular diffusion, and wind pumping of gases in the interstitial air. The model includes gas phase chemical reactions both in the interstitial air and the atmosphere. Heterogeneous and multiphase chemistry on atmospheric aerosol is considered explicitly. The chemical interaction of interstitial air with snow grains is simulated assuming chemistry in a liquid-like layer (LLL) on the grain surface. The coupled model, referred to as MISTRA-SNOW, was used to investigate snow as the source of nitrogen oxides (NOx) and gas phase reactive bromine in the atmospheric boundary layer in the remote snow covered Arctic (over the Greenland ice sheet) as well as to investigate the link between halogen cycling and ozone depletion that has been observed in interstitial air. The model is validated using data taken 10 June-13 June, 2008 as part of the Greenland Sum mit Halogen-HOx experiment (GSHOX). The model predicts that reactions involving bromide and nitrate impurities in the surface snow can sustain atmospheric NO and BrO mixing ratios measured at Summit, Greenland during this period. [ABSTRACT FROM AUTHOR]

Nitrous acid (HONO) often plays an important role in tropospheric photochemistry as a major precursor of the hydroxyl radical (OH) in early morning hours and potentially during the day. However, the processes leading to formation of HONO and its vertical distribution at night, which can have a considerable impact on daytime ozone formation, are currently poorly characterized by observations and models. Long-path differential optical absorption spectroscopy (LP-DOAS) measurements of HONO during the 2006 TexAQS II Radical and Aerosol Measurement Project (TRAMP), near downtown Houston, TX, show nocturnal vertical profiles of HONO, with mixing ratios of up to 2.2 ppb near the surface and below 100 ppt aloft. Three night-time periods of HONO, NO2 and O3 observations during TRAMP were used to perform model simulations of vertical mixing ratio profiles. By adjusting vertical mixing and NO emissions the modeled NO2 and O3 mixing ratios showed very good agreement with the observations. Using a simple conversion of NO2 to HONO on the ground, direct HONO emissions, as well as HONO loss at the ground and on aerosol, the observed HONO profiles were reproduced by the model for 1-2 and 7-8 September in the nocturnal boundary layer (NBL). The unobserved increase of HONO to NO2 ratio (HONO/NO2) with altitude that was simulated by the initial model runs was found to be clue to HONO uptake being too small on aerosol and too large on the ground. Refined model runs, with adjusted HONO uptake coefficients, showed much better agreement of HONO and HONO/NO2 for two typical nights, except during morning rush hour, when other HONO formation pathways are most likely active. One of the nights analyzed showed an increase of HONO mixing ratios together with decreasing NO2 mixing ratios that the model was unable to reproduce, most likely due to the impact of weak precipitation during this night. HONO formation and removal rates averaged over the lowest 300 m of the atmosphere showed that NO2 to HONO conversion on the ground was the dominant source of HONO, followed by traffic emission. Aerosol did not play an important role in HONO formation. Although ground deposition was also a major removal pathway of HONO, net HONO production at the ground was the main source of HONO in our model studies. Sensitivity studies showed that in the stable NBL, net HONO production at the ground tends to increase with faster vertical mixing and stronger NOx emission. Vertical transport was found to be the dominant source of HONO aloft. [ABSTRACT FROM AUTHOR]

Nocturnal chemistry in the atmospheric boundary layer plays a key role in determining the initial chemical conditions for photochemistry during the following morning as well as influencing the budgets of O3 and NO2. Despite its importance, chemistry in the nocturnal boundary layer (NBL), especially in heavily polluted urban areas, has received little attention so far, which greatly limits the current understanding of the processes involved. In particular, the influence of vertical mixing on chemical processes gives rise to complex vertical profiles of various reactive trace gases and makes nocturnal chemistry altitude-dependent. The processing of pollutants is thus driven by a complicated, and not well quantified, interplay between chemistry and vertical mixing. In order to gain a better understanding of the altitude-dependent nocturnal chemistry in the polluted urban environment, a field study was carried out in the downtown area of Phoenix, AZ, in summer 2001. Vertical profiles of reactive species, such as O3, NO2, and NO3, were observed in the lowest 140m of the troposphere throughout the night. The disappearance of these trace gas vertical gradients during the morning coincided with the morning transition from a stable NBL to a well-mixed convective layer. The vertical gradients of trace gas levels were found to be dependent on both surface NOx emission strength and the vertical stability of the NBL. The vertical gradients of Ox, the sum of O3 and NO2, were found to be much smaller than those of O3 and NO2, revealing the dominant role of NO emissions followed by the O3+NO reaction for the altitude-dependence of nocturnal chemistry in urban areas. Dry deposition, direct emissions, and other chemical production pathways of NO2 also play a role for the Ox distribution. Strong positive vertical gradients of NO3, that are predominantly determined by NO3 loss near the ground, were observed. The vertical profiles of NO3 and the calculated vertical profiles of its reservoir species (N2O5) confirm earlier model results suggesting complex vertical distributions of atmospheric denoxification processes during the night. [ABSTRACT FROM AUTHOR]

We present results of three field campaigns using active longpath DOAS (Differential Optical Absorption Spectroscopy) for the study of reactive halogen species (RHS) BrO, IO, OIO and I2. Two recent field campaigns took place in Spring 2002 in Dagebüll at the German North Sea Coast and in Spring 2003 in Lilia at the French Atlantic Coast of Brittany. In addition, data from a campaign in Mace Head, Ireland in 1998 was partly re-evaluated. During the recent field campaigns volatile halogenated organic compounds (VHOCs) were determined by a capillary gas chromatograph coupled with an electron capture detector and an inductively coupled plasma mass spectrometer (GC/ECD-ICPMS) in air and water. Due to the inhomogeneous distribution of macroalgae at the German North Sea Coast we found a clear connection between elevated levels of VHOCs and the appearance of macroalgae. Extraordinarily high concentrations of several VHOCs, especially CH3I and CH3Br of up to 1830 pptv and 875 pptv, respectively, were observed at the coast of Brittany, demonstrating the outstanding level of bioactivity there. We found CH2I2 at levels of up to 20 pptv, and a clear anti-correlation with the appearance of IO. The IO mixing ratio reached up to 7.7±0.5 ppt (pmol/mol) during the day, in reasonable agreement with model studies designed to represent the meteorological and chemical conditions in Brittany. For the two recent campaigns the DOAS spectra were evaluated for BrO, OIO and I2, but none of these species could be clearly identified (average detection limits around 2 ppt, 3 ppt, 20 ppt, resp., significantly higher in individual cases). Only in the Mace Head spectra evidence was found for the presence of OIO. Since macroalgae under oxidative stress are suggested to be a further source for I2 in the marine boundary layer, we re-analyzed spectra in the 500-600 nm range taken during the 1998 PARFORCE campaign in Mace Head, Ireland, which had not previously been analyzed for I2. We identified molecular iodine above the detection limit (˜ 20 ppt), with peak mixing ratios of 61±12 ppt. Since I2 was undetectable during the Brittany campaign, we suggest that iodine may not be released into the atmosphere by macroalgae in general, but only by a special type of the laminaria species under oxidative stress. Only during periods of extraordinarily low water (spring-tide), the plant is exposed to ambient air and may release gaseous iodine in some way to the atmosphere. The results of our re-analysis of spectra from the PARFORCE campaign in 1998 support this theory. Hence, we feel that we can provide an explanation for the different I2 levels in Brittany and Mace Head. [ABSTRACT FROM AUTHOR]