Lucy J. Carpenter

Short‐lived alkyl iodides and bromides at Mace Head, Ireland: Links to biogenic sources and halogen oxide production

Automated in situ gas chromatograph/mass spectrometer (GC/MS) measurements of a range of predominantly biogenic alkyl halides in air, including CHBr3, CHBr2Cl, CH3Br, C2H5Br, CH3I, C2H5I, CH2ICl, CH2I2, 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/CHBr2Cl and CHBr3/CH2IBr and between the monohalomethane pair CH3I/C2H5I, 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, CH2ICl, 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 CH2I2. 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).

Extensive halogen-mediated ozone destruction over the tropical Atlantic Ocean

Increasing tropospheric ozone levels over the past 150 years have led to a significant climate perturbation; the prediction of future trends in tropospheric ozone will require a full understanding of both its precursor emissions and its destruction processes. A large proportion of tropospheric ozone loss occurs in the tropical marine boundary layer and is thought to be driven primarily by high ozone photolysis rates in the presence of high concentrations of water vapour. A further reduction in the tropospheric ozone burden through bromine and iodine emitted from open-ocean marine sources has been postulated by numerical models, but thus far has not been verified by observations. Here we report eight months of spectroscopic measurements at the Cape Verde Observatory indicative of the ubiquitous daytime presence of bromine monoxide and iodine monoxide in the tropical marine boundary layer. A year-round data set of co-located in situ surface trace gas measurements made in conjunction with low-level aircraft observations shows that the mean daily observed ozone loss is ∼50 per cent greater than that simulated by a global chemistry model using a classical photochemistry scheme that excludes halogen chemistry. We perform box model calculations that indicate that the observed halogen concentrations induce the extra ozone loss required for the models to match observations. Our results show that halogen chemistry has a significant and extensive influence on photochemical ozone loss in the tropical Atlantic Ocean boundary layer. The omission of halogen sources and their chemistry in atmospheric models may lead to significant errors in calculations of global ozone budgets, tropospheric oxidizing capacity and methane oxidation rates, both historically and in the future.

Iodide accumulation provides kelp with an inorganic antioxidant impacting atmospheric chemistry

Brown algae of the Laminariales (kelps) are the strongest accumulators of iodine among living organisms. They represent a major pump in the global biogeochemical cycle of iodine and, in particular, the major source of iodocarbons in the coastal atmosphere. Nevertheless, the chemical state and biological significance of accumulated iodine have remained unknown to this date. Using x-ray absorption spectroscopy, we show that the accumulated form is iodide, which readily scavenges a variety of reactive oxygen species (ROS). We propose here that its biological role is that of an inorganic antioxidant, the first to be described in a living system. Upon oxidative stress, iodide is effluxed. On the thallus surface and in the apoplast, iodide detoxifies both aqueous oxidants and ozone, the latter resulting in the release of high levels of molecular iodine and the consequent formation of hygroscopic iodine oxides leading to particles, which are precursors to cloud condensation nuclei. In a complementary set of experiments using a heterologous system, iodide was found to effectively scavenge ROS in human blood cells.

A modeling study of iodine chemistry in the marine boundary layer

An observationally constrained photochemical box model has been developed to investigate the atmospheric chemistry of iodine in the marine boundary layer, motivated by recent measurements of the iodine monoxide (IO) radical (Allan et al., this issue). Good agreement with the time series of IO measured at a midlatitude coastal station was achieved by using a reaction scheme that included recycling of iodine through marine aerosol. The strong diurnal variation in IO observed in the subtropical Atlantic was satisfactorily modeled by assuming a constant concentration of iodocarbons that photolyzed to produce roughly 1×104 iodine atoms cm−3 s−1 at midday. The significance of the occurrence of IO at concentrations of up to 4 parts per trillion in the marine boundary layer was then considered from three angles. First, the iodine-catalyzed destruction of ozone was shown to be of a magnitude similar to that caused by odd-hydrogen photochemistry, with up to 13% of the available ozone destroyed per day in a marine air mass. Second, the enrichment factor of iodine in marine aerosol compared with surface seawater was predicted to increase to values of several thousand, in sensible accord with observations. Most of the enrichment should be due to the accumulation of iodate, although other iodine species may also be present, depending on the rate of aerosol recycling. Third, the denoxification of the marine boundary layer was found to be significantly enhanced as a result of aerosol uptake of IONO2, formed from the recombination of IO with NO2.

Atmospheric Chemistry of Iodine

Atmospheric Chemistry of Iodine Alfonso Saiz-Lopez,* John M. C. Plane,* Alex R. Baker, Lucy J. Carpenter, Roland von Glasow, Juan C. G omez Martín, Gordon McFiggans, and Russell W. Saunders Laboratory for Atmospheric and Climate Science (CIAC), CSIC, Toledo, Spain School of Chemistry, University of Leeds, Leeds, LS2 9JT, United Kingdom School of Environmental Sciences, University of East Anglia, Norwich NR4 7TJ, United Kingdom Department of Chemistry, University of York, Heslington, York YO10 5DD, United Kingdom School of Earth, Atmospheric & Environmental Sciences, University of Manchester, Manchester, M13 9PL, United Kingdom

On temperate sources of bromoform and other reactive organic bromine gases

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 upper-tropospheric/lower-stratospheric ozone, such a substantial discrepancy in global emission rates is of considerable concern. Here we present new information on air and seawater CHBr3, CH2Br2, and CHBr2Cl 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 worlds 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 2.2×1011 g CHBr3 yr−1 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.

Novel biogenic iodine-containing trihalomethanes and other short-lived halocarbons in the coastal East Atlantic

Reactive halogen photochemistry and its impact on tropospheric oxidant levels have recently attracted intense research interest following the observation of the iodine oxide radical at midlatitudes. During September 1998, short-lived organoiodines including CH3I, C2H5I, CH2ICl, CH2IBr, CH2I2, and the hitherto undetected CHIBr2, as well as the organobromines CHBr3, CH2Br2, CHBr2Cl, CH3Br, and C2H5Br, were measured in air and seawater at and around Mace Head, on the west coast of Ireland. The release rates of organic bromines and iodines from seaweeds were determined from incubations of 10 species of brown, red, and green macroalgae collected in the intertidal or subtidal zones of the rocky shore. For all the brown algae studied, iodine was released mainly as CH2I2. However, for several seaweeds, the novel iodine-containing trihalomethanes CHIBr2 and CHI2Cl represented a significant fraction of the released organic iodine. The macroalgae incubation experiments as well as monitoring of the in situ concentrations in a rock pool indicated that natural halocarbon production by seaweeds was stimulated by incident light. The halocarbon fluxes derived from the seaweed incubations, coupled with published detailed biomass surveys, enabled coastal organohalogen seawater concentrations to be estimated. The CHBr3, CH2Br2, and CHBr2Cl concentrations calculated by this method compared well with coastal surface seawater measurements, implying that macroalgae were the major sources of the polybromomethanes. Measured CH3Br, CH3I, and CH2ICl levels were higher than calculated, which may be due to the existence of additional sources. CH3Br production by macroalgae accounted for less than 10% of measured levels in coastal waters. Short-lived iodocarbons such as CH2I2 and CHIBr2 were depleted in surface seawater compared to calculated levels, implying their photolytic loss within the upper water column.

Commemorating two centuries of iodine research: An interdisciplinary overview of current research

Iodine was discovered as a novel element in 1811 during the Napoleonic Wars. To celebrate the bicentennial anniversary of this event we reflect on the history and highlight the many facets of iodine research that have evolved since its discovery. Iodine has an impact on many aspects of life on Earth as well as on human civilization. It is accumulated in high concentrations by marine algae, which are the origin of strong iodine fluxes into the coastal atmosphere which influence climatic processes, and dissolved iodine is considered a biophilic element in marine sediments. Iodine is central to thyroid function in vertebrates, with paramount implications for human health. Iodine can exist in a wide range of oxidation states and it features a diverse supramolecular chemistry. Iodine is amenable to several analytical techniques, and iodine compounds have found widespread use in organic synthesis. Elemental iodine is produced on an industrial scale and has found a wide range of applications in innovative materials, including semiconductors--in particular, in solar cells.

Iodine and Halocarbon Response of Laminaria digitata to Oxidative Stress and Links to Atmospheric New Particle Production

Environmental Context.Various organic iodine compounds (including CH3I, CH2ClI, CH2BrI, CH2I2) are present throughout the marine boundary layer as a result of their production from seaweeds, phytoplankton, and photolysis reactions occurring in seawater. In air, these compounds rapidly photolyse to give atomic I which subsequently reacts with ozone to form iodine oxide, potentially leading to perturbations of the tropospheric oxidative capacity and nucleation of atmospheric particles. Recent research has identified molecular iodine as an additional source of iodine atoms to coastal areas. Here we study the relative roles and controls of gaseous organic and molecular iodine release from the seaweed Laminaria digitata. Abstract.Changes in the halocarbon, I2 and particle production of the brown algal kelp Laminaria digitata as a response to different chemical stresses have been investigated. Oxidative stress (caused by either exogenous hydrogen peroxide, gaseous ozone or a solution of oligoguluronates, known elicitors of oxidative stress) caused increased halocarbon and I2 production by the seaweed. The maximum I2 release was observed under exposure to O3 (at several hundred parts per billion by volume (ppbv)), whereas oligoguluronates elicited the highest release of iodine-containing halocarbons including CH2I2. Significantly greater production of I2, compared to CH2I2, was observed at atmospheric levels of ozone. Particle production was observed only when the Laminaria samples were exposed to ozone (up to 16 000 cm-3 s-1 per gram fresh weight (FW) of seaweed with a ~2 min residence time and with a total I atom flux of 1.6 × 108 cm-3 s-1 g-1 FW from photolysis of I2); passing O3-free air over the unstressed seaweed followed by secondary mixing with ozone did not result in any measurable particle formation. Our limited data indicate that ozone elicits abiotic production of I2 from Laminaria and that there is a direct relationship between the amount of I2 released and the number of particles formed. The results support the recent hypothesis that molecular iodine rather than volatile organic iodine (e.g. CH2I2) release from exposed seaweeds is the major source of coastal new particle production.

Simultaneous observations of nitrate and peroxy radicals in the marine boundary layer

This paper describes the most extensive set of simultaneous measurements of the concentrations of nitrate (NO3) and peroxy (sum of HO2 + RO2, R = alkyl and acyl) radicals to date. The measurements were made in the coastal marine boundary layer over the North Sea, at the Weybourne Atmospheric Observatory on the North Norfolk coast during the spring and autumn of 1994. In spring the average nighttime concentration of NO3 measured by differential optical absorption spectroscopy, was about 10 parts per trillion (ppt) (maximum 25 ppt). The corresponding peroxy radical concentration, measured by the chemical amplifier technique, averaged about 2 ppt (maximum 6 ppt), although this is likely to be an underestimate of the total radical concentration. There is a significant positive correlation between the two sets of radicals, which has not been reported previously. A box model of the marine boundary layer is used to show that this correlation arises from the processing of reactive organic species by NO3. During spring the relatively long lifetime of NO3 (up to 18 min) at night is controlled by reaction with dimethyl sulfide (DMS), and the model predicts significant production of HNO3, methyl tiomethylen (CH3SCH2O2) and other peroxy radicals, HCHO, and eventually sulfate. A nighttime production rate for the hydroxyl (OH) of about 2 x 10(4) molecules cm(-3) s(-1) is estimated. During one night in autumn the NO3 lifetime of about 3 min is too short to be explained by reaction with unsaturated hydrocarbons, but is satisfactorily accounted for by the heterogeneous loss of N2O5 on deliquesced aerosols in relatively polluted conditions.