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1.
Sci Data ; 6(1): 286, 2019 11 26.
Artigo em Inglês | MEDLINE | ID: mdl-31772255

RESUMO

The marine iodine cycle has significant impacts on air quality and atmospheric chemistry. Specifically, the reaction of iodide with ozone in the top few micrometres of the surface ocean is an important sink for tropospheric ozone (a pollutant gas) and the dominant source of reactive iodine to the atmosphere. Sea surface iodide parameterisations are now being implemented in air quality models, but these are currently a major source of uncertainty. Relatively little observational data is available to estimate the global surface iodide concentrations, and this data has not hitherto been openly available in a collated, digital form. Here we present all available sea surface (<20 m depth) iodide observations. The dataset includes values digitised from published manuscripts, published and unpublished data supplied directly by the originators, and data obtained from repositories. It contains 1342 data points, and spans latitudes from 70°S to 68°N, representing all major basins. The data may be used to model sea surface iodide concentrations or as a reference for future observations.

2.
Proc Natl Acad Sci U S A ; 115(48): 12136-12141, 2018 11 27.
Artigo em Inglês | MEDLINE | ID: mdl-30420500

RESUMO

Iodine is an important nutrient and a significant sink of tropospheric ozone, a climate-forcing gas and air pollutant. Ozone interacts with seawater iodide, leading to volatile inorganic iodine release that likely represents the largest source of atmospheric iodine. Increasing ozone concentrations since the preindustrial period imply that iodine chemistry and its associated ozone destruction is now substantially more active. However, the lack of historical observations of ozone and iodine means that such estimates rely primarily on model calculations. Here we use seasonally resolved records from an Alpine ice core to investigate 20th century changes in atmospheric iodine. After carefully considering possible postdepositional changes in the ice core record, we conclude that iodine deposition over the Alps increased by at least a factor of 3 from 1950 to the 1990s in the summer months, with smaller increases during the winter months. We reproduce these general trends using a chemical transport model and show that they are due to increased oceanic iodine emissions, coupled to a change in iodine speciation over Europe from enhanced nitrogen oxide emissions. The model underestimates the increase in iodine deposition by a factor of 2, however, which may be due to an underestimate in the 20th century ozone increase. Our results suggest that iodine's impact on the Northern Hemisphere atmosphere accelerated over the 20th century and show a coupling between anthropogenic pollution and the availability of iodine as an essential nutrient to the terrestrial biosphere.


Assuntos
Poluentes Atmosféricos/química , Gelo/análise , Iodo/química , Água do Mar/química , Atmosfera , Clima , Europa (Continente) , Ozônio/química , Estações do Ano
3.
J Biol Inorg Chem ; 23(7): 1119-1128, 2018 10.
Artigo em Inglês | MEDLINE | ID: mdl-29523971

RESUMO

This study explores key features of bromine and iodine metabolism in the filamentous brown alga and genomics model Ectocarpus siliculosus. Both elements are accumulated in Ectocarpus, albeit at much lower concentration factors (2-3 orders of magnitude for iodine, and < 1 order of magnitude for bromine) than e.g. in the kelp Laminaria digitata. Iodide competitively reduces the accumulation of bromide. Both iodide and bromide are accumulated in the cell wall (apoplast) of Ectocarpus, with minor amounts of bromine also detectable in the cytosol. Ectocarpus emits a range of volatile halogenated compounds, the most prominent of which by far is methyl iodide. Interestingly, biosynthesis of this compound cannot be accounted for by vanadium haloperoxidase since the latter have not been found to catalyze direct halogenation of an unactivated methyl group or hydrocarbon so a methyl halide transferase-type production mechanism is proposed.


Assuntos
Bromo/metabolismo , Hidrocarbonetos Halogenados/metabolismo , Iodo/metabolismo , Feófitas/metabolismo , Compostos Orgânicos Voláteis/metabolismo , Bromo/química , Halogenação , Hidrocarbonetos Halogenados/química , Iodo/química , Feófitas/química , Feófitas/citologia , Compostos Orgânicos Voláteis/química
4.
Environ Sci Technol ; 52(4): 1817-1826, 2018 02 20.
Artigo em Inglês | MEDLINE | ID: mdl-29370515

RESUMO

Organic matter in the sea surface microlayer (SML) may be transferred to the atmosphere as sea spray and hence influence the composition and properties of marine aerosol. Recent work has demonstrated that the SML contains material capable of heterogeneously nucleating ice, but the nature of this material remains largely unknown. Water-soluble organic matter was extracted from SML and underlying seawater from the Arctic and analyzed using a combination of mass spectrometric approaches. High performance liquid chromatography-ion trap mass spectrometry (LC-IT-MS), and Fourier transform ion cyclotron resonance MS (FT-ICR-MS), showed seawater extracts to be compositionally similar across all stations, whereas microlayer extracts had a different and more variable composition. LC-IT-MS demonstrated the enrichment of particular ions in the microlayer. Ice nucleation ability (defined as the median droplet freezing temperature) appeared to be related to the relative abundances of some ions, although the extracts themselves did not retain this property. Molecular formulas were assigned using LC-quadrupole time-of-flight MS (LC-TOF-MS2) and FT-ICR-MS. The ice nucleation tracer ions were associated with elevated biogenic trace gases, and were also observed in atmospheric aerosol collected during the summer, but not early spring suggesting a biogenic source of ice nuclei in the Arctic microlayer.


Assuntos
Gelo , Água , Aerossóis , Regiões Árticas , Água do Mar
10.
Environ Sci Technol ; 51(18): 10449-10458, 2017 Sep 19.
Artigo em Inglês | MEDLINE | ID: mdl-28752764

RESUMO

We report novel in situ speciated observations of monoterpenes (α- and ß-pinene, myrcene, δ3-carene, ocimene, limonene) in seawater and air during three cruises in the Arctic and Atlantic Oceans, in/over generally oligotrophic waters. Oceanic concentrations of the individual monoterpenes ranged from below the detection limit of <1 pmol L-1 to 5 pmol L-1, with average concentrations of between 0.5 and 2.9 pmol L-1. After careful filtering for contamination, atmospheric mixing ratios varied from below the detection limit (<1 pptv) to 5 pptv, with averages of 0.05-5 pptv; these levels are up to 2 orders of magnitude lower than those reported previously. This could be at least partly due to sampling over waters with much lower biological activity than in previous studies. Unlike in previous studies, no clear relationships of the monoterpenes with biological variables were found. Based on our measured seawater concentrations and a global model simulation, we estimate total global marine monoterpene emissions of 0.16 Tg C yr-1, similar to a previous bottom-up estimate based on laboratory monoculture studies but 2 orders of magnitude lower than a previous top-down estimate of 29.5 Tg C yr-1.


Assuntos
Monoterpenos/análise , Regiões Árticas , Oceano Atlântico , Compostos Bicíclicos com Pontes , Monitoramento Ambiental
11.
Faraday Discuss ; 200: 599-620, 2017 08 24.
Artigo em Inglês | MEDLINE | ID: mdl-28580967

RESUMO

Volatile organic compounds (VOCs) originate from a variety of sources, and play an intrinsic role in influencing air quality. Some VOCs, including benzene, are carcinogens and so directly affect human health, while others, such as isoprene, are very reactive in the atmosphere and play an important role in the formation of secondary pollutants such as ozone and particles. Here we report spatially-resolved measurements of the surface-to-atmosphere fluxes of VOCs across London and SE England made in 2013 and 2014. High-frequency 3-D wind velocities and VOC volume mixing ratios (made by proton transfer reaction - mass spectrometry) were obtained from a low-flying aircraft and used to calculate fluxes using the technique of eddy covariance. A footprint model was then used to quantify the flux contribution from the ground surface at spatial resolution of 100 m, averaged to 1 km. Measured fluxes of benzene over Greater London showed positive agreement with the UK's National Atmospheric Emissions Inventory, with the highest fluxes originating from central London. Comparison of MTBE and toluene fluxes suggest that petroleum evaporation is an important emission source of toluene in central London. Outside London, increased isoprene emissions were observed over wooded areas, at rates greater than those predicted by a UK regional application of the European Monitoring and Evaluation Programme model (EMEP4UK). This work demonstrates the applicability of the airborne eddy covariance method to the determination of anthropogenic and biogenic VOC fluxes and the possibility of validating emission inventories through measurements.

12.
Environ Sci Technol ; 51(5): 2519-2528, 2017 03 07.
Artigo em Inglês | MEDLINE | ID: mdl-28169528

RESUMO

Laboratory studies of atmospheric chemistry characterize the nature of atmospherically relevant processes down to the molecular level, providing fundamental information used to assess how human activities drive environmental phenomena such as climate change, urban air pollution, ecosystem health, indoor air quality, and stratospheric ozone depletion. Laboratory studies have a central role in addressing the incomplete fundamental knowledge of atmospheric chemistry. This article highlights the evolving science needs for this community and emphasizes how our knowledge is far from complete, hindering our ability to predict the future state of our atmosphere and to respond to emerging global environmental change issues. Laboratory studies provide rich opportunities to expand our understanding of the atmosphere via collaborative research with the modeling and field measurement communities, and with neighboring disciplines.


Assuntos
Mudança Climática , Ozônio/química , Poluição do Ar , Atmosfera/química , Ecossistema , Humanos
13.
Nat Commun ; 7: 10267, 2016 Jan 13.
Artigo em Inglês | MEDLINE | ID: mdl-26758808

RESUMO

Air parcels with mixing ratios of high O3 and low H2O (HOLW) are common features in the tropical western Pacific (TWP) mid-troposphere (300-700 hPa). Here, using data collected during aircraft sampling of the TWP in winter 2014, we find strong, positive correlations of O3 with multiple biomass burning tracers in these HOLW structures. Ozone levels in these structures are about a factor of three larger than background. Models, satellite data and aircraft observations are used to show fires in tropical Africa and Southeast Asia are the dominant source of high O3 and that low H2O results from large-scale descent within the tropical troposphere. Previous explanations that attribute HOLW structures to transport from the stratosphere or mid-latitude troposphere are inconsistent with our observations. This study suggest a larger role for biomass burning in the radiative forcing of climate in the remote TWP than is commonly appreciated.

15.
Talanta ; 137: 214-9, 2015 May.
Artigo em Inglês | MEDLINE | ID: mdl-25770627

RESUMO

Gaseous molecular iodine (I2) is an important source of reactive iodine in the marine atmosphere, but the sources of I2 are not well understood due to the lack of an easily accessible, sensitive and robust technique for analysis. In this study a microfluidic derivatisation technique combined with GC-MS has been developed to measure gaseous I2. Good linearity in the range of 0.2-416 ppb and low detection limits varying from 6 to 25 ppt for different derivatisation reagents have been achieved, which is a substantial improvement in sensitivity compared with the spectrophotometric method (detection limit of 1.20 ppb) in our previous study [L.J. Carpenter, S.M. MacDonald, M.D. Shaw, R. Kumar, R.W. Saunders, R. Parthipan, J. Wilson, J.M.C. Plane, Nature Geoscience, 6 (2013) 108-111]. The microfluidic technique was employed to quantify I2 produced from the heterogeneous reactions of potassium iodide solution and ozone. Good agreement was observed between the results of the microfluidic technique and the simulation of a coupled surface water-air kinetic model in the amount of I2 produced on the ozonolysis of iodide solutions.

16.
Environ Sci Technol ; 47(19): 10947-54, 2013 Oct 01.
Artigo em Inglês | MEDLINE | ID: mdl-24004338

RESUMO

The reaction between gaseous ozone (O3) and aqueous iodide (I(-)) at the surface microlayer (SML) is believed to be a major chemical contributor to the oceanic dry deposition of O3 over open ocean waters and has also recently been shown to produce environmentally significant quantities of gaseous molecular iodine (I2). Here we investigate how this reaction is affected by the presence of dissolved organic carbon (DOC) of marine origin, using a heterogeneous flow reactor and detection of gaseous I2 by solvent trapping and UV/vis spectroscopy. Ozone deposition measurements over coastal seawater implied an O3 reactivity (λ) toward coastal marine DOC of ∼500 (420-580) s(-1), 2-5 times higher than that toward iodide at typical ocean concentrations (∼0.5-1 × 10(-7) M). We added varying amounts of highly concentrated DOC extracted from coastal seawater to I(-) solutions (1 × 10(-5) M) such that the relative reactivities of DOC and I(-) toward O3 (λDOC/λI) were in the expected range for natural seawater. The evolution of gaseous I2 and the loss of aqueous I(-) both reduced as DOC concentrations increased, with an overall suppression of I2 emissions of about a factor of 2 under conditions of λDOC/λI representative of open ocean waters (0.5-1). A kinetic model of the SML suggested that neither competition of DOC with I(-) for reaction with interfacial O3, nor direct loss of I2 and hypoiodous acid (HOI) through reaction with increasing quantities of DOC, can fully explain these results. We conclude that the suppression of I2 emissions by DOC is largely a physical effect arising from a decrease in the net transfer of I2 from the aqueous to gas phase, as suggested by recent laboratory studies.


Assuntos
Poluentes Atmosféricos/química , Carbono/química , Iodetos/química , Ozônio/química , Água do Mar/química , Ar , Iodo/química , Modelos Teóricos
17.
J Exp Bot ; 64(10): 2653-64, 2013 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-23606364

RESUMO

The metabolism of bromine in marine brown algae remains poorly understood. This contrasts with the recent finding that the accumulation of iodide in the brown alga Laminaria serves the provision of an inorganic antioxidant - the first case documented from a living system. The aim of this study was to use an interdisciplinary array of techniques to study the chemical speciation, transformation, and function of bromine in Laminaria and to investigate the link between bromine and iodine metabolism, in particular in the antioxidant context. First, bromine and iodine levels in different Laminaria tissues were compared by inductively coupled plasma MS. Using in vivo X-ray absorption spectroscopy, it was found that, similarly to iodine, bromine is predominantly present in this alga in the form of bromide, albeit at lower concentrations, and that it shows similar behaviour upon oxidative stress. However, from a thermodynamic and kinetic standpoint, supported by in vitro and reconstituted in vivo assays, bromide is less suitable than iodide as an antioxidant against most reactive oxygen species except superoxide, possibly explaining why kelps prefer to accumulate iodide. This constitutes the first-ever study exploring the potential antioxidant function of bromide in a living system and other potential physiological roles. Given the tissue-specific differences observed in the content and speciation of bromine, it is concluded that the bromide uptake mechanism is different from the vanadium iodoperoxidase-mediated uptake of iodide in L. digitata and that its function is likely to be complementary to the iodide antioxidant system for detoxifying superoxide.


Assuntos
Antioxidantes/metabolismo , Bromo/metabolismo , Iodo/metabolismo , Kelp/metabolismo , Laminaria/metabolismo , Bromo/análise , Iodeto Peroxidase/genética , Iodeto Peroxidase/metabolismo , Iodo/análise , Kelp/química , Kelp/genética , Laminaria/química , Laminaria/genética
18.
Chem Soc Rev ; 41(19): 6473-506, 2012 Oct 07.
Artigo em Inglês | MEDLINE | ID: mdl-22821066

RESUMO

The oceans contribute significantly to the global emissions of a number of atmospherically important volatile gases, notably those containing sulfur, nitrogen and halogens. Such gases play critical roles not only in global biogeochemical cycling but also in a wide range of atmospheric processes including marine aerosol formation and modification, tropospheric ozone formation and destruction, photooxidant cycling and stratospheric ozone loss. A number of marine emissions are greenhouse gases, others influence the Earth's radiative budget indirectly through aerosol formation and/or by modifying oxidant levels and thus changing the atmospheric lifetime of gases such as methane. In this article we review current literature concerning the physical, chemical and biological controls on the sea-air emissions of a wide range of gases including dimethyl sulphide (DMS), halocarbons, nitrogen-containing gases including ammonia (NH(3)), amines (including dimethylamine, DMA, and diethylamine, DEA), alkyl nitrates (RONO(2)) and nitrous oxide (N(2)O), non-methane hydrocarbons (NMHC) including isoprene and oxygenated (O)VOCs, methane (CH(4)) and carbon monoxide (CO). Where possible we review the current global emission budgets of these gases as well as known mechanisms for their formation and loss in the surface ocean.

20.
Angew Chem Int Ed Engl ; 50(49): 11598-620, 2011 Dec 02.
Artigo em Inglês | MEDLINE | ID: mdl-22113847

RESUMO

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.


Assuntos
Química/história , Iodo/análise , Iodo/metabolismo , Animais , Monitoramento Ambiental , História do Século XIX , História do Século XX , História do Século XXI , Humanos , Iodo/química , Compostos de Iodo/análise , Compostos de Iodo/química , Compostos de Iodo/metabolismo , Glândula Tireoide/metabolismo
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