On the formation of tropical rings of atomic halogens: Causes and implications

Halogens produced by ocean biological and photochemical processes reach the tropical tropopause layer (TTL), where cold temperatures and the prevailing low ozone abundances favor the diurnal photochemical enhancement of halogen atoms. Under these conditions atomic bromine and iodine are modeled to be the dominant inorganic halogen species in the sunlit TTL, surpassing the abundance of the commonly targeted IO and BrO radicals. We suggest that due to the rapid photochemical equilibrium between halogen oxides and halogen atoms a natural atmospheric phenomenon evolves, which we have collectively termed >tropical rings of atomic halogens.> We describe the main causes controlling the modeled appearance and variability of these superposed rings of bare bromine and iodine atoms that circle the tropics following the Sun. Some potential implications for atmospheric oxidizing capacity are also explored. Our model results suggest that if experimentally confirmed, the extent and intensity of the halogen rings would directly respond to changes in oceanic halocarbon emissions, their atmospheric transport, and photochemistry.Peer Reviewe

First observations of iodine oxide from space

We present retrievals of IO total columns from the Scanning Imaging Absorption Spectrometer for Atmospheric Chartography (SCIAMACHY) satellite instrument. We analyze data for October 2005 in the polar regions to demonstrate for the first time the capability to measure IO column abundances from space. During the period of analysis (i.e. Southern Hemisphere springtime), enhanced IO vertical columns over 3 × 10^(13) molecules cm^(−2) are observed around coastal Antarctica; by contrast during that time in the Artic region IO is consistently below the calculated instrumental detection limit for individual radiance spectra (2–4 × 10^(12) molecules cm^(−2) for slant columns). The levels reported here are in reasonably good agreement with previous ground‐based measurements at coastal Antarctica. These results also demonstrate that IO is widespread over sea‐ice covered areas in the Southern Ocean. The occurrence of elevated IO and its hitherto unrecognized spatial distribution suggest an efficient iodine activation mechanism at a synoptic scale over coastal Antarctica

An intrinsic timer specifies distal structures of the vertebrate limb

How the positional values along the proximo-distal axis (stylopod-zeugopod-autopod) of the limb are specified is intensely debated. Early work suggested that cells intrinsically change their proximo-distal positional values by measuring time. Recently, however, it is suggested that instructive extrinsic signals from the trunk and apical ectodermal ridge specify the stylopod and zeugopod/autopod, respectively. Here, we show that the zeugopod and autopod are specified by an intrinsic timing mechanism. By grafting green fluorescent protein-expressing cells from early to late chick wing buds, we demonstrate that distal mesenchyme cells intrinsically time Hoxa13 expression, cell cycle parameters and the duration of the overlying apical ectodermal ridge. In addition, we reveal that cell affinities intrinsically change in the distal mesenchyme, which we suggest results in a gradient of positional values along the proximo-distal axis. We propose a complete model in which a switch from extrinsic signalling to intrinsic timing patterns the vertebrate limb

Bromine partitioning in the tropical tropopause layer: Implications for stratospheric injection

© Author(s) 2014. Very short-lived (VSL) bromocarbons are produced at a prodigious rate by ocean biology and these source compounds (SGVSL), together with their inorganic degradation products (PGVSL), are lofted by vigorous convection to the tropical tropopause layer (TTL). Using a state-of-the-art photochemical mechanism within a global model, we calculate annual average stratospheric injection of total bromine due to VSL sources to be 5 pptv (parts per trillion by volume), with ∼ 3 pptv entering the stratosphere as PGVSL and ∼ 2 pptv as SGVSL. The geographic distribution and partitioning of VSL bromine within the TTL, and its consequent stratospheric injection, is highly dependent on the oceanic flux, the strength of convection and the occurrence of heterogeneous recycling reactions. Our calculations indicate atomic Br should be the dominant inorganic species in large regions of the TTL during daytime, due to the low ozone and cold conditions of this region. We propose the existence of a >tropical ring of atomic bromine> located approximately between 15 and 19 km and between 30°N and 30°S. Daytime Br / BrO ratios of up to ∼ 4 are predicted within this inhomogeneous ring in regions of highly convective transport, such as the tropical Western Pacific. Therefore, we suggest that experimental programs designed to quantify the bromine budget of the TTL and the stratospheric injection of VSL biogenic bromocarbons should include a strategy for the measurement of atomic Br during daytime as well as HOBr and BrCl during nighttime.Peer Reviewe

Fin whales as bioindicators of multi-decadal change in carbon and oxygen stable isotope shifts in the North Atlantic

Global changes, and particularly the massive release of CO2 to the atmosphere and subsequent global warming, have altered the baselines of carbon and oxygen stable isotopic ratios. Temporal shifts in these baselines can be advantageously monitored through cetacean skin samples because these animals are highly mobile and therefore integrate in their tissues the heterogeneity of local environmental signals. In this study, we examine variation of delta C-13 and delta O-18 values in the skin of fin whales sampled over three decades in two different North Atlantic feeding grounds: west Iceland and northwest Spain. These locations are situated about 2700 km apart and thus represent a wide latitudinal range within the North Atlantic Ocean. The delta C-13 decrease in both areas is attributed to the burning of fossil fuels and increased deforestation worldwide, the so-called Suess effect. The dissimilarity in the magnitude of the shift between the two areas is coincidental with previous information on local shifts and lies within the ranges of variation observed. delta O-18 values experienced a minimal, yet significant change in fin whales from W Iceland (a decline of - 0.44 parts per thousand between 1986 and 2013) but not in those from NW Spain. This is in concordance with a higher rise in temperatures in the former area than in the latter. The study validates the use of cetacean skin to monitor temporal and geographical shifts in stable isotopic values and alerts that, when applying this tool to ecological research, comparisons between sample sets should take into account temporal and latitudinal scales

Chemical interactions between ship-originated air pollutants and ocean-emitted halogens

Ocean-going ships supply products from one region to another and contribute to the world's economy. Ship exhaust contains many air pollutants and results in significant changes in marine atmospheric composition. The role of Reactive Halogen Species (RHS) in the troposphere has received increasing recognition and oceans are the largest contributors to their atmospheric burden. However, the impact of shipping emissions on RHS and that of RHS on ship-originated air pollutants have not been studied in detail. Here, an updated WRF-Chem model is utilized to explore the chemical interactions between ship emissions and oceanic RHS over the East Asia seas in summer. The emissions and resulting chemical transformations from shipping activities increase the level of NO and NO2 at the surface, increase O3 in the South China Sea, but decrease O3 in the East China Sea. Such changes in pollutants result in remarkable changes in the levels of RHS as well as in their partitioning. The abundant RHS, in turn, reshape the loadings of air pollutants and those of the oxidants with marked patterns along the ship tracks. We, therefore, suggest that these important chemical interactions of ship-originated emissions with RHS should be considered in the environmental policy assessments of the role of shipping emissions in air quality and climate.Fil: Li, Qinyi. Consejo Superior de Investigaciones Científicas. Instituto de Química Física; EspañaFil: Fernandez, Rafael P.. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mendoza. Instituto Interdisciplinario de Ciencias Básicas. - Universidad Nacional de Cuyo. Instituto Interdisciplinario de Ciencias Básicas; ArgentinaFil: Mahan, Anoop. No especifíca;Fil: Lopez, Ana Isabel. Universidad Tecnológica Nacional. Facultad Regional de Mendoza; ArgentinaFil: Shanshan, Wang. Key Laboratory Atmospheric Particle Pollution Research; ChinaFil: Puliafito, Salvador Enrique. Universidad Tecnológica Nacional. Facultad Regional de Mendoza; ArgentinaFil: Cuevas, Carlos A.. Consejo Superior de Investigaciones Científicas. Instituto de Química Física; EspañaFil: Saiz Lopez, Alfonso. Consejo Superior de Investigaciones Científicas. Instituto de Química Física; EspañaEGU General Assembly 2021AustriaEuropean Geosciences Unio

Role of Iodine Recycling on Sea-Salt Aerosols in the Global Marine Boundary Layer

Heterogeneous uptake of hypoiodous acid (HOI), the dominant inorganic iodine species in the marine boundary layer (MBL), on sea-salt aerosol (SSA) to form iodine monobromide and iodine monochloride has been adopted in models with assumed efficiency. Recently, field measurements have reported a much faster rate of this recycling process than previously assumed in models. Here, we conduct global model simulations to quantify the range of effects of iodine recycling within the MBL, using Conventional, Updated, and Upper-limit coefficients. When considering the Updated coefficient, iodine recycling significantly enhances gaseous inorganic iodine abundance (similar to 40%), increases halogen atom production rates (similar to 40% in I, >100% in Br, and similar to 60% in Cl), and reduces oxidant levels (-7% in O-3, -2% in OH, and -4% in HO2) compared to the simulation without the process. We appeal for further direct measurements of iodine species, laboratory experiments on the controlling factors, and multiscale simulations of iodine heterogeneous recycling.Peer reviewe

First observations of iodine oxide from space

We present retrievals of IO total columns from the Scanning Imaging Absorption Spectrometer for Atmospheric Chartography (SCIAMACHY) satellite instrument. We analyze data for October 2005 in the polar regions to demonstrate for the first time the capability to measure IO column abundances from space. During the period of analysis (i.e. Southern Hemisphere springtime), enhanced IO vertical columns over 3 × 10^(13) molecules cm^(−2) are observed around coastal Antarctica; by contrast during that time in the Artic region IO is consistently below the calculated instrumental detection limit for individual radiance spectra (2–4 × 10^(12) molecules cm^(−2) for slant columns). The levels reported here are in reasonably good agreement with previous ground‐based measurements at coastal Antarctica. These results also demonstrate that IO is widespread over sea‐ice covered areas in the Southern Ocean. The occurrence of elevated IO and its hitherto unrecognized spatial distribution suggest an efficient iodine activation mechanism at a synoptic scale over coastal Antarctica

Wetting of metals and glasses on Mo

The wetting of low melting point metals and Si-Ca-Al-Ti-O glasses on molybdenum has been investigated. The selected metals (Au, Cu, Ag) form a simple eutectic with Mo. Metal spreading occurs under nonreactive conditions without interdiffusion or ridge formation. The metals exhibit low (non-zero) contact angles on Mo but this requires temperatures higher than 1100 C in reducing atmospheres in order to eliminate a layer of adsorbed impurities on the molybdenum surface. By controlling the oxygen activity in the furnace, glass spreading can take place under reactive or nonreactive conditions. We have found that in the glass/Mo system the contact angle does not decrease under reactive conditions. In all cases, adsorption from the liquid seems to accelerate the diffusivity on the free molybdenum surface

Modelling future changes to the stratospheric source gas injection of biogenic bromocarbons

Simulations with a chemistry-climate model (CCM) show a future increase in the stratospheric source gas injection (SGI) of biogenic very short-lived substances (VSLS). For 2000, the modelled SGI of bromine from VSLS is similar to 1.7 parts per trillion (pptv) and largest over the tropical West Pacific. For 2100, this increases to similar to 2.0 and similar to 2.7 pptv when the model is forced with Intergovernmental Panel on Climate Change (IPCC) representative concentration pathways (RCPs) 4.5 and 8.5. The increase is largely due to stronger tropical deep convection transporting more CHBr3 to the lower stratosphere. For CH2Br2, CHBr2Cl, CH2BrCl and CHBrCl2, changes to primary oxidant OH determines their SGI contribution. Under RCP 4.5 (moderate warming), OH increases in a warmer, more humid troposphere. Under RCP 8.5 (extreme warming) OH decreases significantly due to a large methane increase, allowing greater SGI of bromine from these VSLS. Potentially enhanced VSLS emissions in the future would further increase these estimates. Citation: Hossaini, R., et al. (2012), Modelling future changes to the stratospheric source gas injection of biogenic bromocarbons, Geophys. Res. Lett., 39, L20813, doi:10.1029/2012GL053401