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1.
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
2.
Faraday Discuss ; 189: 85-103, 2016 07 18.
Artigo em Inglês | MEDLINE | ID: mdl-27104223

RESUMO

Low cost pollution sensors have been widely publicized, in principle offering increased information on the distribution of air pollution and a democratization of air quality measurements to amateur users. We report a laboratory study of commonly-used electrochemical sensors and quantify a number of cross-interferences with other atmospheric chemicals, some of which become significant at typical suburban air pollution concentrations. We highlight that artefact signals from co-sampled pollutants such as CO2 can be greater than the electrochemical sensor signal generated by the measurand. We subsequently tested in ambient air, over a period of three weeks, twenty identical commercial sensor packages alongside standard measurements and report on the degree of agreement between references and sensors. We then explore potential experimental approaches to improve sensor performance, enhancing outputs from qualitative to quantitative, focusing on low cost VOC photoionization sensors. Careful signal handling, for example, was seen to improve limits of detection by one order of magnitude. The quantity, magnitude and complexity of analytical interferences that must be characterised to convert a signal into a quantitative observation, with known uncertainties, make standard individual parameter regression inappropriate. We show that one potential solution to this problem is the application of supervised machine learning approaches such as boosted regression trees and Gaussian processes emulation.

3.
Atmos Chem Phys ; 24(14): 8317-8342, 2024 Jul 24.
Artigo em Inglês | MEDLINE | ID: mdl-39376463

RESUMO

Non-Methane Volatile Organic Compounds (NMVOCs) generate ozone (O3) when they are oxidized in the presence of oxides of nitrogen, modulate the oxidative capacity of the atmosphere and can lead to the formation of aerosol. Here, we assess the capability of a chemical transport model (GEOS-Chem) to simulate NMVOC concentrations by comparing ethane, propane and higher alkane observations in remote regions from the NOAA Flask Network and the World Meteorological Organization's Global Atmosphere Watch (GAW) network. Using the Community Emissions Data System (CEDS) inventory we find a significant underestimate in the simulated concentration of both ethane (35%) and propane (64%), consistent with previous studies. We run a new simulation where the total mass of anthropogenic NMVOC emitted in a grid box is the same as that used in CEDS, but with the NMVOC speciation derived from regional inventories. For US emissions we use the National Emissions Inventory (NEI), for Europe we use the UK National Atmospheric Emissions Inventory (NAEI), and for China, the Multi-resolution Emission Inventory for China (MEIC). These changes lead to a large increase in the modelled concentrations of ethane, improving the mean model bias from -35% to -4%. Simulated propane also improves (from -64% to -48% mean model bias), but there remains a substantial model underestimate. There were relatively minor changes to other NMVOCs. The low bias in simulated global ethane concentration is essentially removed, resolving one long-term issue in global simulations. Propane concentrations are improved but remain significantly underestimated, suggesting the potential for a missing global propane source. The change in the NMVOC emission speciation results in only minor changes in tropospheric O3 and OH concentrations.

4.
Proc Math Phys Eng Sci ; 477(2247): 20200824, 2021 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-35153549

RESUMO

Iodine is a critical trace element involved in many diverse and important processes in the Earth system. The importance of iodine for human health has been known for over a century, with low iodine in the diet being linked to goitre, cretinism and neonatal death. Research over the last few decades has shown that iodine has significant impacts on tropospheric photochemistry, ultimately impacting climate by reducing the radiative forcing of ozone (O3) and air quality by reducing extreme O3 concentrations in polluted regions. Iodine is naturally present in the ocean, predominantly as aqueous iodide and iodate. The rapid reaction of sea-surface iodide with O3 is believed to be the largest single source of gaseous iodine to the atmosphere. Due to increased anthropogenic O3, this release of iodine is believed to have increased dramatically over the twentieth century, by as much as a factor of 3. Uncertainties in the marine iodine distribution and global cycle are, however, major constraints in the effective prediction of how the emissions of iodine and its biogeochemical cycle may change in the future or have changed in the past. Here, we present a synthesis of recent results by our team and others which bring a fresh perspective to understanding the global iodine biogeochemical cycle. In particular, we suggest that future climate-induced oceanographic changes could result in a significant change in aqueous iodide concentrations in the surface ocean, with implications for atmospheric air quality and climate.

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