Enhanced near-surface ozone under heatwave conditions in a Mediterranean island.

PubMed

Pyrgou, Andri; Hadjinicolaou, Panos; Santamouris, Mat

2018-06-15

Near-surface ozone is enhanced under particular chemical reactions and physical processes. This study showed the seasonal variation of near-surface ozone in Nicosia, Cyprus and focused in summers when the highest ozone levels were noted using a seven year hourly dataset from 2007 to 2014. The originality of this study is that it examines how ozone levels changed under heatwave conditions (defined as 4 consecutive days with daily maximum temperature over 39 °C) with emphasis on specific air quality and meteorological parameters with respect to non-heatwave summer conditions. The influencing parameters had a medium-strong positive correlation of ozone with temperature, UVA and UVB at daytime which increased by about 35% under heatwave conditions. The analysis of the wind pattern showed a small decrease of wind speed during heatwaves leading to stagnant weather conditions, but also revealed a steady diurnal cycle of wind speed reaching a peak at noon, when the highest ozone levels were noted. The negative correlation of NOx budget with ozone was further increased under heatwave conditions leading to steeper lows of ozone in the morning. In summary, this research encourages further analysis into the persistent weather conditions prevalent during HWs stimulating ozone formation for higher temperatures.

Influence of the West Pacific subtropical high on surface ozone daily variability in summertime over eastern China

NASA Astrophysics Data System (ADS)

Zhao, Zijian; Wang, Yuxuan

2017-12-01

The West Pacific subtropical high (WPSH), as one of the most important components of the East Asian summer monsoon (EASM), is the key synoptic-scale circulation pattern influencing summertime precipitation and atmospheric conditions in China. Here we investigate the impacts of the WPSH on surface ozone daily variability over eastern China, using observations from recently established network of ozone monitors and meteorology reanalysis data during summer (June, July, August; JJA) 2014-2016 with a focus on 2014. An empirical orthogonal function (EOF) analysis of daily ozone variations reveals that the dominating eigenvector (EOF1), which contributes a quarter (25.2%) to the total variances, is a marked north-south contrast. This pattern is temporally well correlated (r = -0.66, p < 0.01) with daily anomalies of a normalized WPSH intensity index (WPSH-I). Spatially, the WPSH-I and ozone correlation is positive in North China (NC) but negative in South China (SC), which well correlates with the ozone EOF1 pattern showing the same north-south contrast (r = -0.86, p < 0.01). These associations suggest the dominant component of surface ozone daily variability in eastern China is linked with the variability of the WPSH intensity in that a stronger WPSH leads to a decrease of surface ozone over SC but an increase over NC and vice versa. This is because a stronger WPSH enhances southwesterly transport of moisture into SC, creating such conditions not conducive for ozone formation as higher RH, more cloudiness and precipitation, less UV radiation, and lower temperature. Meanwhile, as most of the rainfall due to the enhanced southwesterly transport of moisture occurs in SC, water vapor is largely depleted in the air masses transported towards NC, creating dry and sunny conditions over NC under a strong WPSH, thereby promoting ozone formation.

A Comparative Study on Ozone Photochemical Formation in the Megacities of Tianjin and Shanghai, China

NASA Astrophysics Data System (ADS)

Ran, L.; Zhao, C.; Xu, W.; Geng, F.; Lu, X.; Han, M.; Lin, W.; Xu, X.

2011-12-01

As one of the most widespread and stubborn environmental issues, the ozone problem has been of particular concern for many years, given the potential adverse effects of high ozone concentrations on public health and agricultural productivity. In the past decades, rapid urbanization and industrialization have given rise to a significant increase in ozone precursor emissions in many regions of China, especially in the densely populated megacities. Due to the highly nonlinear impacts of ozone precursors including nitrogen oxides (NOx) and various volatile organic compounds (VOCs) on ozone photochemistry, formation of ozone affected by different precursor emission patterns in those megacities has exhibited different characteristics. A comparative analysis of ozone photochemical production in the megacities of Tianjin and Shanghai has thus been carried out, using the data sets of surface ozone and its precursors measured respectively at an urban and a suburban site of the two megacities during the summertime. Observation-based analysis indicated an elevated ozone daily peak under photochemistry dominant conditions from the urban center to the suburb in both regions, nevertheless bearing different reasons. Ozone production was generally sensitive to VOCs in the Tianjin region, leading to a relatively higher level of ozone in the suburb where reactive VOCs were abundantly released from a number of industrial facilities, whereas a sensitivity of ozone production to NOx was found in Shanghai. The high level of NOx emitted mainly by motor vehicles in urban Shanghai largely inhibited ozone formation and resulted in a much more rapid decrease in ozone concentrations after reaching the daily maximum around midday compared with the other three areas. Ozone pollution in the megacity of Tianjin was more representative of the regional condition, implying that combined efforts would be needed to bring the ozone problem under control within this region. Improved understanding of ozone formation in the two megacities would be quite imperative and critical to provide a solid scientific basis for designing effective ozone control strategies.

Towards reducing DBP formation potential of drinking water by favouring direct ozone over hydroxyl radical reactions during ozonation.

PubMed

De Vera, Glen Andrew; Stalter, Daniel; Gernjak, Wolfgang; Weinberg, Howard S; Keller, Jurg; Farré, Maria José

2015-12-15

When ozonation is employed in advanced water treatment plants to produce drinking water, dissolved organic matter reacts with ozone (O3) and/or hydroxyl radicals (OH) affecting disinfection byproduct (DBP) formation with subsequently used chlorine-based disinfectants. This study presents the effects of varying exposures of O3 and •OH on DBP concentrations and their associated toxicity generated after subsequent chlorination. DBP formation potential tests and in vitro bioassays were conducted after batch ozonation experiments of coagulated surface water with and without addition of tertiary butanol (t-BuOH, 10 mM) and hydrogen peroxide (H2O2, 1 mg/mg O3), and at different pH (6-8) and transferred ozone doses (0-1 mg/mg TOC). Although ozonation led to a 24-37% decrease in formation of total trihalomethanes, haloacetic acids, haloacetonitriles, and trihaloacetamides, an increase in formation of total trihalonitromethanes, chloral hydrate, and haloketones was observed. This effect however was less pronounced for samples ozonated at conditions favoring molecular ozone (e.g., pH 6 and in the presence of t-BuOH) over •OH reactions (e.g., pH 8 and in the presence of H2O2). Compared to ozonation only, addition of H2O2 consistently enhanced formation of all DBP groups (20-61%) except trihalonitromethanes. This proves that •OH-transformed organic matter is more susceptible to halogen incorporation. Analogously, adsorbable organic halogen (AOX) concentrations increased under conditions that favor •OH reactions. The ratio of unknown to known AOX, however, was greater at conditions that promote direct O3 reactions. Although significant correlation was found between AOX and genotoxicity with the p53 bioassay, toxicity tests using 4 in vitro bioassays showed relatively low absolute differences between various ozonation conditions. Copyright © 2015 Elsevier Ltd. All rights reserved.

Ozone kinetics in low-pressure discharges

NASA Astrophysics Data System (ADS)

Guerra, Vasco; Marinov, Daniil; Guaitella, Olivier; Rousseau, Antoine

2012-10-01

Ozone kinetics is quite well established at atmospheric pressure, due to the importance of ozone in atmospheric chemistry and to the development of industrial ozone reactors. However, as the pressure is decreased and the dominant three-body reactions lose importance, the main mechanisms involved in the creation and destruction of ozone are still surrounded by important uncertainties. In this work we develop a self-consistent model for a pulsed discharge and its afterglow operating in a Pyrex reactor with inner radius 1 cm, at pressures in the range 1-5 Torr and discharge currents of 40-120 mA. The model couples the electron Boltzmann equation with a system of equations for the time evolution of the heavy particles. The calculations are compared with time-dependent measurements of ozone and atomic oxygen. Parametric studies are performed in order to clarify the role of vibrationally excited ozone in the overall kinetics and to establish the conditions where ozone production on the surface may become important. It is shown that vibrationally excited ozone does play a significant role, by increasing the time constants of ozone formation. Moreover, an upper limit for the ozone formation at the wall in these conditions is set at 10(-4).

Lusaka, Zambia, during SAFARI-2000: Convergence of local and imported ozone pollution

NASA Astrophysics Data System (ADS)

Thompson, Anne M.; Witte, Jacquelyn C.; Freiman, M. Tal; Phahlane, N. Agnes; Coetzee, Gert J. R.

2002-10-01

In August and September, throughout south central Africa, seasonal clearing of dry vegetation and other fire-related activities lead to intense smoke haze and ozone formation. The first ozone soundings in the heart of the southern African burning region were taken at Lusaka, Zambia (15.5S, 28E) in early September 2000. Maximum surface ozone was over 90 ppbv and column tropospheric ozone exceeded 50 DU. These values are higher than concurrent measurements over Nairobi (1S, 38E) and Irene (25S, 28E, near Pretoria). At least 30% of Lusaka surface ozone appears to be from local sources. A layer at 800-500 hPa has ozone >120 ppbv and originates from trans-boundary recirculation. Starting out over Zambia, Angola, and Namibia, ozone-rich air travels east to the Indian Ocean, before heading back toward Mozambique, Zimbabwe and Zambia. Thus, Lusaka collects local and imported pollution, consistent with its location within the southern African gyre.

Reaction of a phospholipid monolayer with gas-phase ozone at the air-water interface: measurement of surface excess and surface pressure in real time.

PubMed

Thompson, Katherine C; Rennie, Adrian R; King, Martin D; Hardman, Samantha J O; Lucas, Claire O M; Pfrang, Christian; Hughes, Brian R; Hughes, Arwel V

2010-11-16

The reaction between gas-phase ozone and monolayers of the unsaturated lipid 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine, POPC, on aqueous solutions has been studied in real time using neutron reflection and surface pressure measurements. The reaction between ozone and lung surfactant, which contains POPC, leads to decreased pulmonary function, but little is known about the changes that occur to the interfacial material as a result of oxidation. The results reveal that the initial reaction of ozone with POPC leads to a rapid increase in surface pressure followed by a slow decrease to very low values. The neutron reflection measurements, performed on an isotopologue of POPC with a selectively deuterated palmitoyl strand, reveal that the reaction leads to loss of this strand from the air-water interface, suggesting either solubilization of the product lipid or degradation of the palmitoyl strand by a reactive species. Reactions of (1)H-POPC on D(2)O reveal that the headgroup region of the lipids in aqueous solution is not dramatically perturbed by the reaction of POPC monolayers with ozone supporting degradation of the palmitoyl strand rather than solubilization. The results are consistent with the reaction of ozone with the oleoyl strand of POPC at the air-water interface leading to the formation of OH radicals. The highly reactive OH radicals produced can then go on to react with the saturated palmitoyl strands leading to the formation of oxidized lipids with shorter alkyl tails.

Reactive nitrogen partitioning and its relationship to winter ozone events in Utah

NASA Astrophysics Data System (ADS)

Wild, R. J.; Edwards, P. M.; Bates, T. S.; Cohen, R. C.; de Gouw, J. A.; Dubé, W. P.; Gilman, J. B.; Holloway, J.; Kercher, J.; Koss, A.; Lee, L.; Lerner, B.; McLaren, R.; Quinn, P. K.; Roberts, J. M.; Stutz, J.; Thornton, J. A.; Veres, P. R.; Warneke, C.; Williams, E.; Young, C. J.; Yuan, B.; Brown, S. S.

2015-08-01

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. Roughly half of the more oxidized forms of nitrogen were composed of nitric acid in 2013, with nighttime nitric acid formation through heterogeneous uptake of N2O5 contributing approximately 6 times more than daytime formation. The nighttime N2O5 lifetime between the high-ozone year 2013 and the low-ozone year 2012 is lower by a factor 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.

3rd hand smoking; heterogeneous oxidation of nicotine and secondary aerosol formation in the indoor environment

NASA Astrophysics Data System (ADS)

Petrick, Lauren; Dubowski, Yael

2010-05-01

Tobacco smoking is well known as a significant source of primary indoor air pollutants. However, only recently has it been recognized that the impact of Tobacco smoking may continue even after the cigarette has been extinguished (i.e., third hand smoke) due to the effect of indoor surfaces. These surfaces may affect the fate of tobacco smoke in the form of secondary reactions and pollutants, including secondary organic aerosol (SOA) formation. Fourier Transform Infrared spectrometry with Attenuated Total Reflection (FTIR-ATR) in tandem with a Scanning Mobility Particle Sizing (SMPS) system was used to monitor the ozonation of cellulose sorbed nicotine and resulting SOA formation. SOA formation began at onset of ozone introduction ([O3] = 60 ± 5 ppb) with a size distribution of dp ≤ 25 nm, and was determined to be a result of heterogeneous reaction (opposed to homogeneous). SOA yield from reacted surface nicotine was on the order of 10 %. Simultaneous to SOA monitoring, FTIR-ATR spectra showed surface changes in the nicotine film as the reaction progressed, revealing a pseudo first-order surface reaction rate of 0.0026 ± 0.0008 min-1. Identified surface oxidation products included: cotinine, myosmine, methylnicotinamide and nicotyrine. Surface reaction rate was found to be partially inhibited at high relative humidity. Given the toxicity of some of the identified products (e.g., cotinine has shown potential mutagenicity and teratogenicity) and that small particles may contribute to adverse health effects, the present study indicates that exposure to 3rd hand smoke ozonation products may pose additional health risks.

Volatilization of low vapor pressure--volatile organic compounds (LVP-VOCs) during three cleaning products-associated activities: Potential contributions to ozone formation.

PubMed

Shin, Hyeong-Moo; McKone, Thomas E; Bennett, Deborah H

2016-06-01

There have been many studies to reduce ozone formation mostly from volatile organic compound (VOC) sources. However, the role of low vapor pressure (LVP)-VOCs from consumer products remains mostly unexplored and unaddressed. This study explores the impact of high production volume LVP-VOCs on ozone formation from three cleaning products-associated activities (dishwashing, clothes washing, and surface cleaning). We develop a model framework to account for the portion available for ozone formation during the use phase and from the down-the-drain disposal. We apply experimental studies that measured emission rates or models that were developed for estimating emission rates of organic compounds during the use phase. Then, the fraction volatilized (fvolatilized) and the fraction disposed down the drain (fdown-the-drain) are multiplied by the portion available for ozone formation for releases to the outdoor air (fO3|volatilized) and down-the-drain (fO3|down-the-drain), respectively. Overall, for chemicals used in three specific cleaning-product uses, fvolatilized is less than 0.6% for all studied LVP-VOCs. Because greater than 99.4% of compounds are disposed of down the drain during the use phase, when combined with fO3|volatilized and fO3|down-the-drain, the portion available for ozone formation from the direct releases to outdoor air and the down-the-drain disposal is less than 0.4% and 0.2%, respectively. The results from this study indicate that the impact of the studied LVP-VOCs on ozone formation is very sensitive to what occurs during the use phase and suggest the need for future research on experimental work at the point of use. Copyright © 2016 Elsevier Ltd. All rights reserved.

Sensitivities of NOx transformation and the effects on surface ozone and nitrate

NASA Astrophysics Data System (ADS)

Lei, H.; Wang, J. X. L.

2013-08-01

As precursors for tropospheric ozone and nitrate aerosols, Nitrogen oxides (NOx) in present atmosphere and its transformation in responding to emission and climate perturbations are studied by CAM-Chem model and air quality measurements including National Emission Inventory (NEI), Clean Air Status and Trends Network (CASTNET) and Environmental Protection Agency Air Quality System (EPA AQS). It is found that not only the surface ozone formation but also the nitrate formation is associated with the relative emissions of NOx and volatile organic compounds (VOC). Due to the availability of VOC and associated NOx titration, ozone productions in industrial regions increase in warmer conditions and slightly decrease against NOx emission increase, which is converse to the response in farming region. The decrease or small increase in ozone concentrations over industrial regions result in the responded nitrate increasing rate staying above the increasing rate of NOx emissions. It is indicated that ozone concentration change is more directly affected by changes in climate and precursor emissions, while nitrate concentration change is also affected by local ozone production types and their seasonal transfer. The sensitivity to temperature perturbations shows that warmer climate accelerates the decomposition of odd nitrogen (NOy) during the night. As a result, the transformation rate of NOx to nitrate decreases. Examinations on the historical emission and air quality records on typical pollution areas further confirm the conclusion drawn from modeling experiments.

Modeling of bromate formation by ozonation of surface waters in drinking water treatment.

PubMed

Legube, Bernard; Parinet, Bernard; Gelinet, Karine; Berne, Florence; Croue, Jean-Philippe

2004-04-01

The main objective of this paper is to try to develop statistically and chemically rational models for bromate formation by ozonation of clarified surface waters. The results presented here show that bromate formation by ozonation of natural waters in drinking water treatment is directly proportional to the "Ct" value ("Ctau" in this study). Moreover, this proportionality strongly depends on many parameters: increasing of pH, temperature and bromide level leading to an increase of bromate formation; ammonia and dissolved organic carbon concentrations causing a reverse effect. Taking into account limitation of theoretical modeling, we proposed to predict bromate formation by stochastic simulations (multi-linear regression and artificial neural networks methods) from 40 experiments (BrO(3)(-) vs. "Ctau") carried out with three sand filtered waters sampled on three different waterworks. With seven selected variables we used a simple architecture of neural networks, optimized by "neural connection" of SPSS Inc./Recognition Inc. The bromate modeling by artificial neural networks gives better result than multi-linear regression. The artificial neural networks model allowed us classifying variables by decreasing order of influence (for the studied cases in our variables scale): "Ctau", [N-NH(4)(+)], [Br(-)], pH, temperature, DOC, alkalinity.

Barriers and opportunities for passive removal of indoor ozone

NASA Astrophysics Data System (ADS)

Gall, Elliott T.; Corsi, Richard L.; Siegel, Jeffrey A.

2011-06-01

This paper presents a Monte Carlo simulation to assess passive removal materials (PRMs) that remove ozone with no additional energy input and minimal byproduct formation. Distributions for air exchange rate in a subset of homes in Houston, Texas, were taken from the literature and combined with background ozone removal rates in typical houses and previous experimentally determined ozone deposition velocities to activated carbon cloth and gypsum wallboard PRMs. The median ratio of indoor to outdoor ozone was predicted to be 0.16 for homes with no PRMs installed and ranged from 0.047 to 0.12 for homes with PRMs. Median values of ozone removal effectiveness in these homes ranged from 22% to 68% for the conditions investigated. Achieving an ozone removal effectiveness above 50% in half of the homes would require installing a large area of PRMs and providing enhanced air speed to transport pollutants to PRM surfaces. Challenges associated with achieving this removal include optimizing indoor transport and aesthetic implications of large surface areas of PRM materials.

Ozonation of 1,2-dihydroxybenzene in the presence of activated carbon.

PubMed

Zaror, C; Soto, G; Valdés, H; Mansilla, H

2001-01-01

This work aims at obtaining experimental data on ozonation of 1,2-dihydroxybenzene (DHB) in the presence of activated carbon, with a view to assessing possible changes in its surface chemical structure and adsorption capacity. Experiments were conducted in a 0.5 L reactor, loaded with 2 g Filtrasorb 400 granular activated carbon, and 1-5 mM DHB aqueous solution at pH 2-8. Ozone gas was generated with an Ozocav generator, and fed into the reactor for a given exposure time, in the range 0.5-240 min, at 25 degrees C and 1 atm. After each run, liquid and activated carbon samples were taken for chemical assays. Soluble organic groups present on the active carbon surface were desorbed and analysed by GC-MS and HPLC. Activated carbon chemical surface properties were analysed using TPD, FT-IR, and XPS techniques. Reactions between ozone and adsorbed DHB were shown to be fast, leading to formation of C-6, C-4 and C-2 by-products. Oxygenated surface groups, particularly, COOH and C = O, increased as a result of ozonation.

Reactive nitrogen partitioning and its relationship to winter ozone events in Utah

NASA Astrophysics Data System (ADS)

Wild, R. J.; Edwards, P. M.; Bates, T. S.; Cohen, R. C.; de Gouw, J. A.; Dubé, W. P.; Gilman, J. B.; Holloway, J.; Kercher, J.; Koss, A. R.; Lee, L.; Lerner, B. M.; McLaren, R.; Quinn, P. K.; Roberts, J. M.; Stutz, J.; Thornton, J. A.; Veres, P. R.; Warneke, C.; Williams, E.; Young, C. J.; Yuan, B.; Zarzana, K. J.; Brown, S. S.

2016-01-01

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.

Analysis of Ozone And CO2 Profiles Measured At A Diary Facility

NASA Astrophysics Data System (ADS)

Ogunjemiyo, S. O.; Hasson, A. S.; Ashkan, S.; Steele, J.; Shelton, T.

2015-12-01

Ozone and carbon dioxide are both greenhouse gasses in the planetary boundary layer. Ozone is a harmful secondary pollutant in the troposphere produced mostly during the day when there is a photochemical reaction in which primary pollutant precursors such as nitrous oxide (NOx) or volatile organic compounds (VOC's) mix with sunlight. As with most pollutants in the lower troposphere, both ozone and carbon dioxide vary in spatial and temporal scale depending on sources of pollution, environmental conditions and the boundary layer dynamics. Among the several factors that influence ozone variation, the seasonal changes in meteorological parameters and availability of ozone precursors are crucial because they control ozone formation and decay. Understanding how the difference in emission sources affect vertical transport of ozone and carbon dioxide is considered crucial to the improvement of their regional inventory sources. The purpose of this study is to characterize vertical transport of ozone and carbon at a diary facility. The study was conducted in the summer of 2011 and 2012 at a commercial dairy facility in Central California and involved profile measurements of ozone and CO2 using electrochemical ozonesondes, meteorological sondes and CO2 probe tethered to a 9 cubic meters helium balloon. On each day of the data collection, multiple balloon launches were made over a period representing different stages of the boundary layer development. The results show ozone and CO2 profiles display different characteristics. Regardless of the time of the day, the CO2 concentration decreases with height with a sharp gradient near the surface that is strengthened by a stable atmospheric condition, a feature suggesting the surface as the source. On the other hand, ozone profiles show greater link to the evolution of the lower boundary layer. Ozone profiles display unique features indicating ozone destruction near the surface. This unusual near the surface, observed even in the afternoon when the boundary layer is fully developed, greatly contrast ozone profiles are typical of urban environment

Investigating the connectivity between emissions of BVOC and rainfall formation in Amazonia using Genetic Programming

NASA Astrophysics Data System (ADS)

Von Randow, Celso; Sanches, Marcos B.; Santos, Rosa Maria N.; Chamecki, Marcelo; Fuentes, Jose D.

2017-04-01

A detailed field experiment measuring turbulent properties, trace gases and BVOCs was carried out from April 2014 to January 2015 within and above a central Amazonian rainforest, with the objective of understanding the role of emissions and reactions of BVOCs, formation and transport of aerosols out of the boundary layer on cloud formation and precipitation triggers. Our measurements show two-way aspects of connectivity: mesoscale convective systems transport ozone down from the middle troposphere, enriching the atmospheric boundary layer as well as the forest canopy and surface layer, and, through multiple chemical transformations, an ozone-enriched atmospheric surface layer that can oxidize rainforest-emitted hydrocarbons and generate aerosols that subsequently activate into cloud condensation nuclei, thereby possibly influencing the formation of new convective precipitation. Qualitatively, we address the connectivity between emissions of BVOCs near the surface and rainfall generation, using the technique of Genetic Programing (GP), introduced by Koza (1992), based on the concepts of natural selection and genetics. The technique involves finding a mathematical expression that fits a given set of data, and constructing a population of mathematical models from different combinations of variables, constants and operators. An advantage of GP is that it can flexibly incorporate multivariate non-linear relations, and obtained numeric solutions are possibly interpreted and checked for physical consistency. A number of state variables (for example, surface fluxes, meteorological conditions, boundary layer stability conditions, BVOC and Ozone vertical profiles, etc), representing possible influences on BVOC emissions and their interrelations along the way through secondary organic aerosol and CCN formation to rainfall will be used.

Generation of ozone by pulsed corona discharge over water surface in hybrid gas liquid electrical discharge reactor

NASA Astrophysics Data System (ADS)

Lukes, Petr; Clupek, Martin; Babicky, Vaclav; Janda, Vaclav; Sunka, Pavel

2005-02-01

Ozone formation by a pulse positive corona discharge generated in the gas phase between a planar high voltage electrode made from reticulated vitreous carbon and a water surface with an immersed ground stainless steel plate electrode was investigated under various operating conditions. The effects of gas flow rate (0.5-3 litre min-1), discharge gap spacing (2.5-10 mm), applied input power (2-45 W) and gas composition (oxygen containing argon or nitrogen) on ozone production were determined. Ozone concentration increased with increasing power input and with increasing discharge gap. The production of ozone was significantly affected by the presence of water vapour formed through vaporization of water at the gas-liquid interface by the action of the gas phase discharge. The highest energy efficiency for ozone production was obtained using high voltage pulses of approximately 150 ns duration in Ar/O2 mixtures with the maximum efficiency (energy yield) of 23 g kW h-1 for 40% argon content.

Optimal Extraction of Tropospheric Ozone Column by Simultaneous Use of OMI and TES Data and the Surface Temperature

NASA Astrophysics Data System (ADS)

Mobasheri, M. R.; Shirazi, H.

2015-12-01

This article aims to increase the accuracy of Ozone data from tropospheric column (TOC) of the OMI and TES satellite instruments. To validate the estimated amount of satellite data, Ozonesonde data is used. The vertical resolution in both instruments in the tropospheric atmosphere decreases so that the degree of freedom signals (DOFS) on the average for TES is reduced to 2 and for OMI is reduced to1. But this decline in accuracy in estimation of tropospheric ozone is more obvious in urban areas so that estimated ozone in both instruments alone in non-urban areas show a high correlation with Ozonesonde. But in urban areas this correlation is significantly reduced, due to the ozone pre-structures and consequently an increase on surface-level ozone in urban areas. In order to improve the accuracy of satellite data, the average tropospheric ozone data from the two instruments were used. The aim is to increase the vertical resolution of ozone profile and the results clearly indicate an increase in correlations, but nevertheless the satellite data have a positive bias towards the earth data. To reduce the bias, with the solar flux and nitrogen dioxide values and surface temperatures are calculated as factors of ozone production on the earth's surface and formation of mathematical equations based on coefficients for each of the mentioned values and multiplication of these coefficients by satellite data and repeated comparison with the values of Ozonesonde, the results showed that bias in urban areas is greatly reduced.

Tropospheric Ozone Assessment Report: Database and Metrics Data of Global Surface Ozone Observations

DOE PAGES

Schultz, Martin G.; Schroder, Sabine; Lyapina, Olga; ...

2017-11-27

In support of the first Tropospheric Ozone Assessment Report (TOAR) a relational database of global surface ozone observations has been developed and populated with hourly measurement data and enhanced metadata. A comprehensive suite of ozone data products including standard statistics, health and vegetation impact metrics, and trend information, are made available through a common data portal and a web interface. These data form the basis of the TOAR analyses focusing on human health, vegetation, and climate relevant ozone issues, which are part of this special feature. Cooperation among many data centers and individual researchers worldwide made it possible to buildmore » the world's largest collection of in-situ hourly surface ozone data covering the period from 1970 to 2015. By combining the data from almost 10,000 measurement sites around the world with global metadata information, new analyses of surface ozone have become possible, such as the first globally consistent characterisations of measurement sites as either urban or rural/remote. Exploitation of these global metadata allows for new insights into the global distribution, and seasonal and long-term changes of tropospheric ozone and they enable TOAR to perform the first, globally consistent analysis of present-day ozone concentrations and recent ozone changes with relevance to health, agriculture, and climate. Considerable effort was made to harmonize and synthesize data formats and metadata information from various networks and individual data submissions. Extensive quality control was applied to identify questionable and erroneous data, including changes in apparent instrument offsets or calibrations. Such data were excluded from TOAR data products. Limitations of a posteriori data quality assurance are discussed. As a result of the work presented here, global coverage of surface ozone data for scientific analysis has been significantly extended. Yet, large gaps remain in the surface observation network both in terms of regions without monitoring, and in terms of regions that have monitoring programs but no public access to the data archive. Therefore future improvements to the database will require not only improved data harmonization, but also expanded data sharing and increased monitoring in data-sparse regions.« less

Tropospheric Ozone Assessment Report: Database and Metrics Data of Global Surface Ozone Observations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schultz, Martin G.; Schroder, Sabine; Lyapina, Olga

In support of the first Tropospheric Ozone Assessment Report (TOAR) a relational database of global surface ozone observations has been developed and populated with hourly measurement data and enhanced metadata. A comprehensive suite of ozone data products including standard statistics, health and vegetation impact metrics, and trend information, are made available through a common data portal and a web interface. These data form the basis of the TOAR analyses focusing on human health, vegetation, and climate relevant ozone issues, which are part of this special feature. Cooperation among many data centers and individual researchers worldwide made it possible to buildmore » the world's largest collection of in-situ hourly surface ozone data covering the period from 1970 to 2015. By combining the data from almost 10,000 measurement sites around the world with global metadata information, new analyses of surface ozone have become possible, such as the first globally consistent characterisations of measurement sites as either urban or rural/remote. Exploitation of these global metadata allows for new insights into the global distribution, and seasonal and long-term changes of tropospheric ozone and they enable TOAR to perform the first, globally consistent analysis of present-day ozone concentrations and recent ozone changes with relevance to health, agriculture, and climate. Considerable effort was made to harmonize and synthesize data formats and metadata information from various networks and individual data submissions. Extensive quality control was applied to identify questionable and erroneous data, including changes in apparent instrument offsets or calibrations. Such data were excluded from TOAR data products. Limitations of a posteriori data quality assurance are discussed. As a result of the work presented here, global coverage of surface ozone data for scientific analysis has been significantly extended. Yet, large gaps remain in the surface observation network both in terms of regions without monitoring, and in terms of regions that have monitoring programs but no public access to the data archive. Therefore future improvements to the database will require not only improved data harmonization, but also expanded data sharing and increased monitoring in data-sparse regions.« less

The influence of changing UVB radiation in near-surface ozone time series

NASA Astrophysics Data System (ADS)

BröNnimann, Stefan; Voigt, Stefan; Wanner, Heinz

2000-04-01

UVB radiation plays an important role in tropospheric photochemistry since it determines the rate of ozone photolysis J(O1D) and subsequent formation of OH radicals. Consequently, changes of UVB radiation, for example due to changes of the stratospheric ozone amount, could alter the concentration of reactive tropospheric gases including ozone. An observation-based attempt is made to quantify the effect of changing UVB radiation on surface ozone peaks on a day-to-day scale using a time series of measurements at a Swiss mountain site. Seven years data of ozone, NO, NOx, and meteorological measurements from Chaumont (1140 m above sea level (asl)), total ozone and UVB measurements from Arosa (1847 m asl), and surface albedo from satellite observations are investigated. The study is restricted to fair weather days with moderately high NOx concentrations. Multiple regression analysis is performed using chemical, meteorological, and UV dependent variables to predict afternoon ozone peaks. From autumn to spring, positive deviations of ozone peaks are clearly connected with positive UVB deviations. The relation is statistically significant only in part of the seasonal data subsets; however, it is consistent with model studies. The estimated net effect on ozone peaks is normally within a range of 4 ppb, a range of about 6 ppb is predicted for large UVB changes. Applying the coefficients for the large interannual variability of the stratospheric ozone layer observed in spring in the last 10 years results in a range of variation of at most 1 to 1.5 ppb for monthly mean ozone peaks. For trends of J(O1D) from 1970 to 1990, a trend bias of surface ozone peaks on polluted fair weather days of less than 0.12 ppb/yr is calculated. Although the numbers are rather small, they may play a role in certain circumstances.

Spectroscopic signatures of ozone at the air–water interface and photochemistry implications

PubMed Central

Anglada, Josep M.; Martins-Costa, Marilia; Ruiz-López, Manuel F.; Francisco, Joseph S.

2014-01-01

First-principles simulations suggest that additional OH formation in the troposphere can result from ozone interactions with the surface of cloud droplets. Ozone exhibits an affinity for the air–water interface, which modifies its UV and visible light spectroscopic signatures and photolytic rate constant in the troposphere. Ozone cross sections on the red side of the Hartley band (290- to 350-nm region) and in the Chappuis band (450–700 nm) are increased due to electronic ozone–water interactions. This effect, combined with the potential contribution of the O3 + hν → O(3P) + O2(X3Σg−) photolytic channel at the interface, leads to an enhancement of the OH radical formation rate by four orders of magnitude. This finding suggests that clouds can influence the overall oxidizing capacity of the troposphere on a global scale by stimulating the production of OH radicals through ozone photolysis by UV and visible light at the air–water interface. PMID:25071195

Ozone formation during an episode over Europe: A 3-D chemical/transport model simulation

NASA Technical Reports Server (NTRS)

Berntsen, Terje; Isaksen, Ivar S. A.

1994-01-01

A 3-D regional photochemical tracer/transport model for Europe and the Eastern Atlantic has been developed based on the NASA/GISS CTM. The model resolution is 4x5 degrees latitude and longitude with 9 layers in the vertical (7 in the troposphere). Advective winds, convection statistics and other meteorological data from the NASA/GISS GCM are used. An extensive gas-phase chemical scheme based on the scheme used in our global 2D model has been incorporated in the 3D model. In this work ozone formation in the troposphere is studied with the 3D model during a 5 day period starting June 30. Extensive local ozone production is found and the relationship between the source regions and the downwind areas are discussed. Variations in local ozone formation as a function of total emission rate, as well as the composition of the emissions (HC/NO(x)) ratio and isoprene emissions) are elucidated. An important vertical transport process in the troposphere is by convective clouds. The 3D model includes an explicit parameterization of this process. It is shown that this process has significant influence on the calculated surface ozone concentrations.

Stratospheric Ozone Response in Experiments G3 and G4 of the Geoengineering Model Intercomparison Project (GeoMIP)

NASA Technical Reports Server (NTRS)

Pitari, Giovanni; Aquila, Valentina; Kravitz, Ben; Watanabe, Shingo; Tilmes, Simone; Mancini, Eva; DeLuca, Natalia; DiGenova, Glauco

2013-01-01

Geoengineering with stratospheric sulfate aerosols has been proposed as a means of temporarily cooling the planet, alleviating some of the side effects of anthropogenic CO2 emissions. However, one of the known side effects of stratospheric injections of sulfate aerosols is a decrease in stratospheric ozone. Here we show results from two general circulation models and two coupled chemistry climate models that have simulated stratospheric sulfate aerosol geoengineering as part of the Geoengineering Model Intercomparison Project (GeoMIP). Changes in photolysis rates and upwelling of ozone-poor air in the tropics reduce stratospheric ozone, suppression of the NOx cycle increases stratospheric ozone, and an increase in available surfaces for heterogeneous chemistry modulates reductions in ozone. On average, the models show a factor 20-40 increase of the sulfate aerosol surface area density (SAD) at 50 hPa in the tropics with respect to unperturbed background conditions and a factor 3-10 increase at mid-high latitudes. The net effect for a tropical injection rate of 5 Tg SO2 per year is a decrease in globally averaged ozone by 1.1-2.1 DU in the years 2040-2050 for three models which include heterogeneous chemistry on the sulfate aerosol surfaces. GISS-E2-R, a fully coupled general circulation model, performed simulations with no heterogeneous chemistry and a smaller aerosol size; it showed a decrease in ozone by 9.7 DU. After the year 2050, suppression of the NOx cycle becomes more important than destruction of ozone by ClOx, causing an increase in total stratospheric ozone. Contribution of ozone changes in this experiment to radiative forcing is 0.23 W m-2 in GISS-E2-R and less than 0.1 W m-2 in the other three models. Polar ozone depletion, due to enhanced formation of both sulfate aerosol SAD and polar stratospheric clouds, results in an average 5 percent increase in calculated surface UV-B.

A Bayesian model for quantifying the change in mortality associated with future ozone exposures under climate change.

PubMed

Alexeeff, Stacey E; Pfister, Gabriele G; Nychka, Doug

2016-03-01

Climate change is expected to have many impacts on the environment, including changes in ozone concentrations at the surface level. A key public health concern is the potential increase in ozone-related summertime mortality if surface ozone concentrations rise in response to climate change. Although ozone formation depends partly on summertime weather, which exhibits considerable inter-annual variability, previous health impact studies have not incorporated the variability of ozone into their prediction models. A major source of uncertainty in the health impacts is the variability of the modeled ozone concentrations. We propose a Bayesian model and Monte Carlo estimation method for quantifying health effects of future ozone. An advantage of this approach is that we include the uncertainty in both the health effect association and the modeled ozone concentrations. Using our proposed approach, we quantify the expected change in ozone-related summertime mortality in the contiguous United States between 2000 and 2050 under a changing climate. The mortality estimates show regional patterns in the expected degree of impact. We also illustrate the results when using a common technique in previous work that averages ozone to reduce the size of the data, and contrast these findings with our own. Our analysis yields more realistic inferences, providing clearer interpretation for decision making regarding the impacts of climate change. © 2015, The International Biometric Society.

Impact of East Asian Summer Monsoon on Surface Ozone Pattern in China

NASA Astrophysics Data System (ADS)

Li, Shu; Wang, Tijian; Huang, Xing; Pu, Xi; Li, Mengmeng; Chen, Pulong; Yang, Xiu-Qun; Wang, Minghuai

2018-01-01

Tropospheric ozone plays a key role in regional and global atmospheric and climate systems. In East Asia, ozone can be affected both in concentration level and spatial pattern by typical monsoon climate. This paper uses three different indices to identify the strength of East Asian summer monsoon (EASM) and explores the possible impact of EASM intensity on the ozone pattern through synthetic and process analysis. The difference in ozone between three strong and three weak monsoon years was analyzed using the simulations from regional climate model RegCM4-Chem. It was found that EASM intensity can significantly influence the spatial distribution of ozone in the lower troposphere. When EASM is strong, ozone in the eastern part of China (28°N - 42° N) is reduced, but the inverse is detected in the north and south. The surface ozone difference ranges from -7 to 7 ppbv during the 3 months (June to August) of the EASM, with the most obvious difference in August. Difference of the 3 months' average ozone ranges from -3.5 to 4 ppbv. Process analysis shows that the uppermost factor controlling ozone level during summer monsoon seasons is the chemistry process. Interannual variability of EASM can impact the spatial distribution of ozone through wind in the lower troposphere, cloud cover, and downward shortwave radiation, which affect the transport and chemical formation of ozone. The phenomenon should be addressed when considering the interaction between ozone and the climate in East Asia region.

Effect of UV-ozone treatment on poly(dimethylsiloxane) membranes: surface characterization and gas separation performance.

PubMed

Fu, Ywu-Jang; Qui, Hsuan-zhi; Liao, Kuo-Sung; Lue, Shingjiang Jessie; Hu, Chien-Chieh; Lee, Kueir-Rarn; Lai, Juin-Yih

2010-03-16

A thin SiO(x) selective surface layer was formed on a series of cross-linked poly(dimethylsiloxane) (PDMS) membranes by exposure to ultraviolet light at room temperature in the presence of ozone. The conversion of the cross-linked polysiloxane to SiO(x) was monitored by attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), energy-dispersive X-ray (EDX) microanalysis, contact angle analysis, and atomic force microscopy (AFM). The conversion of the cross-linked polysiloxane to SiO(x) increased with UV-ozone exposure time and cross-linking agent content, and the surface possesses highest conversion. The formation of a SiO(x) layer increased surface roughness, but it decreased water contact angle. Gas permeation measurements on the UV-ozone exposure PDMS membranes documented interesting gas separation properties: the O(2) permeability of the cross-linked PDMS membrane before UV-ozone exposure was 777 barrer, and the O(2)/N(2) selectivity was 1.9; after UV-ozone exposure, the permeability decreased to 127 barrer while the selectivity increased to 5.4. The free volume depth profile of the SiO(x) layer was investigated by novel slow positron beam. The results show that free volume size increased with the depth, yet the degree of siloxane conversion to SiO(x) does not affect the amount of free volume.

Role of Biomass Burning in the Formation of Tropospheric Ozone Laminae

NASA Astrophysics Data System (ADS)

Nair, U. S.; Wu, Y.; Kuang, S.; Newchurch, M.

2016-12-01

Laminar structure in free-tropospheric ozone profiles is a feature that is frequently observed in ozonesonde and lidar observations. Origins of these features are not well understood and have been linked to tropopause folding, stratospheric warming events and biomass burning emissions. Ozone laminae events with maximum ozone exceeding 80 ppb have been observed by the DIfferential Absorption Lidar (DIAL) instrument in Huntsville, Alabama. While many of the events are linked to tropopause folding, a subset of events located in the mid troposphere (2-6km) coincided with a smoke layer are associated with biomass burning. Satellite observations show the smoke originated from northwestern US wildfire events. Several of these ozone laminae associated with smoke have ozone excess of 20 ppb above the background values and have the potential to impact surface air quality if they enter the boundary layer. This presentation will report on process studies of ozone laminae associated with biomass burning plumes using A-Train satellite, ground based DIAL and ozonesonde observations. Fate and transport of the feature is also examined using WRFChem simulations, in specific transport into the boundary layer and impact on air quality at the surface.

Sulfate aerosols and polar stratospheric cloud formation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tolbert, M.A.

Before the discovery of the Antarctic ozone hole, it was generally assumed that gas-phase chemical reactions controlled the abundance of stratospheric ozone. However, the massive springtime ozone losses over Antarctica first reported by Farman et al in 1985 could not be explained on the basis of gas-phase chemistry alone. In 1986, Solomon et al suggested that chemical reactions occurring on the surfaces of polar stratospheric clouds (PSCs) could be important for the observed ozone losses. Since that time, an explosion of laboratory, field, and theoretical research in heterogeneous atmospheric chemistry has occurred. Recent work has indicated that the most importantmore » heterogeneous reaction on PSCs is ClONO[sub 2] + HCl [yields] Cl[sub 2] + HNO[sub 3]. This reaction converts inert chlorine into photochemically active Cl[sub 2]. Photolysis of Cl[sub 2] then leads to chlorine radicals capable of destroying ozone through very efficient catalytic chain reactions. New observations during the second Airborne Arctic Stratospheric Expedition found stoichiometric loss of ClONO[sub 2] and HCl in air processed by PSCs in accordance with reaction 1. Attention is turning toward understanding what kinds of aerosols form in the stratospheric, their formation mechanism, surface area, and specific chemical reactivity. Some of the latest findings, which underline the importance of aerosols, were presented at a recent National Aeronautics and Space Administration workshop in Boulder, Colorado.« less

The impact of historical land use change from 1850 to 2000 on secondary particulate matter and ozone

NASA Astrophysics Data System (ADS)

Heald, Colette L.; Geddes, Jeffrey A.

2016-12-01

Anthropogenic land use change (LUC) since preindustrial (1850) has altered the vegetation distribution and density around the world. We use a global model (GEOS-Chem) to assess the attendant changes in surface air quality and the direct radiative forcing (DRF). We focus our analysis on secondary particulate matter and tropospheric ozone formation. The general trend of expansion of managed ecosystems (croplands and pasturelands) at the expense of natural ecosystems has led to an 11 % decline in global mean biogenic volatile organic compound emissions. Concomitant growth in agricultural activity has more than doubled ammonia emissions and increased emissions of nitrogen oxides from soils by more than 50 %. Conversion to croplands has also led to a widespread increase in ozone dry deposition velocity. Together these changes in biosphere-atmosphere exchange have led to a 14 % global mean increase in biogenic secondary organic aerosol (BSOA) surface concentrations, a doubling of surface aerosol nitrate concentrations, and local changes in surface ozone of up to 8.5 ppb. We assess a global mean LUC-DRF of +0.017, -0.071, and -0.01 W m-2 for BSOA, nitrate, and tropospheric ozone, respectively. We conclude that the DRF and the perturbations in surface air quality associated with LUC (and the associated changes in agricultural emissions) are substantial and should be considered alongside changes in anthropogenic emissions and climate feedbacks in chemistry-climate studies.

Evolution of the Antarctic polar vortex in spring: Response of a GCM to a prescribed Antarctic ozone hole

NASA Technical Reports Server (NTRS)

Boville, B. A.; Kiehl, J. T.; Briegleb, B. P.

1988-01-01

The possible effect of the Antartic ozone hole on the evolution of the polar vortex during late winter and spring using a general circulation model (GCM) is examined. The GCM is a version of the NCAR Community Climate Model whose domain extends from the surface to the mesosphere and is similar to that described on Boville and Randel (1986). Ozone is not a predicted variable in the model. A zonally averaged ozone distribution is specified as a function of latitude, pressure and month for the radiation parameterization. Rather that explicitly address reasons for the formation of the ozone hole, researchers postulate its existence and ask what effect it has on the subsequent evolution of the vortex. The evolution of the model when an ozone hole is imposed is then discussed.

Device performance and lifetime of polymer:fullerene solar cells with UV-ozone-irradiated hole-collecting buffer layers.

PubMed

Lee, Seungsoo; Nam, Sungho; Lee, Hyena; Kim, Hwajeong; Kim, Youngkyoo

2011-11-18

We report the influence of UV-ozone irradiation of the hole-collecting buffer layers on the performance and lifetime of polymer:fullerene solar cells. UV-ozone irradiation was targeted at the surface of the poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT:PSS) layers by varying the irradiation time up to 600 s. The change of the surface characteristics in the PEDOT:PSS after UV-ozone irradiation was measured by employing optical absorption spectroscopy, photoelectron yield spectroscopy, and contact angle measurements, while Raman and X-ray photoelectron spectroscopy techniques were introduced for more microscopic analysis. Results showed that the UV-ozone irradiation changed the chemical structure/composition of the surface of the PEDOT:PSS layers leading to the gradual increase of ionization potential with irradiation time in the presence of up-and-down variations in the contact angle (polarity). This surface property change was attributed to the formation of oxidative components, as evidenced by XPS and Auger electron images, which affected the sheet resistance of the PEDOT:PSS layers. Interestingly, device performance was slightly improved by short irradiation (up to 10 s), whereas it was gradually decreased by further irradiation. The short-duration illumination test showed that the lifetime of solar cells with the UV-ozone irradiated PEDOT:PSS layer was improved due to the protective role of the oxidative components formed upon UV-ozone irradiation against the attack of sulfonic acid groups in the PEDOT:PSS layer to the active layer. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhancement of bromate formation by pH depression during ozonation of bromide-containing water in the presence of hydroxylamine.

PubMed

Yang, Jingxin; Li, Ji; Dong, Wenyi; Ma, Jun; Yang, Yi; Li, Jiayin; Yang, Zhichao; Zhang, Xiaolei; Gu, Jia; Xie, Wanying; Cang, Yan

2017-02-01

This work investigated the fate of bromate formation during ozonation in the presence of hydroxylamine (HA). Results indicated that pH depression, as a commonly feasible control strategy for bromate formation during ozonation, unexpectedly enhanced the bromate formation during ozonation in the presence of HA. A dramatically high level of bromate was observed at acidic pH in the ozone/HA process. The scavenging experiments demonstrated the essential role of OH produced in the reaction of ozone with HA in bromate formation. In the process, OH mainly oxidizes bromide to Br, which is further oxidized by ozone and eventually converts to bromate. Further investigations suggested that the unexpected enhancement on bromate formation by pH depression can be mainly ascribed to the pH-dependent ozone decay, OH exposures and formation rate of Br. As pH decreased from 7 to 5, the reduced OH scavenging capacity of HA led to higher OH exposures, which contributed to the enhancement of bromate formation. As pH decreased from 5 to 3, the enhanced formation rate of Br largely augmented the formation of bromate. In addition, the ozone decay slowed down by pH depression provided more available ozone for the oxidation of the formed Br to bromate. The enhanced effect of pH depression on bromate formation was still observed in the real water samples in the ozone/HA process. Accordingly, pH depression might be avoided to control the bromate formation during ozonation in the presence of HA. Copyright © 2016 Elsevier Ltd. All rights reserved.

Lusaka, Zambia during SAFARI-2000: A Collection Point for Ozone Pollution

NASA Technical Reports Server (NTRS)

Thompson, Anne M.; Witte, Jacquelyn C.; Freiman, M. Tal; Phahlane, N. Agnes; Coetzee, G. J. R.; Bhartia, P. K. (Technical Monitor)

2002-01-01

In August and September, throughout south central Africa, seasonal clearing of dry vegetation and other fire-related activities lead to intense smoke haze and ozone formation. The first ozone soundings in the heart of the southern African burning region were taken at Lusaka, Zambia (155 deg S, 28 deg E) in early September 2000. Over 90 ppbv ozone was recorded at the surface (1.3 km elevation) and column tropospheric ozone was greater than 50 DU during a stagnant period. These values are much higher than concurrent measurements over Nairobi (1 deg S, 38 deg E) and Irene (25 deg S, 28 deg E, near Pretoria). The heaviest ozone pollution layer (800-500 hPa) over Lusaka is due to recirculated trans-boundary ozone. Starting out over Zambia, Angola, and Namibia, ozone heads east to the Indian Ocean, before turning back over Mozambique and Zimbabwe, heading toward Lusaka. Thus, Lusaka is a collection point for pollution, consistent with a picture of absolutely stable layers recirculating in a gyre over southern Africa.

Urban and Rural Ozone Collect over Lusaka (Zambia, 15.5 S, 28 E) during SAFARI-2000 (September 2000)

NASA Technical Reports Server (NTRS)

Thompson, Anne M.; Witte, Jacquelyn C.; Freiman, M. Tai; Phalane, N. Agnes; Coetzee, Gert J. R.

2002-01-01

In early September, throughout south central Africa, seasonal clearing of dry vegetation and the production of charcoal for cooking leads to intense smoke haze and ozone formation. Ozone soundings made over Lusaka in early September 2000 recorded layers of high ozone (greater than 125 ppbv at 5 km) during two stagnant periods, broken by a frontal passage that reduced boundary layer ozone by 30%. During the 6-day measurement period, surface ozone concentrations ranged from 50-95 ppbv and integrated tropospheric ozone from the soundings was 39-54 Dobson Units (note 1.3 km elevation at the launch site). A stable layer of high ozone at 2-5 km was advected from rural burning regions in western Zambia and neighboring countries, making Lusaka a collection point for transboundary pollution. This is confirmed by trajectories that show ozone leaving Angola, Namibia, Botswana and South Africa before heading toward the Indian Ocean and returning to Lusaka via Mozambique and Zimbabwe. Ozone in the mixed layer at Lusaka is heavily influenced by local sources.

Development of a new plasma reactor for propene removal

NASA Astrophysics Data System (ADS)

Oukacine, Linda; Tatibouët, Jean-Michel

2008-10-01

The purpose of the study is to develop a new plasma reactor being applied to gas phase pollution abatement, involving a surface dielectric barrier discharge (SDBD) at atmospheric pressure. Propene was chosen as a model pollutant. The system can associate a SDBD with a volume dielectric barrier discharge (VDBD). A specific catalyst can be placed in post-plasma site in order to destroy the residual ozone after use it as a strong oxidant for total oxidation of propene and by-products formed by the plasma reactor. A comparative study has been established between the propene removal efficiency of these two plasma geometries. The results demonstrate that SDBD is a promising system for gas cleaning. The experiments show that ozone production depends on plasma system configuration and indicate the effectiveness of combining SDBD and VDBD. The NOx formation remains very low, whereas ozone formation is the highest for the SDBD. The influence of some materials on the propene removal and the ozone production were studied.

Contribution of different PSC types to Arctic ozone depletion caused by chlorine activation and denitrification

NASA Astrophysics Data System (ADS)

Kirner, Oliver; Khosrawi, Farah; Müller, Rolf; Weimer, Michael; Ruhnke, Roland

2017-04-01

Heterogeneous reactions on the surfaces of PSC particles and denitrification of the stratosphere are the cause for polar ozone depletion in spring. In a former study we investigated the impact of different types of PSCs on Antarctic ozone depletion with the help of the chemistry-climate model ECHAM5/MESSy Atmospheric chemistry (EMAC). In this study, we investigate the impact of PSCs on Arctic ozone loss. One standard and four sensitivity EMAC simulations (nudged with ERA-Interim) have been performed to evaluate the contribution of liquid, NAT and ice particles to ozone depletion in the Arctic winters 2010/2011 and 2015/2016 due to chlorine activation by heterogeneous chemistry on their surfaces and due to denitrification of the stratosphere. In the first three sensitivity simulations, we changed the heterogeneous chemistry on PSC particles by switching on and off the chemistry on liquid, NAT and ice particles. One further sensitivity simulation without NAT formation (only liquid and ice particles) was performed to evaluate the contribution of NAT to Arctic ozone depletion due to denitrification of the stratosphere. With the help of these different EMAC simulations, we will show the significance of liquid, NAT and ice particles to Arctic ozone depletion caused by chlorine activation and denitrification.

Detection of oxygen isotopic anomaly in terrestrial atmospheric carbonates and its implications to Mars.

PubMed

Shaheen, R; Abramian, A; Horn, J; Dominguez, G; Sullivan, R; Thiemens, Mark H

2010-11-23

The debate of life on Mars centers around the source of the globular, micrometer-sized mineral carbonates in the ALH84001 meteorite; consequently, the identification of Martian processes that form carbonates is critical. This paper reports a previously undescribed carbonate formation process that occurs on Earth and, likely, on Mars. We identified micrometer-sized carbonates in terrestrial aerosols that possess excess (17)O (0.4-3.9‰). The unique O-isotopic composition mechanistically describes the atmospheric heterogeneous chemical reaction on aerosol surfaces. Concomitant laboratory experiments define the transfer of ozone isotopic anomaly to carbonates via hydrogen peroxide formation when O(3) reacts with surface adsorbed water. This previously unidentified chemical reaction scenario provides an explanation for production of the isotopically anomalous carbonates found in the SNC (shergottites, nakhlaites, chassignites) Martian meteorites and terrestrial atmospheric carbonates. The anomalous hydrogen peroxide formed on the aerosol surfaces may transfer its O-isotopic signature to the water reservoir, thus producing mass independently fractionated secondary mineral evaporites. The formation of peroxide via heterogeneous chemistry on aerosol surfaces also reveals a previously undescribed oxidative process of utility in understanding ozone and oxygen chemistry, both on Mars and Earth.

Detection of oxygen isotopic anomaly in terrestrial atmospheric carbonates and its implications to Mars

PubMed Central

Shaheen, R.; Abramian, A.; Horn, J.; Dominguez, G.; Sullivan, R.; Thiemens, Mark H.

2010-01-01

The debate of life on Mars centers around the source of the globular, micrometer-sized mineral carbonates in the ALH84001 meteorite; consequently, the identification of Martian processes that form carbonates is critical. This paper reports a previously undescribed carbonate formation process that occurs on Earth and, likely, on Mars. We identified micrometer-sized carbonates in terrestrial aerosols that possess excess 17O (0.4–3.9‰). The unique O-isotopic composition mechanistically describes the atmospheric heterogeneous chemical reaction on aerosol surfaces. Concomitant laboratory experiments define the transfer of ozone isotopic anomaly to carbonates via hydrogen peroxide formation when O3 reacts with surface adsorbed water. This previously unidentified chemical reaction scenario provides an explanation for production of the isotopically anomalous carbonates found in the SNC (shergottites, nakhlaites, chassignites) Martian meteorites and terrestrial atmospheric carbonates. The anomalous hydrogen peroxide formed on the aerosol surfaces may transfer its O-isotopic signature to the water reservoir, thus producing mass independently fractionated secondary mineral evaporites. The formation of peroxide via heterogeneous chemistry on aerosol surfaces also reveals a previously undescribed oxidative process of utility in understanding ozone and oxygen chemistry, both on Mars and Earth. PMID:21059939

A 15-year climatology of wind pattern impacts on surface ozone in Houston, Texas

NASA Astrophysics Data System (ADS)

Souri, Amir Hossein; Choi, Yunsoo; Li, Xiangshang; Kotsakis, Alexander; Jiang, Xun

2016-06-01

Houston is recognized for its large petrochemical industrial facilities providing abundant radicals for tropospheric ozone formation. Fortunately, maximum daily 8-h average (MDA8) surface ozone concentrations have declined in Houston (- 0.6 ± 0.3 ppbv yr- 1) during the summers (i.e., May to September) of 2000 to 2014, possibly due to the reductions in precursor emissions by effective control policies. However, it is also possible that changes in meteorological variables have affected ozone concentrations. This study focused on the impact of long-term wind patterns which have the highest impact on ozone in Houston. The analysis of long-term wind patterns can benefit surface ozone studies by 1) providing wind patterns that distinctly changed ozone levels, 2) investigating the frequency of patterns and the respective changes and 3) estimating ozone trends in specific wind patterns that local emissions are mostly involved, thus separating emissions impacts from meteorology to some extent. To this end, the 900-hPa flow patterns in summers of 2000 to 2014 were clustered in seven classes (C1-C7) by deploying an unsupervised partitioning method. We confirm the characteristics of the clusters from a backward trajectory analysis, monitoring networks, and a regional chemical transport model simulation. The results indicate that Houston has experienced a statistically significant downward trend (- 0.6 ± 0.4 day yr- 1) of the cluster of weak easterly and northeasterly days (C4), when the highest fraction of ozone exceedances (MDA8 > 70 ppbv) occurred. This suggests that the reduction in ozone precursors was not the sole reason for the decrease in ozone exceedance days (- 1.5 ± 0.6 day yr- 1). Further, to examine the efficiency of control policies intended to reduce the amount of ozone, we estimated the trend of MDA8 ozone in C4 and C5 (weak winds) days when local emissions are primarily responsible for high ambient ozone levels. Both C4 and C5 show a large reduction in the 95th percentile and summertime trends mainly due to effective control strategies. Based on the 5th percentile daytime ozone for C1 (strong southeasterly wind) in coastal sites, this study found that the cleanest air masses that Houston received became more polluted during the summer of 2000-2014 by 1-3 ppbv. Though this study focused on Houston, the analysis method presented could generally be used to estimate ozone trends in other regions where surface ozone is dominantly influenced by both wind patterns and local emissions.

Interaction of ozone with wooden building products, treated wood samples and exotic wood species

NASA Astrophysics Data System (ADS)

Schripp, Tobias; Langer, Sarka; Salthammer, Tunga

2012-07-01

Wooden building products indoors are known to be able to affect the perceived air quality depending on their emission strength. The indoor application of modern ecological lacquer systems (eco-lacquers or 'green' lacquers) may be a much stronger source than the substrates itself. Especially with regard to the formation of ultrafine particles by gas-to-particle conversion in the presence of ozone or other reactive species the impact of the applied building products on the indoor air quality has to be addressed. The present study reports a two concentration step ozonation of OSB panels, painted beech boards, and a number of solid 'exotic' wood types in a 1 m³ emission test chamber. The emission of volatile organic compounds (VOC) was recorded as well as the formation of ultrafine particles in the range 7-300 nm. The products are characterized on the basis of their ozone deposition velocity; the obtained values of 0.008-0.381 cm s-1 are comparable with previously published data. Within the samples of the present study one eco-lacquer was the strongest source of VOC (total VOC ˜ 60 mg m-3) while the wooden building products (OSB) were of intermediate emission strength. The lowest emission was found for the solid (exotic) wood samples. The VOC release of the samples corresponded roughly to the particle formation potential. However, the strongest UFP formation was measured for one solid wood sample ('Garapa') which showed a strong surface reaction in the presence of ozone and formed a large number of particles <40 nm. Overall, the experiments demonstrated the necessity of real-life samples for the estimation of UFP indoor air pollution from the ozone chemistry of terpenes.

Impact of shipping emissions on ozone levels over Europe: assessing the relative importance of the Standard Nomenclature for Air Pollution (SNAP) categories.

PubMed

Tagaris, Efthimios; Stergiou, Ioannis; Sotiropoulou, Rafaella-Eleni P

2017-06-01

The impact of shipping emissions on ozone mixing ratio over Europe is assessed for July 2006 using the Community Multiscale Air Quality modeling system and the Netherlands Organization for Applied Scientific Research anthropogenic emission inventory. Results suggest that ship-induced ozone contribution to the total surface ozone exceeds 5% over the sea and near the coastline, while an increase up to 5% is simulated over a large portion of the European land. The largest impact (i.e., an increase up to 30%) is simulated over the Mediterranean Sea. In addition, shipping emissions are simulated to increase NO 2 mixing ratio more than 90%, locally, and to modify the oxidizing capacity of the atmosphere through hydroxyl radical formation (increase by 20-60% over the sea along the European coasts and near the coastal zone). Therefore, emissions from ships may counteract the benefits derived from the anthropogenic emissions reduction strategies over the continent. Simulations suggest regions where shipping emissions have a major impact on ozone mixing ratio compared to individual anthropogenic emission sector categories. Shipping emissions are estimated to play an important role on ozone levels compared to road transport sector near the coastal zone. The impact of shipping emissions on ozone formation is also profound over a great part of the European land compared to the rest of anthropogenic emission categories.

Winter Photochemistry Underlying High Ozone in an Oil and Gas Producing Region

NASA Astrophysics Data System (ADS)

Brown, S. S.; Edwards, P. M.; Roberts, J. M.; Ahmadov, R.; Banta, R. M.; De Gouw, J. A.; Dube, W. P.; Field, R. A.; Gilman, J.; Graus, M.; Helmig, D.; Koss, A.; Langford, A. O.; Lefer, B. L.; Lerner, B. M.; McKeen, S. A.; Li, S. M.; Murphy, S. M.; Parrish, D. D.; Senff, C. J.; Stutz, J.; Thompson, C. R.; Trainer, M.; Veres, P. R.; Warneke, C.; Wild, R. J.; Young, C.; Yuan, B.; Zamora, R. J.; Washenfelder, R. A.

2014-12-01

Ozone formation during wintertime in oil and gas producing basins of the Rocky Mountain West now accounts for some of the highest ozone pollutant concentrations observed in the U.S. These events are scientifically challenging, occurring only during cold, snow covered periods when meteorological inversions concentrate pollutants near the surface, but when incident solar actinic flux that initiates photochemical reactions is at or near its minimum. A near-explicit chemical model that incorporates detailed measurements obtained during three successive winter field studies in the Uintah Basin, Utah, accurately reproduces the observed buildup of ozone and other photochemically generated species. It also identifies the sources of free radicals that drive this unusual photochemistry, and quantifies their relative contributions. Although sharing the same basic atmospheric chemistry, winter ozone formation differs from its summertime, urban counterpart in its dependence upon the relative concentrations of volatile organic compounds (VOCs) and nitrogen oxide (NOx) precursors. Observed NO­­x mixing ratios in the Uintah basin are lower than is typical of urban areas, while VOC levels are significantly larger. These extreme VOC concentrations allow for nearly optimal efficiency of ozone production from the available NO­x. This analysis will inform the design of mitigation strategies and provide insight into the response of winter ozone to primary air pollutants in other regions, particularly those where oil and gas development is contemplated.

Modeling and characterization of field-enhanced corona discharge in ozone-generator diode

NASA Astrophysics Data System (ADS)

Patil, Jagadish G.; Vijayan, T.

2010-02-01

Electric field enhanced corona plasma discharge in ozone generator diode of axial symmetry has been investigated and characterized in theory. The cathode K of diode is made of a large number of sharpened nozzles arranged on various radial planes on the axial mast and pervaded in oxygen gas inside the anode cup A, produces high fields over MV/m and aids in the formation of a corona plume of dense ozone cloud over the cathode surface. An r-z finite difference scheme has been devised and employed to numerically determine the potential and electric field distributions inside the diode. The analyses of cathode emissions revealed a field emission domain conformed to modified Child-Langmuir diode-current. Passage of higher currents (over μA) in shorter A-K gaps d gave rise to cathode heated plasma extending from the corona to Saha regimes depending on local temperature. Plasma densities of order 102-106 m-3 are predicted in these. For larger d however, currents are smaller and heating negligible and a negative corona favoring ozone formation is attained. High ozone yields about 20 per cent of oxygen input is predicted in this domain. The generator so developed will be applied to various important applications such as, purification of ambient air /drinking water, ozone therapy, and so on.

Characterization of natural organic matter treated by iron oxide nanoparticle incorporated ceramic membrane-ozonation process.

PubMed

Park, Hosik; Kim, Yohan; An, Byungryul; Choi, Heechul

2012-11-15

In this study, changes in the physical and structural properties of natural organic matter (NOM) were observed during hybrid ceramic membrane processes that combined ozonation with ultrafiltration ceramic membrane (CM) or with a reactive ceramic membrane (RM), namely, an iron oxide nanoparticles (IONs) incorporated-CM. NOM from feed water and NOM from permeate treated with hybrid ceramic membrane processes were analyzed by employing several NOM characterization techniques. Specific ultraviolet absorbance (SUVA), high-performance size exclusion chromatography (HPSEC) and fractionation analyses showed that the hybrid ceramic membrane process effectively removed and transformed relatively high contents of aromatic, high molecular weight and hydrophobic NOM fractions. Fourier transform infrared spectroscopy (FTIR) and 3-dimensional excitation-emission matrix (EEM) fluorescence spectroscopy revealed that this process caused a significant decrease of the aromaticity of humic-like structures and an increase in electron withdrawing groups. The highest removal efficiency (46%) of hydroxyl radical probe compound (i.e., para-Chlorobenzoic acid (pCBA)) in RM-ozonation process compared with that in CM without ozonation process (8%) revealed the hydroxyl radical formation by the surface-catalyzed reaction between ozone and IONs on the surface of RM. In addition, experimental results on flux decline showed that fouling of RM-ozonation process (15%) was reduced compared with that of CM without ozonation process (30%). These results indicated that the RM-ozonation process enhanced the destruction of NOM and reduced the fouling by generating hydroxyl radicals from the catalytic ozonation in the RM-ozonation process. Copyright © 2012 Elsevier Ltd. All rights reserved.

Nitrate formation during ozonation as a surrogate parameter for abatement of micropollutants and the N-nitrosodimethylamine (NDMA) formation potential.

PubMed

Song, Yang; Breider, Florian; Ma, Jun; von Gunten, Urs

2017-10-01

In this study, nitrate formation from ammonium and/or dissolved organic nitrogen (DON) was investigated as a novel surrogate parameter to evaluate the abatement of micropollutants during ozonation of synthetic waters containing natural organic matter (NOM) isolates, a natural water and secondary wastewater effluents. Nitrate formation during ozonation was compared to the changes in UV absorbance at 254 nm (UVA 254 ) including the effect of pH. For low specific ozone doses UVA 254 was abated more efficiently than nitrate was formed. This is due to a relatively slow rate-limiting step for nitrate formation from the reaction between ozone and a proposed nitrogen-containing intermediate. This reaction cannot compete with the fast reactions between ozone and UV-absorbing moieties (e.g., activated aromatic compounds). To further test the kinetics of nitrate formation, two possible intermediates formed during ozonation of DON were tested. At pH 7, nitrate was formed during ozonation of acetone oxime and methyl nitroacetate with second-order rate constants of 256.7 ± 4.7 M -1  s -1 and 149.5 ± 5.8 M -1  s -1 , respectively. The abatement of the selected micropollutants (i.e., 17α-ethinylestradiol (EE2), carbamazepine (CBZ), bezafibrate (BZF), ibuprofen (IBU), and p-chlorobenzoic acid (pCBA)) was investigated for specific ozone doses ≤1.53 mgO 3 /mgDOC and its efficiency depended strongly on the reactivity of the selected compounds with ozone. The relative abatement of micropollutants (i.e., EE2 and CBZ) with high ozone reactivity showed linear relationships with nitrate formation. The abatement of micropollutants with intermediate-low ozone reactivity (BZF, IBU, and pCBA) followed one- and two-phase behaviors relative to nitrate formation during ozonation of water samples containing high and low concentrations of nitrate-forming DON, respectively. During ozonation of a wastewater sample, the N-nitrosodimethylamine formation potential (NDMA-FP) during chloramination decreased with increasing specific ozone doses. A good correlation was obtained between NDMA-FP abatement and nitrate formation. Therefore, nitrate formation after pre-ozonation may be a useful parameter to estimate the reduction of the NDMA-FP during post-chloramination. Overall, the results of this study suggest that nitrate formation (possibly in combination with UVA 254 abatement) during ozonation of DON-containing waters may be a good surrogate for assessing the abatement of micropollutants and the NDMA-FP. Copyright © 2017 Elsevier Ltd. All rights reserved.

Spectroscopic and solubility characteristics of oxidized soots

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chughtai, A.R.; Jassim, J.A.; Peterson, J.H.

1991-01-01

Spectroscopic and solubility studies of reaction products of soot (black carbon) with O{sub 3}, NO{sub 2}/N{sub 2}O{sub 4}, and SO{sub 2} have revealed a relationship between reactivity and product solubility and structure. A remarkably high solubility of ozonated n-hexane soot has its origin in the formation of anhydride and lactone surface structures and their subsequent hydrolysis to carboxylic acid species. Calculations indicate that the rate of surface carboxylation of 0.1-{mu}m diameter spheroidal soot particles, in the presence of 50 ppbv ozone at ambient temperature, is such that solubilization may occur within a 30-minute time frame. Measurements on ambient air aerosolmore » samples in metropolitan Denver are consistent with these observations and demonstrate the high reactivity of soot with ozone even at very low levels in natural systems.« less

Impact of near-surface atmospheric composition on ozone formation in Russia

NASA Astrophysics Data System (ADS)

Berezina, Elena; Moiseenko, Konstantin; Skorokhod, Andrey; Belikov, Igor; Pankratova, Natalia; Elansky, Nikolai

2017-04-01

One of the consequences of the human impact on the atmosphere is increasing in tropospheric ozone concentration, with the highest ozone level being observed in industrially developed and highly populated regions of the world. In these regions, main anthropogenic sources of carbon monoxide (CO), methane (CH4) and volatile organic compounds (VOCs) are concentrated. The oxidation of these compounds, when interacting with hydroxyl and nitrogen oxides at rather high temperature and sunlight, leads to ozone formation. CO and CH4 are slowly oxidized in the atmosphere and cause an increase in global and regional background ozone. However, the oxidation of some VOCs occurs during daylight hours and is accompanied by an increase in ozone concentration near VOCs sources, particularly in urban and industrial areas. The contribution of biogenic VOCs to ozone generation is estimated to be from 40 to 70% of the total contribution of all chemical ozone precursors in the troposphere [1], with isoprene playing the main role in ozone formation [2]. The impact of aromatic hydrocarbons to ozone formation is reported to be about 40% of the total ozone generation from the oxidation of anthropogenic VOCs [3]. In this study, the results of VOCs measurements (isoprene, benzene, toluene, phenol, styrene, xylene and propilbenzene) by proton mass spectrometry in different regions of Russia along the Trans-Siberian railway from Moscow to Vladivostok from TROICA-12 campaign on a mobile laboratory in summer 2008 are analyzed. It is shown that the TROICA-12 measurements were carried out mostly in moderately polluted (2≤NOx<20 ppb) environment ( 78% of measurements) with the remaining part of the measurements divided between weakly polluted (NOx≤2 ppb) and highly polluted (NOx>20 ppb) conditions ( 20 and 2% of measurements, correspondingly). The lower troposphere chemical regime in the campaign is found to be mainly NOx sensitive, both in rural and urban environments, with typical morning NMHC/NOx ratios being well above 20. Hence, ozone production rates are expected to be controlled by regional NOx emissions and their complex interplay with both natural and anthropogenic sources of VOCs. The quantitative contribution of aromatic VOCs to ozone formation in urban areas and in Russian regions along the railway is estimated. The greatest impact of aromatic VOCs to ozone formation (up to 7.5 ppb of O3) is obtained in the large cities along the Trans-Siberian Railway, with the highest concentrations of aromatic VOCs (1-1.7 ppb) and nitrogen oxides (> 20 ppb) being observed. The results show a significant contribution of anthropogenic emissions of VOCs to the photochemical ozone generation (30-50%) in the large cities along the Trans-Siberian railway in hot and dry weather conditions against natural isoprene emissions determining the regional balance of ground-level ozone in summer. This study was supported by the Russian Science Foundation (grant no. 14-47-00049) and by the Russian Foundation for Basic Research (grant no. 16-35-00158). References: 1. Xie, X., Shao, M., Liu, Y., Lu, S., Chang, C. C., and Chen, Z. M. // Atmos. Environ., 2008, 42, pp. 6000-6010. 2. Guenther, A., Geron, C., Pierce, T., Lamb, B., Harley, P., Fall, R. // Atmospheric Environment, 2000, 34, pp. 2205-2230. 3. Dreyfus, G. B., Schade G. W., Goldstein A. H. // J. Geophys. Res., 2002, 107(D19): 4365, doi:10.1029/2001JD001490.

Climate Response to the Increase in Tropospheric Ozone since Preindustrial Times: A Comparison between Ozone and Equivalent CO2 Forcings

NASA Technical Reports Server (NTRS)

Mickley L. J.; Jacob, D. J.; Field, B. D.; Rind, D.

2004-01-01

We examine the characteristics of the climate response to anthropogenic changes in tropospheric ozone. Using a general circulation model, we have carried out a pair of equilibrium climate simulations with realistic present-day and preindustrial ozone distributions. We find that the instantaneous radiative forcing of 0.49 W m(sup -2) due to the increase in tropospheric ozone since preindustrial times results in an increase in global mean surface temperature of 0.28 C. The increase is nearly 0.4 C in the Northern Hemisphere and about 0.2 C in the Southern Hemisphere. The largest increases (greater than 0.8 C) are downwind of Europe and Asia and over the North American interior in summer. In the lower stratosphere, global mean temperatures decrease by about 0.2 C due to the diminished upward flux of radiation at 9.6 micrometers. The largest stratospheric cooling, up to 1.0 C, occurs over high northern latitudes in winter, with possibly important implications for the formation of polar stratospheric clouds. To identify the characteristics of climate forcing unique to tropospheric ozone, we have conducted two additional climate equilibrium simulations: one in which preindustrial tropospheric ozone concentrations were increased everywhere by 18 ppb, producing the same global radiative forcing as present-day ozone but without the heterogeneity; and one in which CO2 was decreased by 25 ppm relative to present day, with ozone at present-day values, to again produce the same global radiative forcing but with the spectral signature of CO2 rather than ozone. In the first simulation (uniform increase of ozone), the global mean surface temperature increases by 0.25 C, with an interhemispheric difference of only 0.03 C, as compared with nearly 0.2 C for the heterogeneous ozone increase. In the second simulation (equivalent CO2), the global mean surface temperature increases by 0.36 C, 30% higher than the increase from tropospheric ozone. The stronger surface warming from CO2 is in part because CO2 forcing (obscured by water vapor) is shifted relatively poleward where the positive ice-albedo feedback amplifies the climate response and in part because the magnitude of the CO2 forcing in the mid-troposphere is double that of ozone. However, we find that CO2 is far less effective than tropospheric ozone in driving lower stratospheric cooling at high northern latitudes in winter.

Laser Spectroscopic Study on Oxygen Isotope Effects in Ozone Surface Decomposition

NASA Astrophysics Data System (ADS)

Minissale, Marco; Boursier, Corinne; Elandaloussi, Hadj; Te, Yao; Jeseck, Pascal; Rouille, Christian; Zanon-Willette, Thomas; Janssen, Christof

2016-04-01

The isotope kinetics of ozone formation in the Chapman reaction [1] O + O2 + M → O3 + M (1) provides the primary example for a chemically induced oxygen isotope anomaly and is associated with large [2] and mass independent [3] oxygen isotope enrichments in the product molecule, linked to a symmetry selection in the ozone formation kinetics [4-5]. The isotopic composition of ozone and its transfer to other molecules is a powerful tracer in the atmospheric and biogeochemical sciences [6] and serves as a primary model for a possible explanation of the oxygen isotopic heterogeneity in the Solar system [7-8]. Recently, the isotope fractionation in the photolytic decomposition process O3 + hν → O2 + O (2) using visible light has been studied in detail [9-10]. Much less is currently known about the isotope fractionation in the dry deposition or in the gas phase thermal decomposition of ozone O3 + M → O2 + O +M. (3) Here we report on first spectroscopic studies of non-photolytic ozone decomposition using a cw-quantum cascade laser at 9.5 μm. The concentration of individual ozone isotopomers (16O3,16O16O17O, and 16O17O16O) in a teflon coated reaction cell is followed in real time at temperatures between 25 and 150 °C. Observed ozone decay rates depend on homogeneous (reaction (3)) processes in the gas phase and on heterogeneous reactions on the wall. A preliminary analysis reveals agreement with currently recommended ozone decay rates in the gas phase and the absence of a large symmetry selection in the surface decomposition process, indicating the absence of a mass independent fractionation effect. This result is in agreement with previous mass spectrometer (MS) studies on heterogeneous ozone formation on pyrex [11], but contradicts an earlier MS study [12] on ozone surface decomposition on pyrex and quartz. Implications for atmospheric chemistry will be discussed. [1] Morton, J., Barnes, J., Schueler, B. and Mauersberger, K. J. Geophys. Res. 95, 901 - 907 (1990). [2] Mauersberger, K. Geophys. Res. Lett. 8, 935-937 (1981). [3] Thiemens, M. H. and Heidenreich, J. E. Science 219, 1073 - 1075 (1983). [4] Janssen, C., Guenther, J., Mauersberger, K. and Krankowsky, D. Phys. Chem. Chem. Phys. 3, 4718-4721 (2001). [5] Gao, Y. Q. and Marcus, R. A. Science 293, 259-263 (2001). [6] Brenninkmeijer, C. A. M. et al. Chem. Rev. 103, 5125 - 5162 (2003). [7] Thiemens, M. H. and Shaheen, in Treatise on Geochemistry, Holland H. and Turekian K. eds., 151 - 177 (2014). [8] Marcus, R. A. J. Chem. Phys. 121, 8201 - 8211 (2004). [9] Früchtl, M., Janssen, C. and Röckmann, T. J. Geophys. Res. Atmos. 120, 4398 - 4416 (2015). [10] Früchtl, M., Janssen, C., Taraborrelli, D., Gromov, S. and Röckmann, T. Geophys. Res. Lett. (2015). [11] Janssen, C. and Tuzson, B. J. Phys. Chem. A 114, 9709-9719 (2010). [12] Chakraborty, S. and Bhattacharya, S. K. Chem. Phys. Lett. 369, 662-667 (2003).

A room temperature method for the formation of ultrathin silicon oxide films

NASA Astrophysics Data System (ADS)

Muisener, Richard John

Growing interest surrounds the use of thin films to impart unique surface properties without adversely affecting those of the bulk. One such example is the formation of a stable high-energy silicon oxide surface on polymers. Thin silicon oxide films have been used to tailor the surface properties of many materials. Conventional methods for SiOx film fabrication such as chemical vapor deposition require either high temperature or expensive vacuum chambers. This research focuses on the intrinsically inexpensive process of UV-ozone to form ultrathin SiOx films from polysiloxane precursors at room temperature and atmospheric pressure. Chemical evidence suggests a complete conversion from organic polymer to inorganic ceramic. Through XPS, the UV-ozone treatment oxidizes over 95% of the silicone's organic side groups with a resulting stoichiometry Of Si 1O2.2C0.08. The silicon oxidation state changes from 2+ in poly(dimethylsiloxane) to 93% 4+ corresponding to SiO2. IR studies show a total loss of methyl bands and the growth of a new Si-O band centered at 1225 cm-1. Gas phase reaction products suggest a radical driven process. The physical properties also suggest a complete conversion to SiO x. Excellent control of film thickness, as low as 2 nm, has been demonstrated by variable angle spectroscopic ellipsometry. The ellipsometrically determined thickness loss of 55% during treatment corresponds to an SiOx film density of 1.9 g/cm3. The continuity of the film is demonstrated by electrical properties and a very low water contact angle consistent with SiOx. The later property ensures that the SiOx films are anti-fogging in nature. Unique hydrophilic-hydrophobic structures were formed through photo-patterning. The reaction has been successfully modeled as self-limiting based on the diffusion of ozone. The chief reactant, atomic oxygen, is generated by the photochemical dissociation of ozone and quickly generates radical species within the polymer film. The reaction proceeds through a cascade of radical reaction pathways until the resulting oxide is formed. The penetration of ozone is limited to the topmost 30 nm of the film; hence, the formation of SiOx is also surface limited. SiOx films of upto 10 nm are formed at room temperature from polymeric precursors.

Photochemical oxidant processes in the presence of dust: An evaluation of the impact of dust on particulate nitrate and ozone formation

NASA Technical Reports Server (NTRS)

Zhang, Yang; Sunwoo, Young; Kotamarthi, Veerabhadra; Carmichael, Gregory R.

1994-01-01

The influence of dust on the tropospheric photochemical oxidant cycle is studied through the use of a detailed coupled aerosol and gas-phase chemistry model. Dust is a significant component of the troposphere throughout Asia and provides a surface for a variety of heterogeneous reactions. Dust is found to be an important surface for particulate nitrate formation. For dust loading and ambient concentrations representative of conditions in East Asia, particulate nitrate levels of 1.5-11.5 micrograms/cubic meter are predicted, consistent with measured levels in this region. Dust is also found to reduce NO(x) levels by up to 50%, HO2 concentrations by 20%-80%, and ozone production rates by up to 25%. The magnitude of the influence of dust is sensitive to mass concentration of the aerosol, relative humidity, and the value of the accommodation coefficient.

Reaction Mechanisms of the Atomic Layer Deposition of Tin Oxide Thin Films Using Tributyltin Ethoxide and Ozone.

PubMed

Nanayakkara, Charith E; Liu, Guo; Vega, Abraham; Dezelah, Charles L; Kanjolia, Ravindra K; Chabal, Yves J

2017-06-20

Uniform and conformal deposition of tin oxide thin films is important for several applications in electronics, gas sensing, and transparent conducting electrodes. Thermal atomic layer deposition (ALD) is often best suited for these applications, but its implementation requires a mechanistic understanding of the initial nucleation and subsequent ALD processes. To this end, in situ FTIR and ex situ XPS have been used to explore the ALD of tin oxide films using tributyltin ethoxide and ozone on an OH-terminated, SiO 2 -passivated Si(111) substrate. Direct chemisorption of tributyltin ethoxide on surface OH groups and clear evidence that subsequent ligand exchange are obtained, providing mechanistic insight. Upon ozone pulse, the butyl groups react with ozone, forming surface carbonate and formate. The subsequent tributyltin ethoxide pulse removes the carbonate and formate features with the appearance of the bands for CH stretching and bending modes of the precursor butyl ligands. This ligand-exchange behavior is repeated for subsequent cycles, as is characteristic of ALD processes, and is clearly observed for deposition temperatures of 200 and 300 °C. On the basis of the in situ vibrational data, a reaction mechanism for the ALD process of tributyltin ethoxide and ozone is presented, whereby ligands are fully eliminated. Complementary ex situ XPS depth profiles confirm that the bulk of the films is carbon-free, that is, formate and carbonate are not incorporated into the film during the deposition process, and that good-quality SnO x films are produced. Furthermore, the process was scaled up in a cross-flow reactor at 225 °C, which allowed the determination of the growth rate (0.62 Å/cycle) and confirmed a self-limiting ALD growth at 225 and 268 °C. An analysis of the temperature-dependence data reveals that growth rate increases linearly between 200 and 300 °C.

Development and (evidence for) destruction of biofilm with Pseudomonas aeruginosa as architect

NASA Technical Reports Server (NTRS)

Uzcategui, Valerie N.; Donadeo, John J.; Lombardi, Daniel R.; Costello, Michael J.; Sauer, Richard L.

1991-01-01

Disinfection and maintenance of an acceptable level of asepsis in spacecraft potable water delivery systems is a formidable task. The major area of research for this project has been to monitor the formation and growth of biofilm, and biofilm attached microorganisms, on stainless steel surfaces (specifically coupons), and the use of ozone for the elimination of these species in a closed loop system. A number of different techniques have been utilized during the course of a typical run. Scraping and sonication of coupon surfaces with subsequent plating as well as epifluorescence microscopy have been utilized to enumerate biofilm protected Pseudomonas aeruginosa. In addition, scanning electron microscopy is the method of choice to examine the integrity of the biofilm. For ozone determinations, the indigo decolorization spectrophotometric method seems most reliable. Both high- and low-nutrient cultured P. aeruginosa organisms were the target species for the ozone disinfection experiments.

On the role of atmosphere-ocean interactions in the expected long-term changes of the Earth's ozone layer caused by greenhouse gases

NASA Astrophysics Data System (ADS)

Zadorozhny, Alexander; Dyominov, Igor

It is well known that anthropogenic emissions of greenhouse gases into the atmosphere produce a global warming of the troposphere and a global cooling of the stratosphere. The expected stratospheric cooling essentially influences the ozone layer via increased polar stratospheric cloud formation and via temperature dependences of the gas phase reaction rates. One more mechanism of how greenhouse gases influences the ozone layer is enhanced water evaporation from the oceans into the atmosphere because of increasing temperatures of the ocean surface due to greenhouse effect. The subject of this paper is a study of the influence of anthropogenic pollution of the atmosphere by the greenhouse gases CO2, CH4, N2O and ozone-depleting chlorine and bromine compounds on the expected long-term changes of the ozone layer with taking into account an increase of water vapour content in the atmosphere due to greenhouse effect. The study based on 2-D zonally averaged interactive dynamical radiative-photochemical model of the troposphere and stratosphere. The model allows to self-consistently calculating diabatic circulation, temperature, gaseous composition of the troposphere and stratosphere at latitudes from the South to North Poles, as well as distribution of sulphate aerosol particles and polar stratospheric clouds of two types. It was supposed in the model that an increase of the ocean surface temperature caused by greenhouse effect is similar to calculated increase of atmospheric surface temperature. Evaporation rate from the ocean surface was computed in dependence of latitude. The model time-dependent runs were made for the period from 1975 to 2100 using two IPCC scenarios depicting maximum and average expected increases of greenhouse gases in the atmosphere. The model calculations show that anthropogenic increasing of water vapour abundance in the atmosphere due to heating of the ocean surface caused by greenhouse effect gives a sensible contribution to the expected ozone changes. The enhanced evaporation from the ocean increases noticeably a water vapour abundance in the stratosphere that decreases global total ozone and retards the expected recovery of the ozone layer. In polar latitudes, additional stratospheric water vapour increase due to greenhouse effect noticeably strengthens the impact of anthropogenic greenhouse gases on ozone through modification of polar stratospheric clouds and retards the expected recovery of the ozone, too. In the Northern hemisphere, the delay of the ozone recovery is about 5 years, in the Southern hemisphere the delay is about 2 years.

Ozone Production in Irradiated Laboratory Ices Relevant to Europa and Ganymede

NASA Astrophysics Data System (ADS)

Cooper, P. D.; Moore, M. H.; Hudson, R. L.

2005-08-01

Observations suggest ozone (O3) is present on the icy surfaces of Ganymede (1), and Rhea and Dione (2). Molecular oxygen (O2) has also been observed on Europa (3) and Ganymede (4). The formation and trapping of such molecules in ice and their subsequent transportation to a sub-surface ocean may be potentially important for sustaining astrobiological life (5). It is assumed that ozone is produced in these icy surfaces by the addition of an oxygen atom to molecular oxygen, with the latter formed by prior irradiation of the water ice. The infrared absorption band of ozone in ice at 1037 cm-1 is strong and thus makes ozone a good tracer for the presence of molecular oxygen which is difficult to detect. We will present results of water/oxygen ices irradiated with 800 keV protons and show the band position and growth of ozone with increasing radiation dose. The thermal stability of this radiolytically-produced ozone has also been measured and comparisons made to the Jovian satellites. P. Cooper is grateful for the support from the National Academies Research Associateship Program. (1) Noll, K.S., Johnson, R.E., Lane, A.L., Domingue, D.L., Weaver, H.A., Science, 273, 341-343, (1996). (2) Noll, K.S., Roush, T.L., Cruikshank, D.P., Johnson, R.E., Pendleton, Y.J., Nature, 388, 45-47, (1997). (3) Spencer, J.R., Calvin, W.M., Astron. J., 124, 3400-3403, (2002). (4) Spencer, J.R., Calvin, W.M., Person, M. J., J. Geo. Res. 100 (E9), 19049-19056 (1995). (5) Chyba, C.F., Hand, K.P., Science, 292, 2026-2027, (2001).

ROLE OF NITROGEN OXIDES IN NONURBAN OZONE FORMATION IN THE PLANETARY BOUNDARY LAYER OVER N (NORTH) AMERICA, W (WESTERN) EUROPE AND ADJACENT AREAS OF OCEAN

EPA Science Inventory

The status of knowledge on photochemical ozone formation and the effects of nitrogen oxides and peroxyacyl nitrates on such formation has been evaluated. The literature is reviewed on nonurban ozone and nitrogen oxide concentration distributions, ozone lifetimes, nitrogen oxide l...

Impact of downward-mixing ozone on surface ozone accumulation in southern Taiwan.

PubMed

Lin, Ching-Ho

2008-04-01

The ozone that initially presents in the previous day's afternoon mixing layer can remain in the nighttime atmosphere and then be carried over to the next morning. Finally, this ozone can be brought to the ground by downward mixing as mixing depth increases during the daytime, thereby increasing surface ozone concentrations. Variation of ozone concentration during each of these periods is investigated in this work. First, ozone concentrations existing in the daily early morning atmosphere at the altitude range of the daily maximum mixing depth (residual ozone concentrations) were measured using tethered ozonesondes on 52 experimental days during 2004-2005 in southern Taiwan. Daily downward-mixing ozone concentrations were calculated by a box model coupling the measured daily residual ozone concentrations and daily mixing depth variations. The ozone concentrations upwind in the previous day's afternoon mixing layer were estimated by the combination of back air trajectory analysis and known previous day's surface ozone distributions. Additionally, the relationship between daily downward-mixing ozone concentration and daily photochemically produced ozone concentration was examined. The latter was calculated by removing the former from daily surface maximum ozone concentration. The measured daily residual ozone concentrations distributed at 12-74 parts per billion (ppb) with an average of 42 +/- 17 ppb are well correlated with the previous upwind ozone concentration (R2 = 0.54-0.65). Approximately 60% of the previous upwind ozone was estimated to be carried over to the next morning and became the observed residual ozone. The daily downward-mixing ozone contributes 48 +/- 18% of the daily surface maximum ozone concentration, indicating that the downward-mixing ozone is as important as daily photochemically produced ozone to daily surface maximum ozone accumulation. The daily downward-mixing ozone is poorly correlated with the daily photochemically produced ozone and contributes significantly to the daily variation of surface maximum ozone concentrations (R2 = 0.19). However, the contribution of downward-mixing ozone to daily ozone variation is not included in most existing statistical models developed for predicting daily ozone variation. Finally, daily surface maximum ozone concentration is positively correlated with daily afternoon mixing depth, attributable to the downward-mixing ozone.

[Influencing Factors of Assimilable Organic Carbon (AOC) Formation in Drinking Water During Ozonation Process].

PubMed

Dong, Bing-zhi; Zhang, Jia-li; He, Chang

2016-05-15

The influences of ozone dosage, pH and ionic strength on the formation of Assimilable Organic Carbon (AOC) during ozonation were investigated. The result demonstrated that within the range of 1-5 mg · L⁻¹ O₃, the formation of AOC increased with increasing ozone dosage, but higher ozone dosage (9 mg · L⁻¹) resulted in reduction of AOC formation. AOC formation increased with higher pH but decreased with increasing ionic strength. The result also showed that AOC formation with hydrophobic fraction (HPO) was the most, followed by transphilic fraction (TPI), and charged hydrophilic fraction (CHPI), while neutral hydrophilic fraction (NHPI) was the least. It was found that AOC formation related closely with SUVA of small molecular weight organics, and the lower SUVA produced more AOC.

Urban and Rural Ozone Pollution Over Lusaka (Zambia, 15.5S, 25E) During SAFARI-2000 (September 2000)

NASA Technical Reports Server (NTRS)

Thompson, Anne M.; Herman, J. R.; Witte, J. C.; Phahlane, A.; Coetzee, G. J. R.; Mukula, C.; Hudson, R. D.; Frolov, A. D.; Bhartia, P. K. (Technical Monitor)

2001-01-01

In early September, throughout south central Africa, seasonal clearing of dry vegetation and the production of charcoal for cooking leads to intense smoke haze and ozone formation. Ozone soundings made over Lusaka during a six-day period in early September 2000 recorded layers of high ozone (greater than 125 ppbv at 5 km) during two stagnant periods, interspersed by a frontal passage that reduced boundary layer ozone by 30 percent. Smoke aerosol column variations aloft and total ozone were monitored by a sun photometer. During the 6-day measurement period, surface ozone concentrations ranged from 50-95 ppbv and integrated tropospheric ozone from the soundings was 39- 54 Dobson Units (note 1.3 km elevation at the launch site). High ozone concentrations above the mixed and inversion layers were advected from rural burning regions in western Zambia where SAFARI aircraft and ground-based instruments observed intense biomass fires and elevated aerosol and trace gas amounts. TOMS tropospheric ozone and smoke aerosols products show the distribution of biomass burning and associated pollution throughout southern Africa in September 2000. Animations of satellite images and trajectories confirm pollutant recirculation over south central African fires, exit of ozone from Mozambique and Tanzania to the Indian Ocean and the characteristic buildup of tropospheric ozone over the Atlantic from western African outflow.

Nimbus-7 Total Ozone Mapping Spectrometer (TOMS) Data Products User's Guide

NASA Technical Reports Server (NTRS)

McPeters, Richard D.; Bhartia, P. K.; Krueger, Arlin J.; Herman, Jay R.; Schlesinger, Barry M.; Wellemeyer, Charles G.; Seftor, Colin J.; Jaross, Glen; Taylor, Steven L.; Swissler, Tom;

Atmospheric Transport and Photochemistry of Ozone Over Central Southern Africa During the Southern Africa Fire-Atmosphere Research Initiative

NASA Technical Reports Server (NTRS)

Tyson, P. D.; Garstang, M.; Thompson, A. M.; DAbreton, P.; Diab, R. D.; Browell, E. V.

1997-01-01

Vertically integrated back and forward trajectories for the 300-200, 700-500 and surface-800 hPa levels are calculated using Pretoria as point of origin for the Southern Africa Fire-Atmosphere Research Initiative (SAFARI) period September-October 1992. The transport fields are then combined to show both horizontal and vertical transport of air to and from Pretoria at the different levels. Air transport patterns in the vertical are linked to the occurrence of absolutely stable layers which are also evident in the 16 ozonesonde profiles recorded at Pretoria during SAFARI. The coherence of the stratification based on dynamical and ozone analysis permits the use of mean ozone profiles with air volume fluxes to interpret the ozone in terms of photochemistry and transport within stable layers. Extensive recirculation across the meridional plane at Pretoria implies that advection of ozone is slow and that photochemistry is responsible for the observed vertical structure over central southern Africa in September and October 1992. Requisite ozone formation rates are supported by model analysis of ozone and ozone precursors measured from SAFARI and Transport and Atmospheric Research Chemistry near the Equator-Atlantic aircraft.

Characterization of surface dielectric barrier discharge influenced by intermediate frequency for ozone production

NASA Astrophysics Data System (ADS)

Abdelaziz, Ayman A.; Ishijima, Tatsuo; Seto, Takafumi; Osawa, Naoki; Wedaa, Hassan; Otani, Yoshio

2016-06-01

The aim of this study is to investigate the effect of the intermediate frequency (1-10 kHz) of the sinusoidal driving voltage on the characteristics of a developed surface dielectric barrier discharge (SDBD)-based reactor having spikes on its discharge electrode. Moreover, its influence on the production of ozone and nitrogen oxide byproducts is evaluated. The results show that SDBD is operated in the filamentary mode at all the frequencies. Nevertheless, the pulses of the discharge current at high frequencies are much denser and have higher amplitudes than those at low frequencies. The analysis of the power consumed in the reactor shows that a small portion of the input power is dissipated in the dielectric material of SDBD source, whereas the major part of the power is consumed in the plasma discharge. The results of the ozone production show that higher frequencies have a slightly adverse effect on the ozone production at relatively high energy density values, where the ozone concentration is slightly decreased when the frequency is increased at the same energy density. The temperature of the discharge channels and gas is not a crucial factor for the decomposition of ozone in this reactor, while the results of the measurements of nitrogen oxides characteristics indicate that the formation of NO and NO2 has a significant adverse effect on the production efficiency of ozone due to their oxidation to another nitrogen oxides and their catalytic effect.

A novel catalytic ceramic membrane fabricated with CuMn2O4 particles for emerging UV absorbers degradation from aqueous and membrane fouling elimination.

PubMed

Guo, Yang; Song, Zilong; Xu, Bingbing; Li, Yanning; Qi, Fei; Croue, Jean-Philippe; Yuan, Donghai

2018-02-15

A novel catalytic ceramic membrane (CM) for improving ozonation and filtration performance was fabricated by surface coating CuMn 2 O 4 particles on a tubular CM. The degradation of ultraviolet (UV) absorbers, reduction of toxicity, elimination of membrane fouling and catalytic mechanism were investigated. The characterization results suggested the particles were well-fixed on membrane surface. The modified membrane showed improved benzophenone-3 removal performance (from 28% to 34%), detoxification (EC 50 as 12.77%) and the stability of catalytic activity. In the degradation performance of model UV absorbers, the developed membrane significantly decreased the UV254 and DOC values in effluent. Compared with a virgin CM, this CM ozonation increased water flux as 29.9% by in-situ degrade effluent organic matters. The CuMn 2 O 4 modified membrane enhanced the ozone self-decompose to generate O 2 - and initiated the chain reaction of ozone decomposition, and subsequently reacted with molecule ozone to produce OH. Additionally, CM was able to promote the interaction between ozone and catalyst/organic chemicals to form H 2 O 2 that promoted the formation of OH. This catalytic ceramic membrane combining with ozonation showed potential applications in emerging pollutant degradation and membrane fouling elimination, and acted as a novel ternary technology for wastewater treatment and water reuse. Copyright © 2017 Elsevier B.V. All rights reserved.

Total Ozone Mapping Spectrometer (TOMS) Level-3 Data Products User's Guide

NASA Technical Reports Server (NTRS)

McPeters, Richard D.; Bhartia, P. K.; Krueger, Arlin J.; Herman, Jay R.; Wellemeyer, Charles G.; Seftor, Colin J.; Byerly, William; Celarier, Edward A.

2000-01-01

Data from the TOMS series of instruments span the time period from November 1978, through the present with about a one and a-half year gap from January 1994 through July 1996. A set of four parameters derived from the TOMS measurements have been archived in the form of daily global maps or Level-3 data products. These products are total column ozone, effective surface reflectivity, aerosol index, and erythermal ultraviolet estimated at the Earth surface. A common fixed grid of I degree latitude by 1.25 degree longitude cells over the entire globe is provided daily for each parameter. These data are archived at the Goddard Space Flight Center Distributed Active Archive Center (DAAQ in Hierarchical Data Format (HDF). They are also available in a character format through the TOMS web site at http://toms.gsfc.nasa.gov. The derivations of the parameters, the mapping algorithm, and the data formats are described. The trend uncertainty for individual TOMS instruments is about 1% decade, but additional uncertainty exists in the combined data record due to uncertainty in the relative calibrations of the various TOMS.

The influence of meteorological factors and biomass burning on surface ozone concentrations at Tanah Rata, Malaysia

NASA Astrophysics Data System (ADS)

Toh, Ying Ying; Lim, Sze Fook; von Glasow, Roland

2013-05-01

The surface ozone concentrations at the Tanah Rata regional Global Atmosphere Watch (GAW) station, Malaysia (4°28‧N, 101°23‧E, 1545 m above Mean Sea Level (MSL)) from June 2006 to August 2008 were analyzed in this study. Overall the ozone mixing ratios are very low; the seasonal variations show the highest mixing ratios during the Southwest monsoon (average 19.1 ppb) and lowest mixing ratios during the spring intermonsoon (average 14.2 ppb). The diurnal variation of ozone is characterised by an afternoon maximum and night time minimum. The meteorological conditions that favour the formation of high ozone levels at this site are low relative humidity, high temperature and minimum rainfall. The average ozone concentration is lower during precipitation days compared to non-precipitation days. The hourly averaged ozone concentrations show significant correlations with temperature and relative humidity during the Northeast monsoon and spring intermonsoon. The highest concentrations are observed when the wind is blowing from the west. We found an anticorrelation between the atmospheric pressure tide and ozone concentrations. The ozone mixing ratios do not exceed the recommended Malaysia Air Quality Guidelines for 1-h and 8-h averages. Five day backward trajectories on two high ozone episodes in 07 August 2006 (40.0 ppb) and 24 February 2008 (45.7 ppb) are computed using the HYbrid Single-Particle Lagrangian Integrated Trajectory (HYSPLIT) model to investigate the origin of the pollutants and influence of regional transport. The high ozone episode during 07 August 2006 (burning season during southwest monsoon) is mainly attributed to regional transport from biomass burning in Sumatra, whereas favourable meteorological conditions (i.e. low relative humidity, high temperature and solar radiation, zero rainfall) and long range transport from Indo-China have elevated the ozone concentrations during 24 February 2008.

N-nitrosodimethylamine (NDMA) formation during ozonation of wastewater and water treatment polymers.

PubMed

Sgroi, Massimiliano; Roccaro, Paolo; Oelker, Gregg; Snyder, Shane A

2016-02-01

N-Nitrosodimethylamine (NDMA) formation by ozonation was investigated in the effluents of four different wastewater treatment plants destined for alternative reuse. Very high levels of NDMA formation were observed in wastewaters from treatment plants non operating with biological nitrogen removal. Selected experiments showed that hydroxyl radical did not have a significant role in NDMA formation during ozonation of wastewater. Furthermore, ozonation of three different polymers used for water treatment, including polyDADMAC, anionic polyacrylamide, and cationic polyacrylamide, spiked in wastewater did not increase the NDMA formation. Effluent organic matter (EfOM) likely reduced the availability of ozone in water able to react with polymers and quenched the produced ·OH radicals which limited polymer degradation and subsequent NDMA production. Excellent correlations were observed between NDMA formation, UV absorbance at 254 nm, and total fluorescence reduction. These data provide evidence that UV and fluorescence surrogates could be used for monitoring and/or controlling NDMA formation during ozonation. Copyright © 2015 Elsevier Ltd. All rights reserved.

Ozone studies in the Paso del Norte region

NASA Astrophysics Data System (ADS)

Becerra-Davila, Fernando

The Paso del Norte region forms the largest contiguous bi-national conglomerate on the US-Mexico border. With a combined population of around 2 million inhabitants, the Paso del Norte region is isolated, more than 500 km away from the nearest urban area of comparable size, thus making it an ideal location for air quality studies of an isolated urban environment. The meteorological conditions leading to a high ozone episode in this region, such as the historical ozone episode of June 2006, are analyzed. It is well known that stagnation and minimal winds, high temperatures, and pressure ridges over the region are conducive to high ozone episodes. In addition, the planetary boundary height is studied to understand its impact on high ozone episodes. Several studies report that ground level ozone non-attainment regulations could be caused not only by local emissions, but also by atmospheric transport. In this work the atmospheric advection of pollutants into the region is analyzed using HYSPLIT backward trajectories. Furthermore, a novel backward trajectory clustering technique is implemented for the summer of 2006. The "ozone weekend effect" (OWE) is a phenomenon by which in some geographical regions ambient ozone concentrations tend to be higher on weekends than on weekdays, despite the lower emissions of ozone precursors during those days. The observed local OWE has never previously been studied in terms of the photolysis rates of four of the main ozone precursors. In this research a novel method that allows the calculation of actinic fluxes, photolysis frequencies and photolysis rates with a high degree of accuracy and reliability has been developed. This method utilizes a combination of the experimental data available for this region in conjunction with a radiative transfer model (TUV model). Three weekend-weekday cases during summers 2006, 2009 and 2010 are studied in this work. In this research, the photolysis impact on the local OWE is studied. The results obtained from this photolysis study demonstrate that the local ground level ozone formation is not only influenced by the strong solar radiation and changing aerosol makeup, but also by other heterogeneous factors and reactions. In addition, this research provided good evidence that the ground level ozone precursor regime in El Paso during the ozone episode of June 2006 was mostly VOC-limited. Much of this estimation was derived from measurements of local ambient VOC/NOx ratios. This finding shows that at least during June 2006, the non-linear surface ozone production increased during weekends compared to workdays in a habitually VOC-limited regime. The seasonal variations of columnar ozone as measured by a Multi-filter Rotating Shadowband instrument installed at the UTEP campus are analyzed for the first time for this region and results are presented. This investigation has addressed the problem of ground-level ozone formation in the Paso del Norte region. Urban ozone is a complex problem with many aspects that are not fully understood. In this investigation, a range of techniques has been used to address the study of local surface ozone episodes with the purpose of acquiring new insights and knowledge that will help understand and remediate the diverse atmospheric pollution events that affect this bi-national region recurrently. Innovative techniques were developed and used, ranging from the use of local ambient atmospheric pollution data to the utilization of complex modeling techniques to achieve the best possible computer results. Finally, the influence of ground level ozone concentrations in admissions to hospitals for this region due to respiratory diseases is analyzed. The comprehensive results obtained in this work will help to better understand ozone formation in the Paso del Norte Region for future policy regulation implementations.

Effect of high concentrations of inorganic seed aerosols on secondary organic aerosol formation in the m-xylene/NO x photooxidation system

NASA Astrophysics Data System (ADS)

Lu, Zifeng; Hao, Jiming; Takekawa, Hideto; Hu, Lanhua; Li, Junhua

High concentrations (>15 μm 3 cm -3) of CaSO 4, Ca(NO 3) 2 and (NH 4) 2SO 4 were selected as surrogates of dry neutral, aqueous neutral and dry acidic inorganic seed aerosols, respectively, to study the effects of inorganic seeds on secondary organic aerosol (SOA) formation in irradiated m-xylene/NO x photooxidation systems. The results indicate that neither ozone formation nor SOA formation is significantly affected by the presence of neutral aerosols (both dry CaSO 4 and aqueous Ca(NO 3) 2), even at elevated concentrations. The presence of high concentrations of (NH 4) 2SO 4 aerosols (dry acidic) has no obvious effect on ozone formation, but it does enhance SOA generation and increase SOA yields. In addition, the effect of dry (NH 4) 2SO 4 on SOA yield is found to be positively correlated with the (NH 4) 2SO 4 surface concentration, and the effect is pronounced only when the surface concentration reaches a threshold value. Further, it is proposed that the SOA generation enhancement is achieved by particle-phase heterogeneous reactions induced and catalyzed by the acidity of dry (NH 4) 2SO 4 seed aerosols.

Ozone and Ozone By-Products in the Cabins of Commercial Aircraft

PubMed Central

Weisel, Clifford; Weschler, Charles J.; Mohan, Kris; Vallarino, Jose; Spengler, John D.

2013-01-01

The aircraft cabin represents a unique indoor environment due to its high surface-to-volume ratio, high occupant density and the potential for high ozone concentrations at cruising altitudes. Ozone was continuously measured and air was sampled on sorbent traps, targeting carbonyl compounds, on 52 transcontinental U.S. or international flights between 2008 and 2010. The sampling was predominantly on planes that did not have ozone scrubbers (catalytic converters). Peak ozone levels on aircraft without catalytic convertors exceeded 100 ppb, with some flights having periods of more than an hour when the ozone levels were > 75ppb. Ozone was greatly reduced on relatively new aircraft with catalytic convertors, but ozone levels on two flights whose aircraft had older convertors were similar to those on planes without catalytic convertors. Hexanal, heptanal, octanal, nonanal, decanal and 6-methyl-5-hepten-2-one (6-MHO) were detected in the aircraft cabin at sub- to low ppb levels. Linear regression models that included the log transformed mean ozone concentration, percent occupancy and plane type were statistically significant and explained between 18 and 25% of the variance in the mixing ratio of these carbonyls. Occupancy was also a significant factor for 6-MHO, but not the linear aldehydes, consistent with 6-MHO’s formation from the reaction between ozone and squalene, which is present in human skin oils. PMID:23517299

Extreme value modeling for the analysis and prediction of time series of extreme tropospheric ozone levels: a case study.

PubMed

Escarela, Gabriel

2012-06-01

The occurrence of high concentrations of tropospheric ozone is considered as one of the most important issues of air management programs. The prediction of dangerous ozone levels for the public health and the environment, along with the assessment of air quality control programs aimed at reducing their severity, is of considerable interest to the scientific community and to policy makers. The chemical mechanisms of tropospheric ozone formation are complex, and highly variable meteorological conditions contribute additionally to difficulties in accurate study and prediction of high levels of ozone. Statistical methods offer an effective approach to understand the problem and eventually improve the ability to predict maximum levels of ozone. In this paper an extreme value model is developed to study data sets that consist of periodically collected maxima of tropospheric ozone concentrations and meteorological variables. The methods are applied to daily tropospheric ozone maxima in Guadalajara City, Mexico, for the period January 1997 to December 2006. The model adjusts the daily rate of change in ozone for concurrent impacts of seasonality and present and past meteorological conditions, which include surface temperature, wind speed, wind direction, relative humidity, and ozone. The results indicate that trend, annual effects, and key meteorological variables along with some interactions explain the variation in daily ozone maxima. Prediction performance assessments yield reasonably good results.

Degradation of sulfamethoxazole using ozone and chlorine dioxide - Compound-specific stable isotope analysis, transformation product analysis and mechanistic aspects.

PubMed

Willach, Sarah; Lutze, Holger V; Eckey, Kevin; Löppenberg, Katja; Lüling, Michelle; Terhalle, Jens; Wolbert, Jens-Benjamin; Jochmann, Maik A; Karst, Uwe; Schmidt, Torsten C

2017-10-01

The sulfonamide antibiotic sulfamethoxazole (SMX) is a widely detected micropollutant in surface and groundwaters. Oxidative treatment with e.g. ozone or chlorine dioxide is regularly applied for disinfection purposes at the same time exhibiting a high potential for removal of micropollutants. Especially for nitrogen containing compounds such as SMX, the related reaction mechanisms are largely unknown. In this study, we systematically investigated reaction stoichiometry, product formation and reaction mechanisms in reactions of SMX with ozone and chlorine dioxide. To this end, the neutral and anionic SMX species, which may occur at typical pH-values of water treatment were studied. Two moles of chlorine dioxide and approximately three moles of ozone were consumed per mole SMX degraded. Oxidation of SMX with ozone and chlorine dioxide leads in both cases to six major transformation products (TPs) as revealed by high-resolution mass spectrometry (HRMS). Tentatively formulated TP structures from other studies could partly be confirmed by compound-specific stable isotope analysis (CSIA). However, for one TP, a hydroxylated SMX, it was not possible by HRMS alone to identify whether hydroxylation occurred at the aromatic ring, as suggested in literature before, or at the anilinic nitrogen. By means of CSIA and an analytical standard it was possible to identify sulfamethoxazole hydroxylamine unequivocally as one of the TPs of the reaction of SMX with ozone as well as with chlorine dioxide. H-abstraction and electron transfer at the anilinic nitrogen are suggested as likely initial reactions of ozone and chlorine dioxide, respectively, leading to its formation. Oxidation of anionic SMX with ozone did not show any significant isotopic fractionation whereas the other reactions studied resulted in a significant carbon isotope fractionation. Copyright © 2017 Elsevier Ltd. All rights reserved.

Ozone in the marine boundary layer of Bay of Bengal and Arabian Sea during post winter period - continental influence

NASA Astrophysics Data System (ADS)

Nair, Prabha R.; George, Susan K.; David, Liji Mary; Parameswaran, Krishnaswamy

Ozone plays a key role in controlling the oxidation capacity of the troposphere and hence the lifetime of a variety of trace gases in the atmosphere. In pristine marine boundary layer (MBL), entire chemistry is initiated by the photolysis of ozone and the subsequent formation of OH radical from water vapour. Also in such environment, photochemical destruction is considered as a major sink in global ozone budget. Even though large number of studies on near surface ozone has been carried out over land such studies are very few over oceanic environments. This paper presents the observational results on the spatial variations of near-surface ozone over Bay of Bengal and Arabian Sea as revealed by the cruise-based measurements (cruise No. SK223) conducted as part of Integrated Campaign for Aerosol gases and Radiation Budget (ICARB) under the Geosphere Biosphere Programme of Indian Space Research Organisation (IGBP). Online measurements of ozone have been carried out by using a UV Photometric Analyser (model 49C of Thermo Electron Corporation, USA). Ozone mixing ratio was observed to be significantly high over northern Bay of Bengal (20-28 ppb) compared to southern Bay of Bengal and Arabian Sea. Minimum levels of ozone ( 5 ppb) have been measured in the central Bay of Bengal region. Over Arabian Sea latitudinal variation was not prominently observed. The over all latitudinal gradient is estimated to be 1.2 ppb/o latitude over Bay of Bengal with longitudinal gradient showing variation depending on the latitude sector. It was maximum (of 1.2ppb/o longitude) over the mid Bay of Bengal region ( 15o N). Longitudinal variation was not significant over northern and southern regions. A close examination of surface airflow patterns and the air mass back trajectories revealed increase in ozone level associated with continental outflow from the northern and central parts of the subcontinent. The diurnal pattern also showed variations depending on the proximity to inhabited land mass and also with meteorological parameters.

BROMIDE'S EFFECT ON DBP FORMATION, SPECIATION, AND CONTROL: PART 1, OZONATION

EPA Science Inventory

The effect of variable ozone dosage and bromide concentration on the formation of organic disinfection byproducts (DBPs) and bromate were evaluated. Low ozone dosages resulted in oxidation of organic precursors, yielding decreases in the formation potential for total trihalometha...

Recent changes in the ventilation of the southern oceans.

PubMed

Waugh, Darryn W; Primeau, Francois; Devries, Tim; Holzer, Mark

2013-02-01

Surface westerly winds in the Southern Hemisphere have intensified over the past few decades, primarily in response to the formation of the Antarctic ozone hole, and there is intense debate on the impact of this on the ocean's circulation and uptake and redistribution of atmospheric gases. We used measurements of chlorofluorocarbon-12 (CFC-12) made in the southern oceans in the early 1990s and mid- to late 2000s to examine changes in ocean ventilation. Our analysis of the CFC-12 data reveals a decrease in the age of subtropical subantarctic mode waters and an increase in the age of circumpolar deep waters, suggesting that the formation of the Antarctic ozone hole has caused large-scale coherent changes in the ventilation of the southern oceans.

Bromate formation in a hybrid ozonation-ceramic membrane filtration system.

PubMed

Moslemi, Mohammadreza; Davies, Simon H; Masten, Susan J

2011-11-01

The effect of pH, ozone mass injection rate, initial bromide concentration, and membrane molecular weight cut off (MWCO) on bromate formation in a hybrid membrane filtration-ozonation reactor was studied. Decreasing the pH, significantly reduced bromate formation. Bromate formation increased with increasing gaseous ozone mass injection rate, due to increase in dissolved ozone concentrations. Greater initial bromide concentrations resulted in higher bromate concentrations. An increase in the bromate concentration was observed by reducing MWCO, which resulted in a concomitant increase in the retention time in the system. A model to estimate the rate of bromate formation was developed. Good correlation between the model simulation and the experimental data was achieved. Copyright © 2011 Elsevier Ltd. All rights reserved.

Mechanism insight of pollutant degradation and bromate inhibition by Fe-Cu-MCM-41 catalyzed ozonation.

PubMed

Chen, Weirui; Li, Xukai; Tang, Yiming; Zhou, Jialu; Wu, Dan; Wu, Yin; Li, Laisheng

2018-03-15

A flexible catalyst, Fe-Cu-MCM-41, was employed to enhance diclofenac (DCF) mineralization and inhibit bromate formation in catalytic ozonation process. Greater TOC removal was achieved in Fe-Cu-MCM-41/O 3 process (78%) than those in Fe-MCM-41/O 3 (65%), Cu-MCM-41/O 3 (73%) and sole ozonation (42%). But it was interesting that both Cu-MCM-41/O 3 and Fe-MCM-41/O 3 achieved 93% bromate inhibition efficiency, only 71% inhibition efficiency was observed in Fe-Cu-MCM-41/O 3 . Influence of pH, TBA/NaHSO 3 and detection of by-products were conducted to explore the mechanism. By Pyridine adsorption-IR and XPS, a relationship was found among activity of catalysts, Lewis acid sites and electron transfer effect between Fe (II/III) and Cu (I/II). Fe-Cu-MCM-41 promoted ozone decomposition to generate OH, which accounted for enhanced DCF mineralization. The consumption of aqueous O 3 also suppressed the oxidative of Br - and HBrO/Br - . More HBrO/BrO - accumulated in catalytic ozonation process and less bromate generated. Bromate formation in Fe-Cu-MCM-41/O 3 process was sensitive with pH value, the acidic condition was not favor for bromate formation. Both DCF mineralization and bromate inhibition were influenced by surface reaction. Moreover, Fe-Cu-MCM-41 showed excellent catalytic performance in suppressing the accumulation of carboxylic acid, especially for oxalic acid. Nearly no oxalic acid was detected during Fe-Cu-MCM-41/O 3 process. Copyright © 2017 Elsevier B.V. All rights reserved.

Effect of operational and water quality parameters on conventional ozonation and the advanced oxidation process O3/H2O2: Kinetics of micropollutant abatement, transformation product and bromate formation in a surface water.

PubMed

Bourgin, Marc; Borowska, Ewa; Helbing, Jakob; Hollender, Juliane; Kaiser, Hans-Peter; Kienle, Cornelia; McArdell, Christa S; Simon, Eszter; von Gunten, Urs

2017-10-01

The efficiency of ozone-based processes under various conditions was studied for the treatment of a surface water (Lake Zürich water, Switzerland) spiked with 19 micropollutants (pharmaceuticals, pesticides, industrial chemical, X-ray contrast medium, sweetener) each at 1 μg L -1 . Two pilot-scale ozonation reactors (4-5 m 3  h -1 ), a 4-chamber reactor and a tubular reactor, were investigated by either conventional ozonation and/or the advanced oxidation process (AOP) O 3 /H 2 O 2 . The effects of selected operational parameters, such as ozone dose (0.5-3 mg L -1 ) and H 2 O 2 dose (O 3 :H 2 O 2  = 1:3-3:1 (mass ratio)), and selected water quality parameters, such as pH (6.5-8.5) and initial bromide concentration (15-200 μg L -1 ), on micropollutant abatement and bromate formation were investigated. Under the studied conditions, compounds with high second-order rate constants k O3 >10 4  M -1  s -1 for their reaction with ozone were well abated (>90%) even for the lowest ozone dose of 0.5 mg L -1 . Conversely, the abatement efficiency of sucralose, which only reacts with hydroxyl radicals (OH), varied between 19 and 90%. Generally, the abatement efficiency increased with higher ozone doses and higher pH and lower bromide concentrations. H 2 O 2 addition accelerated the ozone conversion to OH, which enables a faster abatement of ozone-resistant micropollutants. Interestingly, the abatement of micropollutants decreased with higher bromide concentrations during conventional ozonation due to competitive ozone-consuming reactions, except for lamotrigine, due to the suspected reaction of HOBr/OBr - with the primary amine moieties. In addition to the abatement of micropollutants, the evolution of the two main transformation products (TPs) of hydrochlorothiazide (HCTZ) and tramadol (TRA), chlorothiazide (CTZ) and tramadol N-oxide (TRA-NOX), respectively, was assessed by chemical analysis and kinetic modeling. Both selected TPs were quickly formed initially to reach a maximum concentration followed by a decrease of their concentrations for longer contact times. For the studied conditions, the TP's concentrations at the outlet of the reactors ranged from 0 to 61% of the initial parent compound concentration, CTZ being a more persistent TP against further oxidation than TRA-NOX. Finally, it was demonstrated in both reactors that the formation of bromate (BrO 3 - ), a potentially carcinogenic oxidation by-product, could be controlled by H 2 O 2 addition with a general improvement on micropollutant abatement. Post-treatment by granular activated carbon (GAC) filtration enabled the reduction of micropollutants and TPs concentrations but no changes in bromate were observed. The combined algae assay showed that water quality was significantly improved after oxidation and GAC post-treatment, driven by the abatement of the spiked pesticides (diuron and atrazine). Copyright © 2017 Elsevier Ltd. All rights reserved.

Earth's UV Reflectivity Data from the Ozone Monitoring Instrument on EOS-Aura

NASA Astrophysics Data System (ADS)

Larko, D. E.; Mao, J.; Herman, J. R.; Huang, L.; Qin, W.; Labow, G. J.; Lloyd, S. A.; DeLand, M. T.

2011-12-01

The Lambert Equivalent Reflectivity (LER), derived from satellite ultraviolet (UV) radiance measurements, represents the equivalent scene reflectivity of the Earth's surface and atmosphere without Rayleigh scattering. It provides a better opportunity to quantify variations of the planetary reflectance and albedo associated with snow/ice, atmospheric aerosols and clouds, since UV reflectance is very low over most land surfaces and water. LER values at 340 nm from the Ozone Monitoring Instrument (OMI) on EOS-Aura have been generated as a new product from the OMI TO3 ozone retrieval algorithm and provided to users in HDF format. The wide field of view of OMI (~2200 km) provides complete global coverage every day with 13 km x 24 km resolution at nadir. These data are then mapped to 1 degree x 1 degree latitude-longitude grid as daily and monthly means for weather and climate studies. The OMI LER data set has been used to validate other UV LER data sets from NOAA and NASA polar orbiting satellites, and has been combined with these data sets to construct a continuous long-term data record of terrestrial UV reflectivity. This paper will present details about the data processing and format of the OMI LER product. Applications of this data set in global climate studies will be demonstrated and discussed in this presentation.

Measurement, modeling, and analysis of nonmethane hydrocarbons and ozone in the southeast United States national parks

NASA Astrophysics Data System (ADS)

Kang, Daiwen

In this research, the sources, distributions, transport, ozone formation potential, and biogenic emissions of VOCs are investigated focusing on three Southeast United States National Parks: Shenandoah National Park, Big Meadows site (SHEN), Great Smoky Mountains National Park at Cove Mountain (GRSM) and Mammoth Cave National Park (MACA). A detailed modeling analysis is conducted using the Multiscale Air Quality SImulation Platform (MAQSIP) focusing on nonmethane hydrocarbons and ozone characterized by high O3 surface concentrations. Nine emissions perturbation using the Multiscale Air Quality SImulation Platform (MAQSIP) focusing on nonmethane hydrocarbons and ozone characterized by high O 3 surface concentrations. In the observation-based analysis, source classification techniques based on correlation coefficient, chemical reactivity, and certain ratios were developed and applied to the data set. Anthropogenic VOCs from automobile exhaust dominate at Mammoth Cave National Park, and at Cove Mountain, Great Smoky Mountains National Park, while at Big Meadows, Shenandoah National Park, the source composition is complex and changed from 1995 to 1996. The dependence of isoprene concentrations on ambient temperatures is investigated, and similar regressional relationships are obtained for all three monitoring locations. Propylene-equivalent concentrations are calculated to account for differences in reaction rates between the OH and individual hydrocarbons, and to thereby estimate their relative contributions to ozone formation. Isoprene fluxes were also estimated for all these rural areas. Model predictions (base scenario) tend to give lower daily maximum O 3 concentrations than observations by 10 to 30%. Model predicted concentrations of lumped paraffin compounds are of the same order of magnitude as the observed values, while the observed concentrations for other species (isoprene, ethene, surrogate olefin, surrogate toluene, and surrogate xylene) are usually an order of magnitude higher than the predictions. Detailed sensitivity and process analyses in terms of ozone and VOC scenarios including the base scenario are designed and utilized in the model simulations. Model predictions are compared with the observed values at the three locations for the same time period. Detailed sensitivity and process analyses in terms of ozone and VOC budgets, and relative importance of various VOCs species are provided. (Abstract shortened by UMI.)

Water disinfection: A relationship between ozone and aldehyde production

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gilli, G.; Scursatone, E.; Palin, L.

In the water potabilization plant of Turin city (Italy), the oxidation process is carried out with ozone. Due to its well-known insufficient performance, it is necessary to add alternative oxidants (hypochlorite ion and chlorine dioxide). In this paper, the authors discuss the formation of linear carbonyl groups during surface water treatment in Turni. The results obtained in the field confirm the synthesis of some aliphatic carbonyl compounds of low molecular weight. This phenomenon happens preeminently during the ozone disinfection process and, secondarily, during the other disinfection processes. Experimental results show that, in this last event, chlorine reacts with organic substances,more » and in a second moment, after organics consumption, if chlorine is still in a sufficient concentration, oxidizing them.« less

Oxidation of Cyclohexene Catalyzed by Nanoporous Au(Ag) in Liquid Phase

DOE PAGES

Dou, Jian; Tang, Yu; Nguyen, Luan; ...

2016-12-22

Nanoporous gold with minor silver content has been identified as a new type of gold based catalyst for selective oxidation of cyclohexene with molecular oxygen in liquid. By oxidation of the leached nanoporous gold foils in ozone, the minor silver content was oxidized in this paper to form silver oxide nanoclusters on the surface of nanoporous gold. With further treatment in methanol, the surface silver oxide was reduced and surface alloy was formed on gold ligaments. Both nanoporous gold treated with ozone only and the one with ozone and then methanol are very active for selective oxidation of cyclohexene withmore » molecular oxygen in liquid of cyclohexene with a turn-over-frequency (TOF) of 0.55–0.99 molecules per surface Au atom per second under a solvent-free and initiator- free condition. The total selectivity for production of 2-cyclohexene-1-one, 2-cyclohexene-1-ol, and cyclohexene oxide was increased from 57.5 % to 80.8 % by an additional treatment of nanoporous gold in methanol after activation in zone. Finally, the correlation of catalytic selectivity for the production of the three products and corresponding surface chemistry of ligament suggests that (1) the formed Au–Ag alloy surface is favorable for the formation of 2-cyclohexen-1-one, 2-cyclohexene-1-ol, and cyclohexene oxide and (2) the surface silver oxide is favorable for the production of cyclohexenyl hydroperoxide.« less

Oxidation of Cyclohexene Catalyzed by Nanoporous Au(Ag) in Liquid Phase

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dou, Jian; Tang, Yu; Nguyen, Luan

Nanoporous gold with minor silver content has been identified as a new type of gold based catalyst for selective oxidation of cyclohexene with molecular oxygen in liquid. By oxidation of the leached nanoporous gold foils in ozone, the minor silver content was oxidized in this paper to form silver oxide nanoclusters on the surface of nanoporous gold. With further treatment in methanol, the surface silver oxide was reduced and surface alloy was formed on gold ligaments. Both nanoporous gold treated with ozone only and the one with ozone and then methanol are very active for selective oxidation of cyclohexene withmore » molecular oxygen in liquid of cyclohexene with a turn-over-frequency (TOF) of 0.55–0.99 molecules per surface Au atom per second under a solvent-free and initiator- free condition. The total selectivity for production of 2-cyclohexene-1-one, 2-cyclohexene-1-ol, and cyclohexene oxide was increased from 57.5 % to 80.8 % by an additional treatment of nanoporous gold in methanol after activation in zone. Finally, the correlation of catalytic selectivity for the production of the three products and corresponding surface chemistry of ligament suggests that (1) the formed Au–Ag alloy surface is favorable for the formation of 2-cyclohexen-1-one, 2-cyclohexene-1-ol, and cyclohexene oxide and (2) the surface silver oxide is favorable for the production of cyclohexenyl hydroperoxide.« less

Contribution of low vapor pressure-volatile organic compounds (LVP-VOCs) from consumer products to ozone formation in urban atmospheres

NASA Astrophysics Data System (ADS)

Shin, Hyeong-Moo; McKone, Thomas E.; Bennett, Deborah H.

2015-05-01

Because recent laboratory testing indicates that some low vapor pressure-volatile organic compounds (LVP-VOC) solvents readily evaporate at ambient conditions, LVP-VOCs used in some consumer product formulations may contribute to ozone formation. The goal of this study is to determine the fraction of LVP-VOCs available for ozone formation from the use of consumer products for two hypothetical emissions. This study calculates and compares the fraction of consumed product available for ozone formation as a result of (a) volatilization to air during use and (b) down-the-drain disposal. The study also investigates the impact of different modes of releases on the overall fraction available in ambient air for ozone formation. For the portion of the LVP-VOCs volatilized to air during use, we applied a multi-compartment mass-balance model to track the fate of emitted LVP-VOCs in a multimedia urban environment. For the portion of the LVP-VOCs disposed down the drain, we used a wastewater treatment plant (WWTP) fate model to predict the emission rates of LVP-VOCs to ambient air at WWTPs or at the discharge zone of the facilities and then used these results as emissions in the multimedia urban environment model. In a WWTP, the LVP-VOCs selected in this study are primarily either biodegraded or removed via sorption to sludge depending on the magnitude of the biodegradation half-life and the octanol-water partition coefficient. Less than 0.2% of the LVP-VOCs disposed down the drain are available for ozone formation. In contrast, when the LVP-VOC in a consumer product is volatilized from the surface to which it has been applied, greater than 90% is available for photochemical reactions either at the source location or in the downwind areas. Comparing results from these two modes of releases allows us to understand the importance of determining the fraction of LVP-VOCs volatilized versus disposed down the drain when the product is used by consumers. The results from this study provide important information and modeling tools to evaluate the impact of LVP-VOCs on air quality and suggest the need for future research on emissions of LVP-VOCs at the point of use.

Modeling of Particulate Emissions

DTIC Science & Technology

2011-12-01

Concern Local Air Quality - A Continuing Concern Ground Level Troposphere Ozone Layer Depletion • H2O Ozone Depletion (ice formation) 5 Modeling... Ozone & Smog Formation Health Effects Local Air Quality 33,000-58,000 ft• NOx •Traffic Growth • CO2* • NOx O3* • NOx Reduces CH4 • H2O Vapor...Particulates • SOx Cloud Formation Global Warming * - Greenhouse Gases Ozone Layer Depletion - Not an Immediate Concern Global Warming - An Emerging

Transport and deposition of nitrogen oxides and ozone in the atmospheric surface layer

NASA Astrophysics Data System (ADS)

Li, Yongxian

Tropospheric ozone is an important photochemical air pollutant, which increases respiratory-related diseases, decreases crop yields, and causes other environmental problems. This research has focused on the measurement of soil biogenic emissions of nitric oxide (NO), one of the precursors for ozone formation, from intensively managed soils in the Southeast US, and examined the transport and deposition of NOx (NO + NO2) and ozone in the atmospheric surface layer, and the effects of NO emissions and its chemical reactions on ozone flux and deposition to the earth's surface. Emissions of nitric oxide were measured from an intensively managed agricultural soil, in the lower coastal plain of North Carolina (near Plymouth, NC), using a dynamic chamber technique. Measurements of soil NO emissions in several crop canopies were conducted at four different sites in North Carolina during late spring and summer of 1994-1996. The turbulent fluxes of NO2 and O3 at 5 m and 10 m above the ground were measured using the eddy-correlation technique near Plymouth, NC during late spring of 1995 and summer of 1996, concurrent with measurements of soil NO emissions using the dynamic chamber system. Soil NO emission from within the corn field was high averaging approximately 35 ng N/m2/s during the measurement period of 1995. In another study, vertical measurements of ozone were made on a 610 m tall tower located 15 km Southeast of Raleigh, NC during the summers of 1993-1997, as part of an effort by the State of North Carolina to develop a State Implementation Plan (SIP) for ozone control in the Raleigh Metropolitan Statistical Area. A strong correlation was observed between the nighttime and early morning ozone concentrations in the residual layer (CR) above the NBL and the maximum ground level concentration (C o max) the following afternoon. Based on this correlation, an empirical regression equation (Co max = 27.67*exp(0.016 CR)) was developed for predicting maximum ground level ozone concentrations during the summer months. (Abstract shortened by UMI.)

Formation and emissions of carbonyls during and following gas-phase ozonation of indoor materials

NASA Astrophysics Data System (ADS)

Poppendieck, D. G.; Hubbard, H. F.; Weschler, C. J.; Corsi, R. L.

Ozone concentrations that are several orders of magnitude greater than typical urban ambient concentrations are necessary for gas-phase ozonation of buildings, either for deodorization or for disinfection of biological agents. However, there is currently no published literature on the interaction of building materials and ozone under such extreme conditions. It would be useful to understand, for example in the case of building re-occupation planning, what types and amounts of reaction products may form and persist in a building after ozonation. In this study, 24 materials were exposed to ozone at concentrations of 1000 ppm in the inlet stream of experimental chambers. Fifteen target carbonyls were selected and measured as building ozonation by-products (BOBPs). During the 36 h that include the 16 h ozonation and 20 h persistence phase, the total BOBP mass released from flooring and wall coverings ranged from 1 to 20 mg m -2, with most of the carbonyls being of lower molecular weight (C 1-C 4). In contrast, total BOBP mass released from wood-based products ranged from 20 to 100 mg m -2, with a greater fraction of the BOBPs being heavier carbonyls (C 5-C 9). The total BOBP mass released during an ozonation event is a function of both the total surface area of the material and the BOBP emission rate per unit area of material. Ceiling tile, carpet, office partition, and gypsum wallboard with flat latex paint often have large surface areas in commercial buildings and these same materials exhibited relatively high BOBP releases. The greatest overall BOBP mass releases were observed for three materials that building occupants might have significant contact with: paper, office partition, and medium density fiberboard, e.g., often used in office furniture. These materials also exhibited extended BOBP persistence following ozonation; some BOBPs (e.g., nonanal) persist for months or more at emission rates large enough to result in indoor concentrations that exceed their odor threshold.

Inquiry Based Projects Using Student Ozone Measurements and the Status of Using Plants as Bio-Indicators

NASA Astrophysics Data System (ADS)

Ladd, I. H.; Fishman, J.; Pippin, M.; Sachs, S.; Skelly, J.; Chappelka, A.; Neufeld, H.; Burkey, K.

2006-05-01

Students around the world work cooperatively with their teachers and the scientific research community measuring local surface ozone levels using a hand-held optical scanner and ozone sensitive chemical strips. Through the GLOBE (Global Learning and Observations to Benefit the Environment) Program, students measuring local ozone levels are connected with the chemistry of the air they breathe and how human activity impacts air quality. Educational tools have been developed and correlated with the National Science and Mathematics Standards to facilitate integrating the study of surface ozone with core curriculum. Ozone air pollution has been identified as the major pollutant causing foliar injury to plants when they are exposed to concentrations of surface ozone. The inclusion of native and agricultural plants with measuring surface ozone provides an Earth system approach to understanding surface ozone. An implementation guide for investigating ozone induced foliar injury has been developed and field tested. The guide, Using Sensitive Plants as Bio-Indicators of Ozone Pollution, provides: the background information and protocol for implementing an "Ozone Garden" with native and agricultural plants; and, a unique opportunity to involve students in a project that will develop and increase their awareness of surface ozone air pollution and its impact on plants.

Impacts of stratospheric sulfate geoengineering on tropospheric ozone

NASA Astrophysics Data System (ADS)

Xia, Lili; Nowack, Peer J.; Tilmes, Simone; Robock, Alan

2017-10-01

A range of solar radiation management (SRM) techniques has been proposed to counter anthropogenic climate change. Here, we examine the potential effects of stratospheric sulfate aerosols and solar insolation reduction on tropospheric ozone and ozone at Earth's surface. Ozone is a key air pollutant, which can produce respiratory diseases and crop damage. Using a version of the Community Earth System Model from the National Center for Atmospheric Research that includes comprehensive tropospheric and stratospheric chemistry, we model both stratospheric sulfur injection and solar irradiance reduction schemes, with the aim of achieving equal levels of surface cooling relative to the Representative Concentration Pathway 6.0 scenario. This allows us to compare the impacts of sulfate aerosols and solar dimming on atmospheric ozone concentrations. Despite nearly identical global mean surface temperatures for the two SRM approaches, solar insolation reduction increases global average surface ozone concentrations, while sulfate injection decreases it. A fundamental difference between the two geoengineering schemes is the importance of heterogeneous reactions in the photochemical ozone balance with larger stratospheric sulfate abundance, resulting in increased ozone depletion in mid- and high latitudes. This reduces the net transport of stratospheric ozone into the troposphere and thus is a key driver of the overall decrease in surface ozone. At the same time, the change in stratospheric ozone alters the tropospheric photochemical environment due to enhanced ultraviolet radiation. A shared factor among both SRM scenarios is decreased chemical ozone loss due to reduced tropospheric humidity. Under insolation reduction, this is the dominant factor giving rise to the global surface ozone increase. Regionally, both surface ozone increases and decreases are found for both scenarios; that is, SRM would affect regions of the world differently in terms of air pollution. In conclusion, surface ozone and tropospheric chemistry would likely be affected by SRM, but the overall effect is strongly dependent on the SRM scheme. Due to the health and economic impacts of surface ozone, all these impacts should be taken into account in evaluations of possible consequences of SRM.

N-nitrosodimethylamine (NDMA) formation from the ozonation of model compounds.

PubMed

Marti, Erica J; Pisarenko, Aleksey N; Peller, Julie R; Dickenson, Eric R V

2015-04-01

Nitrosamines are a class of toxic disinfection byproducts commonly associated with chloramination, of which several were included on the most recent U.S. EPA Contaminant Candidate List. Nitrosamine formation may be a significant barrier to ozonation in water reuse applications, particularly for direct or indirect potable reuse, since recent studies show direct formation during ozonation of natural water and treated wastewaters. Only a few studies have identified precursors which react with ozone to form N-nitrosodimethylamine (NDMA). In this study, several precursor compound solutions, prepared in ultrapure water and treated wastewater, were subjected to a 10 M excess of ozone. In parallel experiments, the precursor solutions in ultrapure water were exposed to gamma radiation to determine NDMA formation as a byproduct of reactions of precursor compounds with hydroxyl radicals. The results show six new NDMA precursor compounds that have not been previously reported in the literature, including compounds with hydrazone and carbamate moieties. Molar yields in deionized water were 61-78% for 3 precursors, 12-23% for 5 precursors and <4% for 2 precursors. Bromide concentration was important for three compounds (1,1-dimethylhydrazine, acetone dimethylhydrazone and dimethylsulfamide), but did not enhance NDMA formation for the other precursors. NDMA formation due to chloramination was minimal compared to formation due to ozonation, suggesting distinct groups of precursor compounds for these two oxidants. Hydroxyl radical reactions with the precursors will produce NDMA, but formation is much greater in the presence of molecular ozone. Also, hydroxyl radical scavenging during ozonation leads to increased NDMA formation. Molar conversion yields were higher for several precursors in wastewater as compared to deionized water, which could be due to catalyzed reactions with constituents found in wastewater or hydroxyl radical scavenging. Copyright © 2014 Elsevier Ltd. All rights reserved.

Ozone formation behind pulsed-laser-generated blast waves in oxygen

NASA Astrophysics Data System (ADS)

Stricker, J.; Parker, J. G.

1984-12-01

The formation of ozone behind blast waves in oxygen generated by a pulsed laser has been investigated both experimentally and theoretically, over cell pressure range of 0.68-27 atm. Ozone buildup formed by successive pulses was monitored by recording UV absorption at 2540 Å. It was found that, as the number of pulses increase, the rate of ozone formation decreased until finally an equilibrium concentration was reached. This equilibrium magnitude was determined by the condition that the number of ozone molecules produced by the wave equals the number decomposed by the same wave. The decomposition and formation of O3 during a single pulse were monitored by time-resolved UV absorption measurements. In order to provide a fundamental basis for interpretation of the mechanism of ozone formation, a mathematical model was developed. Although qualitatively measurements and theory agree, the data, mainly on the number of O3 molecules produced per pulse, is in significant disagreement. Several possible explanations of this discrepancy are given.

Tropospheric ozone maxima observed over the Arabian Sea during the pre-monsoon

NASA Astrophysics Data System (ADS)

Jia, Jia; Ladstätter-Weißenmayer, Annette; Hou, Xuewei; Rozanov, Alexei; Burrows, John P.

2017-04-01

An enhancement of the tropospheric ozone column (TOC) over Arabian Sea (AS) during the pre-monsoon season is reported in this study. The potential sources of the AS spring ozone pool are investigated by use of multiple data sets (e.g., SCIAMACHY Limb-Nadir-Matching TOC, OMI/MLS TOC, TES TOC, MACC reanalysis data, MOZART-4 model and HYSPLIT model). Three-quarters of the enhanced ozone concentrations are attributed to the 0-8 km height range. The main source of the ozone enhancement is considered to be caused by long-range transport of ozone pollutants from India (˜ 50 % contributions to the lowest 4 km, ˜ 20 % contributions to the 4-8 km height range), the Middle East, Africa and Europe (˜ 30 % in total). In addition, the vertical pollution accumulation in the lower troposphere, especially at 4-8 km, was found to be important for the AS spring ozone pool formation. Local photochemistry, on the other hand, plays a negligible role in producing ozone at the 4-8 km height range. In the 0-4 km height range, ozone is quickly removed by wet deposition. The AS spring TOC maxima are influenced by the dynamical variations caused by the sea surface temperature (SST) anomaly during the El Niño period in 2005 and 2010 with a ˜ 5 DU decrease.

Endogenous Generation of Singlet Oxygen and Ozone in Human and Animal Tissues: Mechanisms, Biological Significance, and Influence of Dietary Components.

PubMed

Onyango, Arnold N

2016-01-01

Recent studies have shown that exposing antibodies or amino acids to singlet oxygen results in the formation of ozone (or an ozone-like oxidant) and hydrogen peroxide and that human neutrophils produce both singlet oxygen and ozone during bacterial killing. There is also mounting evidence that endogenous singlet oxygen production may be a common occurrence in cells through various mechanisms. Thus, the ozone-producing combination of singlet oxygen and amino acids might be a common cellular occurrence. This paper reviews the potential pathways of formation of singlet oxygen and ozone in vivo and also proposes some new pathways for singlet oxygen formation. Physiological consequences of the endogenous formation of these oxidants in human tissues are discussed, as well as examples of how dietary factors may promote or inhibit their generation and activity.

Endogenous Generation of Singlet Oxygen and Ozone in Human and Animal Tissues: Mechanisms, Biological Significance, and Influence of Dietary Components

PubMed Central

2016-01-01

Recent studies have shown that exposing antibodies or amino acids to singlet oxygen results in the formation of ozone (or an ozone-like oxidant) and hydrogen peroxide and that human neutrophils produce both singlet oxygen and ozone during bacterial killing. There is also mounting evidence that endogenous singlet oxygen production may be a common occurrence in cells through various mechanisms. Thus, the ozone-producing combination of singlet oxygen and amino acids might be a common cellular occurrence. This paper reviews the potential pathways of formation of singlet oxygen and ozone in vivo and also proposes some new pathways for singlet oxygen formation. Physiological consequences of the endogenous formation of these oxidants in human tissues are discussed, as well as examples of how dietary factors may promote or inhibit their generation and activity. PMID:27042259

Impacts of Ozone-vegetation Interactions and Biogeochemical Feedbacks on Atmospheric Composition and Air Quality Under Climate Change

NASA Astrophysics Data System (ADS)

Sadeke, M.; Tai, A. P. K.; Lombardozzi, D.; Val Martin, M.

2015-12-01

Surface ozone pollution is one of the major environmental concerns due to its damaging effects on human and vegetation. One of the largest uncertainties of future surface ozone prediction comes from its interaction with vegetation under a changing climate. Ozone can be modulated by vegetation through, e.g., biogenic emissions, dry deposition and transpiration. These processes are in turn affected by chronic exposure to ozone via lowered photosynthesis rate and stomatal conductance. Both ozone and vegetation growth are expected to be altered by climate change. To better understand these climate-ozone-vegetation interactions and possible feedbacks on ozone itself via vegetation, we implement an online ozone-vegetation scheme [Lombardozzi et al., 2015] into the Community Earth System Model (CESM) with active atmospheric chemistry, climate and land surface components. Previous overestimation of surface ozone in eastern US, Canada and Europe is shown to be reduced by >8 ppb, reflecting improved model-observation comparison. Simulated surface ozone is lower by 3.7 ppb on average globally. Such reductions (and improvements) in simulated ozone are caused mainly by lower isoprene emission arising from reduced leaf area index in response to chronic ozone exposure. Effects via transpiration are also potentially significant but require better characterization. Such findings suggest that ozone-vegetation interaction may substantially alter future ozone simulations, especially under changing climate and ambient CO2 levels, which would further modulate ozone-vegetation interactions. Inclusion of such interactions in Earth system models is thus necessary to give more realistic estimation and prediction of surface ozone. This is crucial for better policy formulation regarding air quality, land use and climate change mitigation. Reference list: Lombardozzi, D., et al. "The Influence of Chronic Ozone Exposure on Global Carbon and Water Cycles." Journal of Climate 28.1 (2015): 292-305.

Interaction between isoprene and ozone fluxes at ecosystem level in a poplar plantation and its impact at European level

NASA Astrophysics Data System (ADS)

Zenone, T.; Hendriks, C.; Brilli, F.; Gioli, B.; Portillo Estrada, M.; Schaap, M.; Ceulemans, R.

2015-12-01

The emissions of Biogenic volatile organic compounds (BVOCs) from vegetation, mainly in form of isoprenoids, play an important role in the tropospheric ozone (O3) formation. The potential large expansion of isoprene emitter species (e.g. poplar) as biofuels feedstock might impact the ground level O3 formation. Here we report the simultaneous observations, using the eddy covariance (EC) technique, of isoprene, O3 and CO2 fluxes in a short rotation coppice (SRC) of poplar. The impact of current poplar plantations and associated isoprene emissions on ground level ozone concentrations for Europe was evaluated using a chemistry transport model (CTM) LOTOS-EUROS. The isoprene fluxes showed a well-defined seasonal and daily cycle that mirrored with the stomata O3 uptake. The isoprene emission and the stomata O3 uptake showed significant statistical relationship especially at elevated temperature. Isoprene was characterized by a remarkable peak of emissions (e.g. 38 nmol m-2s-1) occurring for few days as a consequence of the rapid variation of the air and surface temperature. During these days the photosynthetic apparatus (i.e. the CO2 fluxes) and transpiration rates did not show significant variation while we did observe a variation of the energy exchange and a reduction of the bowen ratio. The response of isoprene emissions to ambient O3 concentration follows the common form of the hormetic dose-response curve with a considerable reduction of the isoprene emissions at [O3] > 80 ppbv indicating a potential damping effect of the O3 levels on isoprene. Under the current condition the impact of SRC plantations on ozone concentrations / formation is very limited in Europe. Our findings indicate that, even with future scenarios with more SRC, or conventional poplar plantations, the impact on Ozone formation is negligible.

Surface ozone concentrations in Europe: Links with the regional-scale atmospheric circulation

NASA Astrophysics Data System (ADS)

Davies, T. D.; Kelly, P. M.; Low, P. S.; Pierce, C. E.

1992-06-01

Daily surface ozone observations from 1978 (1976 for some analyses) to 1988 for Bottesford (United Kingdom), Cabauw, Kloosterburen (The Netherlands), Hohenpeissenberg, Neuglobsow, Hamburg, and Arkona (Germany) are used to analyze links between surface ozone variations and the atmospheric circulation. A daily Europe-wide synoptic classification highlights marked differences between surface ozone/meteorology relationships in summer and winter. These relationships are characterized by correlations between daily surface ozone concentrations at each station and a local subregional surface pressure gradient (a wind speed index). Although there are geographical variations, which are explicable in terms of regional climatology, there are distinct annual cycles. In summer, the surface ozone/wind speed relationship exhibits the expected negative sign; however, in winter, the relationship is, in the main, strongly positive, especially at those stations which are more influenced by the vigorous westerlies. Spring and autumn exhibit negative, positive, or transitional (between summer and winter) behavior, depending on geographical position. It is suggested that these relationships reflect the importance of vertical exchange from the free troposphere to the surface in the nonsummer months. Composite surface pressure patterns and surface pressure anomaly (from the long-term mean) patterns associated with high surface ozone concentrations on daily and seasonal time scales are consistent with the surface ozone/wind speed relationships. Moreover, they demonstrate that high surface ozone concentrations, in a climatological time frame, can be associated with mean surface pressure patterns which have a synoptic reality and are robust. Such an approach may be useful in interpreting past variations in surface ozone and may help to isolate the effect of human activity. It is also possible that assessments can be made of the effect of projected future changes in the atmospheric circulation. This potential is illustrated by the fact that up to 65% of the interannual variance in 6-month mean surface ozone concentrations can be explained by the subregional wind speed index.

Reduction of N-nitrosodimethylamine formation from ranitidine by ozonation preceding chloramination: influencing factors and mechanisms.

PubMed

Zou, Rusen; Liao, Xiaobin; Zhao, Lei; Yuan, Baoling

2018-05-01

Formation of toxic N-nitrosodimethylamine (NDMA) by chloramination of ranitidine, a drug to block histamine, was still an ongoing issue and posed a risk to human health. In this study, the effect of ozonation prior to chloramination on NDMA formation and the transformation pathway were determined. Influencing factors, including ozone dosages, pH, hydroxyl radical scavenger, bromide, and NOM, were studied. The results demonstrated that small ozone dosage (0.5 mg/L) could effectively control NDMA formation from subsequent chloramination (from 40 to 0.8%). The NDMA molar conversion was not only influenced by pH but also by ozone dosages at various pre-ozonation pH (reached the highest value of 5% at pH 8 with 0.5 mg/L O 3 but decreased with the increasing pH with 1 mg/L O 3 ). The NDMA molar yield by chloramination of ranitidine without pre-ozonation was reduced by the presence of bromide ion due to the decomposition of disinfectant. However, due to the formation of brominated intermediate substances (i.e., dimethylamine (DMA), dimethyl-aminomethyl furfuryl alcohol (DFUR)) with higher NDMA molar yield than their parent substances, more NDMA was formed than that without bromide ion upon ozonation. Natural organic matter (NOM) and hydroxyl radical scavenger (tert-butyl alcohol, tBA) enhanced NDMA generation because of the competition of ozone and more ranitidine left. The NDMA reduction mechanism by pre-ozonation during chloramination of ranitidine may be due to the production of oxidation products with less NDMA yield (such as DMA) than parent compound. Based on the result of Q-TOF and GC-MS/MS analysis, three possible transformation pathways were proposed. Different influences of oxidation conditions and water quality parameters suggest that strategies to reduce NDMA formation should vary with drinking water sources and choose optimal ozone dosage.

Reaction of chlorine nitrate with hydrogen chloride and water at Antarctic stratospheric temperatures

NASA Technical Reports Server (NTRS)

Tolbert, Margaret A.; Rossi, Michel J.; Malhotra, Ripudaman; Golden, David M.

1987-01-01

Laboratory studies of heterogeneous reactions important for ozone depletion over Antarctica are reported. The reaction of chlorine nitrate (ClONO2) with H2O and HCl on surfacers that simulate polar stratospheric clouds are studied at temperatures relevant to the Antarctic stratosphere. The gaseous products of the resulting reactions, HOCl, Cl2O, and Cl2, could readily photolyze in the Antarctic spring to produce active chlorine for ozone depletion. Furthermore, the additional formation of condensed-phase HNO3 could serve as a sink for odd nitrogen species that would otherwise scavenge the active chlorine.

Source apportionment of surface ozone in the Yangtze River Delta, China in the summer of 2013

NASA Astrophysics Data System (ADS)

Li, L.; An, J. Y.; Shi, Y. Y.; Zhou, M.; Yan, R. S.; Huang, C.; Wang, H. L.; Lou, S. R.; Wang, Q.; Lu, Q.; Wu, J.

2016-11-01

We applied ozone source apportionment technology (OSAT) with tagged tracers coupled within the Comprehensive Air Quality Model with Extensions (CAMx) to study the region and source category contribution to surface ozone in the Yangtze River Delta area in summer of 2013. Results indicate that the daytime ozone concentrations in the YRD region are influenced by emissions both locally, regionally and super-regionally. At urban Shanghai, Hangzhou and Suzhou receptors, the ozone formation is mainly VOC-limited, precursor emissions form Zhejiang province dominate their O3 concentrations. At the junction area among two provinces and Shanghai city, the ozone is usually influenced by all the three areas. The daily max O3 at the Dianshan Lake in July are contributed by Zhejiang (48.5%), Jiangsu (11.7%), Anhui (11.6%) and Shanghai (7.4%), long-range transport constitutes around 20.9%. At Chongming site, the BVOC emissions rate is higher than urban region. Regional contribution results show that Shanghai constitutes 15.6%, Jiangsu contributes 16.2% and Zhejiang accounts for 25.5% of the daily max O3. The analysis of the source category contribution to high ozone in the Yangtze River Delta region indicates that the most significant anthropogenic emission source sectors contributing to O3 pollution include industry, vehicle exhaust, although the effects vary with source sector and selected pollution episodes. Emissions of NOx and VOCs emitted from the fuel combustion of industrial boilers and kilns, together with VOCs emissions from industrial process contribute a lot to the high concentrations in urban Hangzhou, Suzhou and Shanghai. The contribution from regional elevated power plants cannot be neglected, especially to Dianshan Lake. Fugitive emissions of volatile pollution sources also have certain contribution to regional O3. These results indicate that the regional collaboration is of most importance to reduce ambient ozone pollution, particularly during high ozone episodes.

Discharge Characteristics of Series Surface/Packed-Bed Discharge Reactor Diven by Bipolar Pulsed Power

NASA Astrophysics Data System (ADS)

Hu, Jian; Jiang, Nan; Li, Jie; Shang, Kefeng; Lu, Na; Wu, Yan; Mizuno, Akira

2016-03-01

The discharge characteristics of the series surface/packed-bed discharge (SSPBD) reactor driven by bipolar pulse power were systemically investigated in this study. In order to evaluate the advantages of the SSPBD reactor, it was compared with traditional surface discharge (SD) reactor and packed-bed discharge (PBD) reactor in terms of the discharge voltage, discharge current, and ozone formation. The SSPBD reactor exhibited a faster rising time and lower tail voltage than the SD and PBD reactors. The distribution of the active species generated in different discharge regions of the SSPBD reactor was analyzed by optical emission spectra and ozone analysis. It was found that the packed-bed discharge region (3.5 mg/L), rather than the surface discharge region (1.3 mg/L) in the SSPBD reactor played a more important role in ozone generation. The optical emission spectroscopy analysis indicated that more intense peaks of the active species (e.g. N2 and OI) in the optical emission spectra were observed in the packed-bed region. supported by National Natural Science Foundation of China (No. 51177007), the Joint Funds of National Natural Science Foundation of China (No. U1462105), and Dalian University of Technology Fundamental Research Fund of China (No. DUT15RC(3)030)

The effect of zero-point energy differences on the isotope dependence of the formation of ozone: a classical trajectory study.

PubMed

Schinke, Reinhard; Fleurat-Lessard, Paul

2005-03-01

The effect of zero-point energy differences (DeltaZPE) between the possible fragmentation channels of highly excited O(3) complexes on the isotope dependence of the formation of ozone is investigated by means of classical trajectory calculations and a strong-collision model. DeltaZPE is incorporated in the calculations in a phenomenological way by adjusting the potential energy surface in the product channels so that the correct exothermicities and endothermicities are matched. The model contains two parameters, the frequency of stabilizing collisions omega and an energy dependent parameter Delta(damp), which favors the lower energies in the Maxwell-Boltzmann distribution. The stabilization frequency is used to adjust the pressure dependence of the absolute formation rate while Delta(damp) is utilized to control its isotope dependence. The calculations for several isotope combinations of oxygen atoms show a clear dependence of relative formation rates on DeltaZPE. The results are similar to those of Gao and Marcus [J. Chem. Phys. 116, 137 (2002)] obtained within a statistical model. In particular, like in the statistical approach an ad hoc parameter eta approximately 1.14, which effectively reduces the formation rates of the symmetric ABA ozone molecules, has to be introduced in order to obtain good agreement with the measured relative rates of Janssen et al. [Phys. Chem. Chem. Phys. 3, 4718 (2001)]. The temperature dependence of the recombination rate is also addressed.

The study of excited oxygen molecule gas species production and quenching on thermal protection system materials

NASA Technical Reports Server (NTRS)

Nordine, Paul C.; Fujimoto, Gordon T.; Greene, Frank T.

1987-01-01

The detection of excited oxygen and ozone molecules formed by surface catalyzed oxygen atom recombination and reaction was investigated by laser induced fluorescence (LIF), molecular beam mass spectrometric (MBMS), and field ionization (FI) techniques. The experiment used partially dissociated oxygen flows from a microwave discharge at pressures in the range from 60 to 400 Pa or from an inductively coupled RF discharge at atmospheric pressure. The catalyst materials investigated were nickel and the reaction cured glass coating used for Space Shuttle reusable surface insulation tiles. Nonradiative loss processes for the laser excited states makes LIF detection of O2 difficult such that formation of excited oxygen molecules could not be detected in the flow from the microwave discharge or in the gaseous products of atom loss on nickel. MBMS experiments showed that ozone was a product of heterogeneous O atom loss on nickel and tile surfaces at low temperatures and that ozone is lost on these materials at elevated temperatures. FI was separately investigated as a method by which excited oxygen molecules may be conveniently detected. Partial O2 dissociation decreases the current produced by FI of the gas.

Indoor air purification by dielectric barrier discharge combined with ionic wind: physical and microbiological investigations

NASA Astrophysics Data System (ADS)

Timmermann, E.; Prehn, F.; Schmidt, M.; Höft, H.; Brandenburg, R.; Kettlitz, M.

2018-04-01

A non-thermal plasma source based on a surface dielectric barrier discharge (DBD) is developed for purification of recirculating air in operating theatres in hospitals. This is a challenging application due to high flow rates, short treatment times and the low threshold for ozone in the ventilated air. Therefore, the surface DBD was enhanced in order to generate an ionic wind, which can deflect and thus, filter out airborne microorganisms. Electrical and gas diagnostics as well as microbiological experiments were performed in a downscaled plasma source under variation of various electrical parameters, but application-oriented airflow velocity and humidity. The dependence of electrical power and ozone concentration as well as charged particles in the plasma treated air on frequency, voltage and relative humidity is presented and discussed. The presence of humidity causes a more conductive dielectric surface and thus a weaker plasma formation, especially at low frequency. The airborne test bacteria, Escherichia coli, showed significant effect to plasma treatment (up to 20% reduction) and to plasma with ionic wind (up to 90% removal); especially a configuration with 70% removal and an accompanying ozone concentration of only 360 ppb is promising for future application.

Observations of the vertical distributions of summertime atmospheric pollutants and the corresponding ozone production in Shanghai, China

NASA Astrophysics Data System (ADS)

Xing, Chengzhi; Liu, Cheng; Wang, Shanshan; Chan, Ka Lok; Gao, Yang; Huang, Xin; Su, Wenjing; Zhang, Chengxin; Dong, Yunsheng; Fan, Guangqiang; Zhang, Tianshu; Chen, Zhenyi; Hu, Qihou; Su, Hang; Xie, Zhouqing; Liu, Jianguo

2017-12-01

Ground-based multi-axis differential optical absorption spectroscopy (MAX-DOAS) and lidar measurements were performed in Shanghai, China, during May 2016 to investigate the vertical distribution of summertime atmospheric pollutants. In this study, vertical profiles of aerosol extinction coefficient, nitrogen dioxide (NO2) and formaldehyde (HCHO) concentrations were retrieved from MAX-DOAS measurements using the Heidelberg Profile (HEIPRO) algorithm, while vertical distribution of ozone (O3) was obtained from an ozone lidar. Sensitivity study of the MAX-DOAS aerosol profile retrieval shows that the a priori aerosol profile shape has significant influences on the aerosol profile retrieval. Aerosol profiles retrieved from MAX-DOAS measurements with Gaussian a priori profile demonstrate the best agreements with simultaneous lidar measurements and vehicle-based tethered-balloon observations among all a priori aerosol profiles. Tropospheric NO2 vertical column densities (VCDs) measured with MAX-DOAS show a good agreement with OMI satellite observations with a Pearson correlation coefficient (R) of 0.95. In addition, measurements of the O3 vertical distribution indicate that the ozone productions do not only occur at surface level but also at higher altitudes (about 1.1 km). Planetary boundary layer (PBL) height and horizontal and vertical wind field information were integrated to discuss the ozone formation at upper altitudes. The results reveal that enhanced ozone concentrations at ground level and upper altitudes are not directly related to horizontal and vertical transportation. Similar patterns of O3 and HCHO vertical distributions were observed during this campaign, which implies that the ozone productions near the surface and at higher altitudes are mainly influenced by the abundance of volatile organic compounds (VOCs) in the lower troposphere.

Evaluation of emission control strategies to reduce ozone pollution in the Paso del Norte region using a photochemical air quality modeling system

NASA Astrophysics Data System (ADS)

Valenzuela, Victor Hugo

Air pollution emissions control strategies to reduce ozone precursor pollutants are analyzed by applying a photochemical modeling system. Simulations of air quality conditions during an ozone episode which occurred in June, 2006 are undertaken by increasing or reducing area source emissions in Ciudad Juarez, Chihuahua, Mexico. Two air pollutants are primary drivers in the formation of tropospheric ozone. Oxides of nitrogen (NOx) and volatile organic compounds (VOC) undergo multiple chemical reactions under favorable meteorological conditions to form ozone, which is a secondary pollutant that irritates respiratory systems in sensitive individuals especially the elderly and young children. The U.S. Environmental Protection Agency established National Ambient Air Quality Standards (NAAQS) to limit ambient air pollutants such as ozone by establishing an 8-hour average concentration of 0.075 ppm as the threshold at which a violation of the standard occurs. Ozone forms primarily due reactions in the troposphere of NOx and VOC emissions generated primarily by anthropogenic sources in urban regions. Data from emissions inventories indicate area sources account for ˜15 of NOx and ˜45% of regional VOC emissions. Area sources include gasoline stations, automotive paint bodyshops and nonroad mobile sources. Multiplicity of air pollution emissions sources provides an opportunity to investigate and potentially implement air quality improvement strategies to reduce emissions which contribute to elevated ozone concentrations. A baseline modeling scenario was established using the CAMx photochemical air quality model from which a series of sensitivity analyses for evaluating air quality control strategies were conducted. Modifications to area source emissions were made by varying NOx and / or VOC emissions in the areas of particular interest. Model performance was assessed for each sensitivity analysis. Normalized bias (NB) and normalized error (NE) were used to identify variability of the PREDICTED to OBSERVED ozone concentrations of both BASELINE model and simulations with modified emissions assessed by the sensitivity analysis. All simulations were found to vary within acceptable ranges of these two criteria variables. Simulation results indicate ozone formation in the PdN region is VOC-limited. Under VOC-limited conditions, modifications to NOx emissions do not produce a marked increase or decrease in ozone concentrations. Modifications to VOC emissions generated the highest variability in ozone concentrations. Increasing VOC emissions by 75% produced results which minimized model bias and error when comparing PREDICTED and OBSERVED ozone concentrations. Increasing VOC emissions by 75% either alone or in combination with a 75% increase in NOx emissions generated PREDICTED ozone concentrations very near to OBSERVED ozone. By evaluating the changes in ambient ozone concentrations through photochemical modeling, air quality planners may identify the most efficient or effective VOC emissions control strategies for area sources. Among the strategies to achieve emissions reductions are installation of gasoline vapor recovery systems, replacing high-pressure low-volume surface coating paint spray guns with high-volume low-pressure spray paint guns, requiring emissions control booths for surface coating operations as well as undertaking solvent management practices, requiring the sale of low VOC paint solvents in the surface-coating industry, and requiring low-VOC solvents in the dry cleaning industry. Other strategies to reduce VOC emissions include initiating Eco-Driving strategies to reduce fuel consumption from mobile sources and minimize vehicle idling at the international ports of entry by reducing bridge wait times. This dissertation depicts a tool for evaluating impacts of emissions on regional air quality by addressing the highly unresolved fugitive emissions in the Paso del Norte region. It provides a protocol for decision makers to assess the effects of various emission control strategies in the region. Impacts of specific source categories such as the international ports of entry, gasoline stations, paint body shops, truck stops, and military installations on the regional air quality can be easily and systematically addressed in a timely manner in the future.

Growth behavior and properties of atomic layer deposited tin oxide on silicon from novel tin(II)acetylacetonate precursor and ozone

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kannan Selvaraj, Sathees; Feinerman, Alan; Takoudis, Christos G., E-mail: takoudis@uic.edu

In this work, a novel liquid tin(II) precursor, tin(II)acetylacetonate [Sn(acac){sub 2}], was used to deposit tin oxide films on Si(100) substrate, using a custom-built hot wall atomic layer deposition (ALD) reactor. Three different oxidizers, water, oxygen, and ozone, were tried. Resulting growth rates were studied as a function of precursor dosage, oxidizer dosage, reactor temperature, and number of ALD cycles. The film growth rate was found to be 0.1 ± 0.01 nm/cycle within the wide ALD temperature window of 175–300 °C using ozone; no film growth was observed with water or oxygen. Characterization methods were used to study the composition, interface quality, crystallinity, microstructure,more » refractive index, surface morphology, and resistivity of the resulting films. X-ray photoelectron spectra showed the formation of a clean SnO{sub x}–Si interface. The resistivity of the SnO{sub x} films was calculated to be 0.3 Ω cm. Results of this work demonstrate the possibility of introducing Sn(acac){sub 2} as tin precursor to deposit conducting ALD SnO{sub x} thin films on a silicon surface, with clean interface and no formation of undesired SiO{sub 2} or other interfacial reaction products, for transparent conducting oxide applications.« less

Background ozone in North China: trends, photochemical and transport impacts

NASA Astrophysics Data System (ADS)

Xu, X.; Lin, W.; Ge, B.

2011-12-01

Tropospheric ozone is one of the key greenhouse gases and plays an important role in atmospheric chemistry. Being a strong oxidant, ozone in the surface layer has significant impacts on human and vegetation health. Long-term measurements of surface ozone are highly needed for climate change assessment and environmental policy-making. Such measurements are scarce, particularly from the background regions. Since 2004, surface ozone and some related reactive gases have been observed at Shangdianzi (SDZ), a Global Atmosphere Watch (GAW) station in North China. Located at the north edge of the Northern China Plain (NCP), the SDZ station is an ideal site for capturing polluted air masses from the NCP sector (southwest) and clean air masses from the background sector (northeast). This facilitates the investigation of impacts of regional transport on surface ozone. In this study, we present long-term measurements of surface ozone made at SDZ, discuss the trends of surface ozone levels in different seasons. Results about the observation-based ozone production efficiency (OPE) for the site will be presented, along with impacts from horizontal and vertical air transport.

Background ozone in North China: trends, photochemical and transport impacts

NASA Astrophysics Data System (ADS)

Xu, X.; Lin, W.; Ge, B.

2012-04-01

Tropospheric ozone is one of the key greenhouse gases and plays an important role in atmospheric chemistry. Being a strong oxidant, ozone in the surface layer has significant impacts on human and vegetation health. Long-term measurements of surface ozone are highly needed for climate change assessment and environmental policy-making. Such measurements are scarce, particularly from the background regions. Since 2004, surface ozone and some related reactive gases have been observed at Shangdianzi (SDZ), a Global Atmosphere Watch (GAW) station in North China. Located at the north edge of the Northern China Plain (NCP), the SDZ station is an ideal site for capturing polluted air masses from the NCP sector (southwest) and clean air masses from the background sector (northeast). This facilitates the investigation of impacts of regional transport on surface ozone. In this study, we present long-term measurements of surface ozone made at SDZ, discuss the trends of surface ozone levels in different seasons. Results about the observation-based ozone production efficiency (OPE) for the site will be presented, along with impacts from horizontal and vertical air transport.

Effect of Climate Change on Surface Ozone over North America, Europe, and East Asia

NASA Technical Reports Server (NTRS)

Schnell, Jordan L.; Prather, Michael J.; Josse, Beatrice; Naik, Vaishali; Horowitz, Larry W.; Zeng, Guang; Shindell, Drew T.; Faluvegi, Greg

2016-01-01

The effect of future climate change on surface ozone over North America, Europe, and East Asia is evaluated using present-day (2000s) and future (2100s) hourly surface ozone simulated by four global models. Future climate follows RCP8.5, while methane and anthropogenic ozone precursors are fixed at year-2000 levels. Climate change shifts the seasonal surface ozone peak to earlier in the year and increases the amplitude of the annual cycle. Increases in mean summertime and high-percentile ozone are generally found in polluted environments, while decreases are found in clean environments. We propose climate change augments the efficiency of precursor emissions to generate surface ozone in polluted regions, thus reducing precursor export to neighboring downwind locations. Even with constant biogenic emissions, climate change causes the largest ozone increases at high percentiles. In most cases, air quality extreme episodes become larger and contain higher ozone levels relative to the rest of the distribution.

Modeling the oxidative capacity of the atmosphere of the south coast air basin of California. 1. Ozone formation metrics.

PubMed

Griffin, Robert J; Revelle, Meghan K; Dabdub, Donald

2004-02-01

Metrics associated with ozone (O3) formation are investigated using the California Institute of Technology (CIT) three-dimensional air-quality model. Variables investigated include the O3 production rate (P(O3)), O3 production efficiency (OPE), and total reactivity (the sum of the reactivity of carbon monoxide (CO) and all organic gases that react with the hydroxyl radical). Calculations are spatially and temporally resolved; surface-level and vertically averaged results are shown for September 9, 1993 for three Southern California locations: Central Los Angeles, Azusa, and Riverside. Predictions indicate increasing surface-level O3 concentrations with distance downwind, in line with observations. Surface-level and vertically averaged P(O3) values peak during midday and are highest downwind; surface P(O3) values are greater than vertically averaged values. Surface OPEs generally are highest downwind and peak during midday in downwind locations. In contrast, peaks occur in early morning and late afternoon in the vertically averaged case. Vertically averaged OPEs tend to be greater than those for the surface. Total reactivities are highest in upwind surface locations and peak during rush hours; vertically averaged reactivities are smaller and tend to be more uniform temporally and spatially. Total reactivity has large contributions from CO, alkanes, alkenes, aldehydes, unsubstituted monoaromatics, and secondary organics. Calculations using estimated emissions for 2010 result in decreases in P(O3) values and reactivities but increases in OPEs.

Photocatalytic ozonation of terephthalic acid: a by-product-oriented decomposition study.

PubMed

Fuentes, Iliana; Rodríguez, Julia L; Poznyak, Tatyana; Chairez, Isaac

2014-11-01

Terephthalic acid (TA) is considered as a refractory model compound. For this reason, the TA degradation usually requires a prolonged reaction time to achieve mineralization. In this study, vanadium oxide (VxOy) supported on titanium oxide (TiO2) served as a photocatalyst in the ozonation of the TA with light-emitting diodes (LEDs), having a bandwidth centered at 452 nm. The modified catalyst (VxOy/TiO2) in combination with ozone and LEDs improved the TA degradation and its by-products. The results obtained by this system were compared with photolysis, single ozonation, catalytic ozonation, and photocatalytic ozonation of VxOy/TiO2 with UV lamp. The LED-based photocatalytic ozonation showed almost the same decomposition efficiency of the TA, but it was better in comparison with the use of UV lamp. The oxalic acid accumulation, as the final product of the TA decomposition, was directly influenced by either the presence of VxOy or/and the LED irradiation. Several by-products formed during the TA degradation, such as muconic, fumaric, and oxalic acids, were identified. Besides, two unidentified by-products were completely removed during the observed time (60 min). It was proposed that the TA elimination in the presence of VxOy/TiO2 as catalyst was carried out by the combination of different mechanisms: molecular ozone reaction, indirect mechanism conducted by ·OH, and the surface complex formation.

ADEOS Total Ozone Mapping Spectrometer (TOMS) Data Products User's Guide

NASA Technical Reports Server (NTRS)

Krueger, A.; Bhartia, P. K.; McPeters, R.; Herman, J.; Wellemeyer, C.; Jaross, G.; Seftor, C.; Torres, O.; Labow, G.; Byerly, W.;

Earth Probe Total Ozone Mapping Spectrometer (TOMS) Data Product User's Guide

NASA Technical Reports Server (NTRS)

McPeters, R.; Bhartia, P. K.; Krueger, A.; Herman, J.; Wellemeyer, C.; Seftor, C.; Jaross, G.; Torres, O.; Moy, L.; Labow, G.;

UV-Vis, infrared, and mass spectroscopy of electron irradiated frozen oxygen and carbon dioxide mixtures with water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jones, Brant M.; Kaiser, Ralf I.; Strazzulla, Giovanni

2014-02-01

Ozone has been detected on the surface of Ganymede via observation of the Hartley band through the use of ultraviolet spectroscopy and is largely agreed upon to be formed by radiolytic processing via interaction of magnetospheric energetic ions and/or electrons with oxygen-bearing ices on Ganymede's surface. Interestingly, a clearly distinct band near 300 nm within the shoulder of the UV-Vis spectrum of Ganymede was also observed, but currently lacks an acceptable physical or chemical explanation. Consequently, the primary motivation behind this work was the collection of UV-Vis absorption spectroscopy of ozone formation by energetic electron bombardment of a variety ofmore » oxygen-bearing ices (oxygen, carbon dioxide, water) relevant to this moon as well as other solar system. Ozone was indeed synthesized in pure ices of molecular oxygen, carbon dioxide and a mixture of water and oxygen, in agreement with previous studies. The Hartley band of the ozone synthesized in these ice mixtures was observed in the UV-Vis spectra and compared with the spectrum of Ganymede. In addition, a solid state ozone absorption cross section of 6.0 ± 0.6 × 10{sup –17} cm{sup 2} molecule{sup –1} was obtained from the UV-Vis spectral data. Ozone was not produced in the irradiated carbon dioxide-water mixtures; however, a spectrally 'red' UV continuum is observed and appears to reproduce well what is observed in a large number of icy moons such as Europa.« less

Characterization of N-nitrosodimethylamine formation from the ozonation of ranitidine.

PubMed

Lv, Juan; Wang, Lin; Li, Yongmei

2017-08-01

N-nitrosodimethylamine (NDMA) is an emerging disinfection by-product which is formed during water disinfection in the presence of amine-based precursors. Ranitidine, as one kind of amine-based pharmaceuticals, has been identified as NDMA precursor with high NDMA molar conversion during chloramination. This study focused on the characterization of NDMA formation during ozonation of ranitidine. Influences of operational variables (ozone dose, pH value) and water matrix on NDMA generation as well as ranitidine degradation were evaluated. The results indicate high reactivity of ranitidine with ozone. Dimethylamine (DMA) and NDMA were generated due to ranitidine oxidation. High pH value caused more NDMA accumulation. NDMA formation was inhibited under acid conditions (pH≤5) mainly due to the protonation of amines. Water matrix such as HCO 3 - and humic acid impacted NDMA generation due to OH scavenging. Compared with OH, ozone molecules dominated the productions of DMA and NDMA. However, OH was a critical factor in NDMA degradation. Transformation products of ranitidine during ozonation were identified using gas chromatography-mass spectrometry. Among these products, just DMA and N,N-dimethylformamide could contribute to NDMA formation due to the DMA group in the molecular structures. The NDMA formation pathway from ranitidine ozonation was also proposed. Copyright © 2017. Published by Elsevier B.V.

The efficacy of gaseous ozone against different forms of Candida albicans

PubMed Central

Zargaran, M; Fatahinia, M; Zarei Mahmoudabadi, A

2017-01-01

Background and Purpose: Ozone is an inorganic molecule with effective antimicrobial properties. Clinical treatment of ozonated water was used for the elimination of Candida albicans, Enterococcus faecalis, endotoxins, and biofilms from root canals. In addition, its therapeutic effects for tinea pedis, ulcers, and leishmaniasis were investigated. The purpose of the present study was to evaluate the fungicidal effects of ozone on different forms of C. albicans. In addition, antifungal susceptibility profile of strains was assessed before and after exposure to ozone. Materials and Methods: Fifty strains of C. albicans were exposed to gaseous ozone at different times. Furthermore, biofilm formation and germ tube production were evaluated when yeast suspensions were exposed to ozone. In addition, antifungal susceptibility of ozone resistant colonies was investiagted as compared to controls. Results: Ozone was highly effective in killing C. albicans in yeast form and inhibition of germ tube formation during 210 and 180 s, respectively. Although with increasing exposure time biofilm production was considerably decreased, resistance to ozone was much higher among vaginal and nail isolates even after 60 min. All the strains were sensitive to fluconazole, caspofungin, and terbinafine pre- and post-ozone exposure. Resistance to amphotericin B was significantly enhanced after exposure to ozone. Conclusion: Although ozone was highly effective on the yeast form of C. albicans and it can inhibit the formation of germ tubes in C. albicans, the complete removal of biofilms did not happen even after 60 min. It seems that ozone therapy induces resistance to amphotericin B. PMID:29354778

Effect of ozonation on minocycline degradation and N-Nitrosodimethylamine formation.

PubMed

Lv, Juan; Li, Yong M

2018-06-07

The objective of this study was to assess reactivity of Minocycline (MNC) towards ozone and determine the effects of ozone dose, pH value, and water matrix on MNC degradation as well as to characterize N-Nitrosodimethylamine (NDMA) formation from MNC ozonation. The MNC initial concentration of the solution was set in the range of 2-20 mg/L to investigate NDMA formation during MNC ozonation. Four ozone doses (22.5, 37.2, 58.0, and 74.4 mg/min) were tested to study the effect of ozone dose. For the evaluation of effects of pH value, pH was adjusted from 5 to 9 in the presence of phosphate buffer. MNC ozonation experiments were also conducted in natural water to assess the influence of water matirx. The influence of the typical component of natural water was also investigated with the addition of HA and NaHCO 3 solution. Results indicated that ozone was effective in MNC removal. Consequently, NDMA and dimethylamine (DMA) were generated from MNC oxidation. Increasing pH value enhanced MNC removal but led to greater NDMA generation. Water matrices, such as HCO 3 - and humic acid, affected MNC degradation. Conversely, more NDMA accumulated due to the inhibition of NDMA oxidation by oxidant consumption. Though ⋅OH can enhance MNC degradation, ozone molecules were heavily involved in NDMA production. Seven transformation products were identified. However, only DMA and the unidentified tertiary amine containing DMA group contributed to NDMA formation.

[Ru/AC catalyzed ozonation of recalcitrant organic compounds].

PubMed

Wang, Jian-Bing; Hou, Shao-Pei; Zhou, Yun-Rui; Zhu, Wan-Peng; He, Xu-Wen

2009-09-15

Ozonation and Ru/AC catalyzed ozonation of dimethyl phthalate (DMP), phenols and disinfection by-products precursors were studied. It shows that Ru/AC catalyst can obviously enhance the mineralization of organic compounds. In the degradation of DMP, TOC removal was 28.84% by ozonation alone while it was 66.13% by catalytic ozonation. In the oxidation of 23 kinds of phenols, TOC removals were 9.57%-56.08% by ozonation alone while they were 41.81%-82.32% by catalytic ozonation. Compared to ozonation alone, Ru/AC catalyzed ozonation was more effective for the reduction of disinfection by-products formation potentials in source water. The reduction of haloacetic acids formation potentials was more obvious than thichlomethane formation potentials. After the treatment by catalytic ozonation, the haloacetic acids formation potentials decreased from 144.02 microg/L to 58.50 microg/L, which was below the standard value of EPA. However ozonation alone could not make it reach the standard. The treatments of source water by BAC, O3 + BAC, O3/AC + BAC and Ru/AC + O3 + BAC were also studied. In the four processes, TOC removal was 3.80%, 20.14%, 27.45% and 48.30% respectively, COD removal was 4.37%, 27.22%, 39.91% and 50.00% respectively, UV254 removal was 8.16%, 62.24%, 67.03% and 84.95% respectively. Ru/AC + O3 + BAC process is more effective than the other processes for the removal of TOC, COD and UV254 and no ruthenium leaching observed in the solution. It is a promising process for the treatment of micro polluted source water.

75 FR 48582 - Approval and Promulgation of Implementation Plans and Operating Permits Program; State of Nebraska

Federal Register 2010, 2011, 2012, 2013, 2014

2010-08-11

... the basis that these compounds make a negligible contribution to tropospheric ozone formation. These... has a negligible contribution to tropospheric ozone formation, and need not be considered in..., Incorporation by reference, Intergovernmental relations, Nitrogen dioxide, Ozone, Particulate matter, Reporting...

Surface ozone in China: present-day distribution and long-term changes

NASA Astrophysics Data System (ADS)

Xu, X.; Lin, W.; Xu, W.

2017-12-01

Reliable knowledge of spatio-temporal variations of surface ozone is highly needed to assess the impacts of ozone on human health, ecosystem and climate. Although regional distributions and trends of surface ozone in European and North American countries have been well characterized, little is known about the variability of surface ozone in many other countries, including China, where emissions of ozone precursors have been changing rapidly in recent decades. Here we present the first comprehensive description of present-day (2013-2017) distribution and long-term changes of surface ozone in mainland China. Recent ozone measurements from China's air quality monitoring network (AQMN) are analyzed to show present-day distributions of a few ozone exposure metrics for urban environment. Long-term measurements of ozone at six background sites, a rural site and an urban are used to study the trends of ozone in background, rural and urban air, respectively. The average levels of ozone at the AQMN sites (mainly urban) are close to those found at many European and North American sites. However, ozone at most of the sites shows very large diurnal and seasonal variations so that ozone nonattainment can occur in many cities, particularly those in the North China Plain (NCP), the south of Northeast China (NEC), the Yangtze River Delta (YRD), the Pearl River Delta (PRD), and the Sichuan Basin-Chongqing region (SCB). In all these regions, particularly in the NCP, the maximum daily 8-h average (MDA8) ozone concentration can significantly exceed the national limit (75 ppb). High annual sum of ozone means over 35 ppb (SOMO35) exist mainly in the NCP, NEC and YRD, with regional averages over 4000 ppb·d. Surface ozone has significantly increased at Waliguan (a baseline site in western China) and Shangdianzi (a background site in the NCP), and decreased in winter and spring at Longfengshan (a background site in Northeast China). No clear trend can be derived from long-term measurements of ozone at other sites. Further attention should be paid to future changes of ozone in populated regions of China. Actions are urgently needed to control ozone pollution in the NCP and YRD.

Ozone risk for crops and pastures in present and future climates

NASA Astrophysics Data System (ADS)

Fuhrer, Jürg

2009-02-01

Ozone is the most important regional-scale air pollutant causing risks for vegetation and human health in many parts of the world. Ozone impacts on yield and quality of crops and pastures depend on precursor emissions, atmospheric transport and leaf uptake and on the plant’s biochemical defence capacity, all of which are influenced by changing climatic conditions, increasing atmospheric CO2 and altered emission patterns. In this article, recent findings about ozone effects under current conditions and trends in regional ozone levels and in climatic factors affecting the plant’s sensitivity to ozone are reviewed in order to assess implications of these developments for future regional ozone risks. Based on pessimistic IPCC emission scenarios for many cropland regions elevated mean ozone levels in surface air are projected for 2050 and beyond as a result of both increasing emissions and positive effects of climate change on ozone formation and higher cumulative ozone exposure during an extended growing season resulting from increasing length and frequency of ozone episodes. At the same time, crop sensitivity may decline in areas where warming is accompanied by drying, such as southern and central Europe, in contrast to areas at higher latitudes where rapid warming is projected to occur in the absence of declining air and soil moisture. In regions with rapid industrialisation and population growth and with little regulatory action, ozone risks are projected to increase most dramatically, thus causing negative impacts major staple crops such as rice and wheat and, consequently, on food security. Crop improvement may be a way to increase crop cross-tolerance to co-occurring stresses from heat, drought and ozone. However, the review reveals that besides uncertainties in climate projections, parameters in models for ozone risk assessment are also uncertain and model improvements are necessary to better define specific targets for crop improvements, to identify regions most at risk from ozone in a future climate and to set robust effect-based ozone standards.

Ozone-surface interactions: Investigations of mechanisms, kinetics, mass transport, and implications for indoor air quality

DOE Office of Scientific and Technical Information (OSTI.GOV)

Morrison, Glenn Charles

1999-12-01

In this dissertation, results are presented of laboratory investigations and mathematical modeling efforts designed to better understand the interactions of ozone with surfaces. In the laboratory, carpet and duct materials were exposed to ozone and measured ozone uptake kinetics and the ozone induced emissions of volatile organic compounds. To understand the results of the experiments, mathematical methods were developed to describe dynamic indoor aldehyde concentrations, mass transport of reactive species to smooth surfaces, the equivalent reaction probability of whole carpet due to the surface reactivity of fibers and carpet backing, and ozone aging of surfaces. Carpets, separated carpet fibers, andmore » separated carpet backing all tended to release aldehydes when exposed to ozone. Secondary emissions were mostly n-nonanal and several other smaller aldehydes. The pattern of emissions suggested that vegetable oils may be precursors for these oxidized emissions. Several possible precursors and experiments in which linseed and tung oils were tested for their secondary emission potential were discussed. Dynamic emission rates of 2-nonenal from a residential carpet may indicate that intermediate species in the oxidation of conjugated olefins can significantly delay aldehyde emissions and act as reservoir for these compounds. The ozone induced emission rate of 2-nonenal, a very odorous compound, can result in odorous indoor concentrations for several years. Surface ozone reactivity is a key parameter in determining the flux of ozone to a surface, is parameterized by the reaction probability, which is simply the probability that an ozone molecule will be irreversibly consumed when it strikes a surface. In laboratory studies of two residential and two commercial carpets, the ozone reaction probability for carpet fibers, carpet backing and the equivalent reaction probability for whole carpet were determined. Typically reaction probability values for these materials were 10 -7, 10 -5, and 10 -5 respectively. To understand how internal surface area influences the equivalent reaction probability of whole carpet, a model of ozone diffusion into and reaction with internal carpet components was developed. This was then used to predict apparent reaction probabilities for carpet. He combines this with a modified model of turbulent mass transfer developed by Liu, et al. to predict deposition rates and indoor ozone concentrations. The model predicts that carpet should have an equivalent reaction probability of about 10 -5, matching laboratory measurements of the reaction probability. For both carpet and duct materials, surfaces become progressively quenched (aging), losing the ability to react or otherwise take up ozone. He evaluated the functional form of aging and find that the reaction probability follows a power function with respect to the cumulative uptake of ozone. To understand ozone aging of surfaces, he developed several mathematical descriptions of aging based on two different mechanisms. The observed functional form of aging is mimicked by a model which describes ozone diffusion with internal reaction in a solid. He shows that the fleecy nature of carpet materials in combination with the model of ozone diffusion below a fiber surface and internal reaction may explain the functional form and the magnitude of power function parameters observed due to ozone interactions with carpet. The ozone induced aldehyde emissions, measured from duct materials, were combined with an indoor air quality model to show that concentrations of aldehydes indoors may approach odorous levels. He shows that ducts are unlikely to be a significant sink for ozone due to the low reaction probability in combination with the short residence time of air in ducts.« less

College Students' Understanding of Atmospheric Ozone Formation

ERIC Educational Resources Information Center

Howard, Kristen E.; Brown, Shane A.; Chung, Serena H.; Jobson, B. Thomas; VanReken, Timothy M.

2013-01-01

Research has shown that high school and college students have a lack of conceptual understanding of global warming, ozone, and the greenhouse effect. Most research in this area used survey methodologies and did not include concepts of atmospheric chemistry and ozone formation. This study investigates college students' understandings of atmospheric…

THE EFFECTS OF COMBINED OZONATION AND FILTRATION ON DISINFECTION BY-PRODUCT FORMATION. (R830908)

EPA Science Inventory

The effects of combined ozonation and membrane filtration on the removal of the natural organic matter (NOM) and the formation of disinfection by-products (DBPs) were investigated. Ozonation/filtration resulted in a reduction of up to 50% in the dissolved organic carbon (DOC) ...

Use of ozone-biofiltration for bulk organic removal and disinfection byproduct mitigation in potable reuse applications.

PubMed

Arnold, Mayara; Batista, Jacimaria; Dickenson, Eric; Gerrity, Daniel

2018-07-01

The purpose of this research was to investigate the impacts of ozone dose and empty bed contact time (EBCT) in ozone-biofiltration systems on disinfection byproduct (DBP) formation potential. The data were used to evaluate the possibility of using DBP formation potential as an alternative guideline for total organic carbon (TOC) removal in potable reuse applications. A pilot-scale ozone-biofiltration system was operated with O 3 /TOC ratios ranging from 0.1 to 2.25 and EBCTs ranging from 2 to 20 min. The biofiltration columns contained anthracite or biological activated carbon (BAC). Bench-scale chlorination was performed using the uniform formation conditions (UFC) approach, and quenched samples were analyzed for total trihalomethanes (TTHMs) and regulated haloacetic acids (HAA5s). The data demonstrated that ozone-biofiltration achieved TOC removals ranging from ∼10 to 30%, depending on operational conditions, but biofiltration without ozone generally achieved <10% TOC removal. UFC testing demonstrated that ozone alone was efficient in transforming bulk organic matter and reducing DBP formation potential by 10-30%. The synergistic combination of ozone and biofiltration achieved average overall reductions in TTHM and HAA5 formation potential of 26% and 51%, respectively. Finally, a maximum TOC concentration of 2.0 mg/L was identified as a recommended treatment target for reliable compliance with TTHM and HAA5 regulations for potable reuse systems in the United States. Copyright © 2018 Elsevier Ltd. All rights reserved.

Indoor secondary pollutants from cleaning product and air freshener use in the presence of ozone

NASA Astrophysics Data System (ADS)

Singer, Brett C.; Coleman, Beverly K.; Destaillats, Hugo; Hodgson, Alfred T.; Lunden, Melissa M.; Weschler, Charles J.; Nazaroff, William W.

This study investigated the formation of secondary pollutants resulting from household product use in the presence of ozone. Experiments were conducted in a 50-m 3 chamber simulating a residential room. The chamber was operated at conditions relevant to US residences in polluted areas during warm-weather seasons: an air exchange rate of 1.0 h -1 and an inlet ozone concentration of approximately 120 ppb, when included. Three products were used in separate experiments. An orange oil-based degreaser and a pine oil-based general-purpose cleaner were used for surface cleaning applications. A plug-in scented-oil air freshener (AFR) was operated for several days. Cleaning products were applied realistically with quantities scaled to simulate residential use rates. Concentrations of organic gases and secondary organic aerosol from the terpene-containing consumer products were measured with and without ozone introduction. In the absence of reactive chemicals, the chamber ozone level was approximately 60 ppb. Ozone was substantially consumed following cleaning product use, mainly by homogeneous reaction. For the AFR, ozone consumption was weaker and heterogeneous reaction with sorbed AFR-constituent VOCs was of similar magnitude to homogeneous reaction with continuously emitted constituents. Formaldehyde generation resulted from product use with ozone present, increasing indoor levels by the order of 10 ppb. Cleaning product use in the presence of ozone generated substantial fine particle concentrations (more than 100 μg m -3) in some experiments. Ozone consumption and elevated hydroxyl radical concentrations persisted for 10-12 h following brief cleaning events, indicating that secondary pollutant production can persist for extended periods.

Effects of stratospheric ozone recovery on photochemistry and ozone air quality in the troposphere

NASA Astrophysics Data System (ADS)

Zhang, H.; Wu, S.; Huang, Y.; Wang, Y.

2014-04-01

There has been significant stratospheric ozone depletion since the late 1970s due to ozone-depleting substances (ODSs). With the implementation of the Montreal Protocol and its amendments and adjustments, stratospheric ozone is expected to recover towards its pre-1980 level in the coming decades. In this study, we examine the implications of stratospheric ozone recovery for the tropospheric chemistry and ozone air quality with a global chemical transport model (GEOS-Chem). With a full recovery of the stratospheric ozone, the projected increases in ozone column range from 1% over the low latitudes to more than 10% over the polar regions. The sensitivity factor of troposphere ozone photolysis rate, defined as the percentage changes in surface ozone photolysis rate for 1% increase in stratospheric ozone column, shows significant seasonal variation but is always negative with absolute value larger than one. The expected stratospheric ozone recovery is found to affect the tropospheric ozone destruction rates much more than the ozone production rates. Significant decreases in surface ozone photolysis rates due to stratospheric ozone recovery are simulated. The global average tropospheric OH decreases by 1.7%, and the global average lifetime of tropospheric ozone increases by 1.5%. The perturbations to tropospheric ozone and surface ozone show large seasonal and spatial variations. General increases in surface ozone are calculated for each season, with increases by up to 0.8 ppbv in the remote areas. Increases in ozone lifetime by up to 13% are found in the troposphere. The increased lifetimes of tropospheric ozone in response to stratospheric ozone recovery enhance the intercontinental transport of ozone and global pollution, in particular for the summertime. The global background ozone attributable to Asian emissions is calculated to increase by up to 15% or 0.3 ppbv in the Northern Hemisphere in response to the projected stratospheric ozone recovery.

Sensitivities of NOx transformation and the effects on surface ozone and nitrate

NASA Astrophysics Data System (ADS)

Lei, H.; Wang, J. X. L.

2014-02-01

As precursors to tropospheric ozone and nitrate, nitrogen oxide (NOx) in the present atmosphere and its transformation in response to emission and climate perturbations are studied by using the CAM-Chem model and air quality measurements from the National Emissions Inventory (NEI), Clean Air Status and Trends Network (CASTNET), and Environmental Protection Agency Air Quality System (EPA AQS). It is found that NOx transformations in present atmospheric conditions show different sensitivities over industrial and non-industrial regions. As a result, the surface ozone and nitrate formations can be divided into several regimes associated with the dominant emission types and relative levels of NOx and volatile organic compounds (VOC). Ozone production in industrial regions (the main NOx emission source areas) increases in warmer conditions and slightly decreases following an increase in NOx emissions due to NOx titration, which is opposite to the response in non-industrial regions. The ozone decrease following a temperature increase in non-industrial regions indicates that ozone production in regions that lack NOx emission sources may be sensitive to NOx transformation in remote source regions. The increase in NO2 from NOx titration over industrial regions results in an increase rate of total nitrate that remains higher than the increase rate of NOx emissions. The presented findings indicate that a change in the ozone concentration is more directly affected by changes in climate and precursor emissions, while a change in the nitrate concentration is affected by local ozone production types and their seasonal transfer. The sensitivity to temperature perturbations shows that a warmer climate accelerates the decomposition of odd nitrogen (NOy) during the night. As a result, the transformation rate of NOx to nitrate decreases. Examinations of the historical emissions and air quality records of a typical NOx-limited area, such as Atlanta and a VOC-limited area, such as Los Angeles further confirm the conclusions drawn from the modeling experiments.

Gas-phase chemiluminescent reactions of ozone with monoterpenes

NASA Astrophysics Data System (ADS)

Arora, P. K.; Chatha, J. P. S.; Vohra, K. G.

1983-08-01

Chemiluminescent reactions of ozone with monoterpenes such as linallol, geraniol, d-limonene and α-pinene have been studied in the gas phase at low pressures. Methylglyoxal phosphorescence has been observed in the first two reactions. Emissions from HCHO( 1A 2) and glyoxal ( 3A u) are observed in the reaction of ozone with d-limonene and formation of excited glyoxal is found to be first order in ozone. The reaction of ozone with β-pinene gives rise to emission from a α-dicarbonyl compound and this is found to be first order in ozone. The mechanisms for the formation of excited species are proposed.

Operational surface UV radiation product from GOME-2 and AVHRR/3 data

NASA Astrophysics Data System (ADS)

Kujanpää, J.; Kalakoski, N.

2015-05-01

The surface ultraviolet (UV) radiation product, version 1.20, generated operationally in the framework of the Satellite Application Facility on Ozone and Atmospheric Chemistry Monitoring (O3M SAF) of the European Organisation for the Exploitation of Meteorological Satellites (EUMETSAT) is described. The product is based on the total ozone column derived from the measurements of the second Global Ozone Monitoring Experiment (GOME-2) instrument aboard EUMETSAT's polar orbiting meteorological operational (Metop) satellites. The input total ozone product is generated by the German Aerospace Center (DLR) also within the O3M SAF framework. Polar orbiting satellites provide global coverage but infrequent sampling of the diurnal cloud cover. The diurnal variation of the surface UV radiation is extremely strong due to modulation by solar elevation and rapidly changing cloud cover. At the minimum, one sample of the cloud cover in the morning and another in the afternoon are needed to derive daily maximum and daily integrated surface UV radiation quantities. This is achieved by retrieving cloud optical depth from the channel 1 reflectance of the third Advanced Very High Resolution Radiometer (AVHRR/3) instrument aboard both Metop in the morning orbit (daytime descending node around 09:30 LT) and Polar Orbiting Environmental Satellites (POES) of the National Oceanic and Atmospheric Administration (NOAA) in the afternoon orbit (daytime ascending node around 14:30 LT). In addition, more overpasses are used at high latitudes where the swaths of consecutive orbits overlap. The input satellite data are received from EUMETSAT's Multicast Distribution System (EUMETCast) using commercial telecommunication satellites for broadcasting the data to the user community. The surface UV product includes daily maximum dose rates and integrated daily doses with different biological weighting functions, integrated UVB and UVA radiation, solar noon UV Index and daily maximum photolysis frequencies of ozone and nitrogen dioxide at the surface level. The quantities are computed in a 0.5° × 0.5° regular latitude-longitude grid and stored as daily files in the hierarchical data format (HDF5) within two weeks from sensing. The product files are archived in the O3M SAF distributed archive and can be ordered via the EUMETSAT Data Centre.

Impacts of biogenic and anthropogenic emissions on summertime ozone formation in the Guanzhong Basin, China

NASA Astrophysics Data System (ADS)

Li, Nan; He, Qingyang; Greenberg, Jim; Guenther, Alex; Li, Jingyi; Cao, Junji; Wang, Jun; Liao, Hong; Wang, Qiyuan; Zhang, Qiang

2018-05-01

This study is the first attempt to understand the synergistic impact of anthropogenic and biogenic emissions on summertime ozone (O3) formation in the Guanzhong (GZ) Basin where Xi'an, the oldest and the most populous city (with a population of 9 million) in northwestern China, is located. Month-long (August 2011) WRF-Chem simulations with different sensitivity experiments were conducted and compared with near-surface measurements. Biogenic volatile organic compounds (VOCs) concentrations was characterized from six surface sites among the Qinling Mountains, and urban air composition was measured in Xi'an city at a tower 100 m a. s. The WRF-Chem control experiment reasonably reproduced the magnitudes and variations of observed O3, VOCs, NOx, PM2.5, and meteorological parameters, with normalized mean biases for each parameter within ±21 %. Subsequent analysis employed the factor separation approach (FSA) to quantitatively disentangle the pure and synergistic impacts of anthropogenic and/or biogenic sources on summertime O3 formation. The impact of anthropogenic sources alone was found to be dominant for O3 formation. Although anthropogenic particles reduced NO2 photolysis by up to 60 %, the anthropogenic sources contributed 19.1 ppb O3 formation on average for urban Xi'an. The abundant biogenic VOCs from the nearby forests promoted O3 formation in urban areas by interacting with the anthropogenic NOx. The calculated synergistic contribution (from both biogenic and anthropogenic sources) was up to 14.4 ppb in urban Xi'an, peaking in the afternoon. Our study reveals that the synergistic impact of individual source contributions to O3 formation should be considered in the formation of air pollution control strategies, especially for big cities in the vicinity of forests.

Future heat waves and surface ozone

NASA Astrophysics Data System (ADS)

Meehl, Gerald A.; Tebaldi, Claudia; Tilmes, Simone; Lamarque, Jean-Francois; Bates, Susan; Pendergrass, Angeline; Lombardozzi, Danica

2018-06-01

A global Earth system model is used to study the relationship between heat waves and surface ozone levels over land areas around the world that could experience either large decreases or little change in future ozone precursor emissions. The model is driven by emissions of greenhouse gases and ozone precursors from a medium-high emission scenario (Representative Concentration Pathway 6.0–RCP6.0) and is compared to an experiment with anthropogenic ozone precursor emissions fixed at 2005 levels. With ongoing increases in greenhouse gases and corresponding increases in average temperature in both experiments, heat waves are projected to become more intense over most global land areas (greater maximum temperatures during heat waves). However, surface ozone concentrations on future heat wave days decrease proportionately more than on non-heat wave days in areas where ozone precursors are prescribed to decrease in RCP6.0 (e.g. most of North America and Europe), while surface ozone concentrations in heat waves increase in areas where ozone precursors either increase or have little change (e.g. central Asia, the Mideast, northern Africa). In the stabilized ozone precursor experiment, surface ozone concentrations increase on future heat wave days compared to non-heat wave days in most regions except in areas where there is ozone suppression that contributes to decreases in ozone in future heat waves. This is likely associated with effects of changes in isoprene emissions at high temperatures (e.g. west coast and southeastern North America, eastern Europe).

The impact of synoptic weather on UK surface ozone and implications for premature mortality

NASA Astrophysics Data System (ADS)

Pope, R. J.; Butt, E. W.; Chipperfield, M. P.; Doherty, R. M.; Fenech, S.; Schmidt, A.; Arnold, S. R.; Savage, N. H.

2016-12-01

Air pollutants, such as ozone, have adverse impacts on human health and cause, for example, respiratory and cardiovascular problems. In the United Kingdom (UK), peak surface ozone concentrations typically occur in the spring and summer and are controlled by emission of precursor gases, tropospheric chemistry and local meteorology which can be influenced by large-scale synoptic weather regimes. In this study we composite surface and satellite observations of summer-time (April to September) ozone under different UK atmospheric circulation patterns, as defined by the Lamb weather types. Anticyclonic conditions and easterly flows are shown to significantly enhance ozone concentrations over the UK relative to summer-time average values. Anticyclonic stability and light winds aid the trapping of ozone and its precursor gases near the surface. Easterly flows (NE, E, SE) transport ozone and precursor gases from polluted regions in continental Europe (e.g. the Benelux region) to the UK. Cyclonic conditions and westerly flows, associated with unstable weather, transport ozone from the UK mainland, replacing it with clean maritime (North Atlantic) air masses. Increased cloud cover also likely decrease ozone production rates. We show that the UK Met Office regional air quality model successfully reproduces UK summer-time ozone concentrations and ozone enhancements under anticyclonic and south-easterly conditions for the summer of 2006. By using established ozone exposure-health burden metrics, anticyclonic and easterly condition enhanced surface ozone concentrations pose the greatest public health risk.

Ensemble simulations of the role of the stratosphere in the attribution of northern extratropical tropospheric ozone variability

NASA Astrophysics Data System (ADS)

Hess, P.; Kinnison, D.; Tang, Q.

2015-03-01

Despite the need to understand the impact of changes in emissions and climate on tropospheric ozone, the attribution of tropospheric interannual ozone variability to specific processes has proven difficult. Here, we analyze the stratospheric contribution to tropospheric ozone variability and trends from 1953 to 2005 in the Northern Hemisphere (NH) mid-latitudes using four ensemble simulations of the free running (FR) Whole Atmosphere Community Climate Model (WACCM). The simulations are externally forced with observed time-varying (1) sea-surface temperatures (SSTs), (2) greenhouse gases (GHGs), (3) ozone depleting substances (ODS), (4) quasi-biennial oscillation (QBO), (5) solar variability (SV) and (6) stratospheric sulfate surface area density (SAD). A detailed representation of stratospheric chemistry is simulated, including the ozone loss due to volcanic eruptions and polar stratospheric clouds. In the troposphere, ozone production is represented by CH4-NOx smog chemistry, where surface chemical emissions remain interannually constant. Despite the simplicity of its tropospheric chemistry, at many NH measurement locations, the interannual ozone variability in the FR WACCM simulations is significantly correlated with the measured interannual variability. This suggests the importance of the external forcing applied in these simulations in driving interannual ozone variability. The variability and trend in the simulated 1953-2005 tropospheric ozone from 30 to 90° N at background surface measurement sites, 500 hPa measurement sites and in the area average are largely explained on interannual timescales by changes in the 30-90° N area averaged flux of ozone across the 100 hPa surface and changes in tropospheric methane concentrations. The average sensitivity of tropospheric ozone to methane (percent change in ozone to a percent change in methane) from 30 to 90° N is 0.17 at 500 hPa and 0.21 at the surface; the average sensitivity of tropospheric ozone to the 100 hPa ozone flux (percent change in ozone to a percent change in the ozone flux) from 30 to 90° N is 0.19 at 500 hPa and 0.11 at the surface. The 30-90° N simulated downward residual velocity at 100 hPa increased by 15% between 1953 and 2005. However, the impact of this on the 30-90° N 100 hPa ozone flux is modulated by the long-term changes in stratospheric ozone. The ozone flux decreases from 1965 to 1990 due to stratospheric ozone depletion, but increases again by approximately 7% from 1990 to 2005. The first empirical orthogonal function of interannual ozone variability explains from 40% (at the surface) to over 80% (at 150 hPa) of the simulated ozone interannual variability from 30 to 90° N. This identified mode of ozone variability shows strong stratosphere-troposphere coupling, demonstrating the importance of the stratosphere in an attribution of tropospheric ozone variability. The simulations, with no change in emissions, capture almost 50% of the measured ozone change during the 1990s at a variety of locations. This suggests that a large portion of the measured change is not due to changes in emissions, but can be traced to changes in large-scale modes of ozone variability. This emphasizes the difficulty in the attribution of ozone changes, and the importance of natural variability in understanding the trends and variability of ozone. We find little relation between the El Niño-Southern Oscillation (ENSO) index and large-scale tropospheric ozone variability over the long-term record.

Spatial and temporal variation of surface ozone, NO and NO₂ at urban, suburban, rural and industrial sites in the southwest of the Iberian Peninsula.

PubMed

Domínguez-López, D; Adame, J A; Hernández-Ceballos, M A; Vaca, F; De la Morena, B A; Bolívar, J P

2014-09-01

Surface ozone is one of the most important photochemical pollutants in the low atmosphere, causing damage to human health, vegetation, materials and climate. The weather (high temperatures and high solar radiation), orography (presence of the Guadalquivir valley) and anthropogenic (the cities of Cádiz, Córdoba, Huelva and Seville and two important industrial complexes) characteristics of the southwestern Iberian Peninsula make this region ideal for the formation and accumulation of ozone. To increase the knowledge of ozone behaviour in this area, the monthly, daily and weekly variations of ozone and its precursors, nitrogen oxides (NO(x) = NO + NO2), were analysed over a 4-year period (2003 to 2006). Using the k-means cluster technique, 12 representative stations of five different areas with different ozone behaviour were selected from a total of 29 monitoring sites. This is the first time that the analysis of these atmospheric pollutants has been carried out for the whole area, allowing therefore a complete understanding of the dynamics and the relationships of these compounds in this region. The results showed an opposite behaviour among ozone and NO and NO2 concentrations in urban and suburban zones, marked by maximums of ozone (minimums NO(x)) in spring and summer and minimums (maximums) in autumn and winter. A seasonal behaviour, with lower amplitude, was also observed in rural and industrial areas for ozone concentrations, with the NO and NO2 concentrations remaining at low and similar values during the year in rural zones due to the absence of emission sources in their surroundings. The daily cycles of ozone in urban, suburban and industrial sites registered a maximum value in the early afternoon (14:00-17:00 UTC) while for NOx two peaks were observed, at 7:00-10:00 UTC and 20:00-22:00. In the case of rural stations, no hourly peak of ozone or NO(x) was registered. The weekend effect was studied by using a statistical contrast tests (Student's t). The results indicated that only areas influenced by important traffic emissions presented a weekend effect for NO and NO2, whereas an ozone weekend effect was not detected in any case.

Cerium incorporated MCM-48 (Ce-MCM-48) as a catalyst to inhibit bromate formation during ozonation of bromide-containing water: Efficacy and mechanism.

PubMed

Li, Weiwei; Lu, Xiaowei; Xu, Ke; Qu, Jiuhui; Qiang, Zhimin

2015-12-01

The composite mesoporous sieve Ce-MCM-48 (cerium incorporated MCM-48) with different Si/Ce molar ratios were synthesized hydrothermally and characterized with X-ray diffraction, X-ray photoelectron spectroscopy, BET surface area, and pHpzc. Results indicate that Ce-MCM-48, especially with a Si/Ce molar ratio of 66 (i.e., Ce66-MCM-48), could significantly inhibit bromate (BrO3(-)) formation during ozonation of Br(-)-containing water, achieving 91% of inhibition efficiency at pH 7.6 and 25 °C. An acidic or alkaline pH decreased the inhibition efficiency of Ce66-MCM-48 to some extent, but reaction temperature ranging from 15 to 30 °C had no significant impact. By comparing the bromine mass balance, aqueous O3 decomposition, and newly formed H2O2 between O3 and O3/Ce66-MCM-48 processes, the inhibition mechanism was proposed: Ce66-MCM-48 promoted aqueous O3 decomposition to generate hydroxyl radicals (OH) that could merge into H2O2, so the oxidative transformation of Br(-) and HOBr/OBr(-) by O3 and OH was primarily suppressed. The catalytic ability of Ce66-MCM-48 was continuously regenerated through the circulating reactions between Ce(III) and Ce(IV) occurring on the catalyst surface. Besides its inhibition on BrO3(-) formation, Ce66-MCM-48 could also enhance the degradation of refractory organic micropollutants. Because of these distinct merits, Ce66-MCM-48 has potential applications to water treatment by ozone. Copyright © 2015 Elsevier Ltd. All rights reserved.

Responses of Surface Ozone Air Quality to Anthropogenic Nitrogen Deposition

NASA Astrophysics Data System (ADS)

Zhang, L.; Zhao, Y.; Tai, A. P. K.; Chen, Y.; Pan, Y.

2017-12-01

Human activities have substantially increased atmospheric deposition of reactive nitrogen to the Earth's surface, inducing unintentional effects on ecosystems with complex environmental and climate consequences. One consequence remaining unexplored is how surface air quality might respond to the enhanced nitrogen deposition through surface-atmosphere exchange. We combine a chemical transport model (GEOS-Chem) and a global land model (Community Land Model) to address this issue with a focus on ozone pollution in the Northern Hemisphere. We consider three processes that are important for surface ozone and can be perturbed by addition of atmospheric deposited nitrogen: emissions of biogenic volatile organic compounds (VOCs), ozone dry deposition, and soil nitrogen oxide (NOx) emissions. We find that present-day anthropogenic nitrogen deposition (65 Tg N a-1 to the land), through enhancing plant growth (represented as increases in vegetation leaf area index (LAI) in the model), could increase surface ozone from increased biogenic VOC emissions, but could also decrease ozone due to higher ozone dry deposition velocities. Meanwhile, deposited anthropogenic nitrogen to soil enhances soil NOx emissions. The overall effect on summer mean surface ozone concentrations show general increases over the globe (up to 1.5-2.3 ppbv over the western US and South Asia), except for some regions with high anthropogenic NOx emissions (0.5-1.0 ppbv decreases over the eastern US, Western Europe, and North China). We compare the surface ozone changes with those driven by the past 20-year climate and historical land use changes. We find that the impacts from anthropogenic nitrogen deposition can be comparable to the climate and land use driven surface ozone changes at regional scales, and partly offset the surface ozone reductions due to land use changes reported in previous studies. Our study emphasizes the complexity of biosphere-atmosphere interactions, which can have important implications for future air quality prediction.

Comparison of permanganate preoxidation and preozonation on algae containing water: cell integrity, characteristics, and chlorinated disinfection byproduct formation.

PubMed

Xie, Pengchao; Ma, Jun; Fang, Jingyun; Guan, Yinghong; Yue, Siyang; Li, Xuchun; Chen, Liwei

2013-12-17

Aqueous suspensions of Microcystis aeruginosa were preoxidized with either ozone or permanganate and then subjected to chlorination under conditions simulating drinking water purification. The impacts of the two oxidants on the algal cells and on the subsequent production of dissolved organic matter and disinfection byproducts were investigated. Preozonation dramatically increased disinfection byproduct formation during chlorination, especially the formation of haloaldehydes, haloacetonitriles, and halonitromethanes. Preoxidation with permanganate had much less effect on disinfection byproduct formation. Preozonation destroyed algal cell walls and cell membranes to release intracellular organic matter (IOM), and less than 2.0% integrated cells were left after preozonation with the dosage as low as 0.4 mg/L. Preoxidation with permanganate mainly released organic matter adsorbed on the cells' surface without causing any damage to the cells' integrity, so the increase in byproduct formation was much less. More organic nitrogen and lower molecular weight precursors were produced in a dissolved phase after preozonation than permanganate preoxidation, which contributes to the significant increase of disinfection byproducts after preozonation. The results suggest that permanganate is a better choice than ozone for controlling algae derived pollutants and disinfection byproducts.

N-nitrosodimethylamine formation upon ozonation and identification of precursors source in a municipal wastewater treatment plant.

PubMed

Sgroi, Massimiliano; Roccaro, Paolo; Oelker, Gregg L; Snyder, Shane A

2014-09-02

Ozone doses normalized to the dissolved organic carbon concentration were applied to the primary influent, primary effluent, and secondary effluent of a wastewater treatment plant producing water destined for potable reuse. Results showed the most N-Nitrosodimethylamine (NDMA) production from primary effluent, and the recycle streams entering the primary clarifiers were identified as the main source of NDMA precursors. The degradation of aminomethylated polyacrylamide (Mannich) polymer used for sludge treatment was a significant cause of precursor occurrence. A strong correlation between NDMA formation and ammonia concentration was found suggesting an important role of ammonia oxidation on NDMA production. During ozonation tests in DI water using dimethylamine (DMA) as model precursor, the NDMA yield significantly increased in the presence of ammonia and bromide due to the formation of hydroxylamine and brominated nitrogenous oxidants. In addition, NDMA formation during ozonation of dimethylformamide (DMF), the other model precursor used in this study, occurred only in the presence of ammonia, and it was attributable to the oxidation of DMF by hydroxyl radicals. Filtered wastewater samples (0.7 μm) produced more NDMA than unfiltered samples, suggesting that ozone reacted with dissolved precursors and supporting the hypothesis of polymer degradation. Particularly, the total suspended solids content similarly affected NDMA formation and the UV absorbance decrease during ozonation due to the different ozone demand created in filtered and unfiltered samples.

Measurements of the potential ozone production rate in a forest

NASA Astrophysics Data System (ADS)

Crilley, L.; Sklaveniti, S.; Kramer, L.; Bloss, W.; Flynn, J. H., III; Alvarez, S. L.; Erickson, M.; Dusanter, S.; Locoge, N.; Stevens, P. S.; Millet, D. B.; Alwe, H. D.

2017-12-01

Biogenic volatile organic compounds (BVOC) are a significant source of organic compounds globally and alongside NOx play a key role in the formation of ozone in the troposphere. Understanding how changes in NOx concentrations feed through to altered ozone production in BVOC dominated environments will aid our understanding of future atmospheric composition, notably as developing nations transition from NOx dominated to NOx limited chemistry as a result of mitigation strategies. Here we empirically investigate this ambient ozone formation potential. We report deployment of a custom built instrument to measure in near real time the potential for in situ chemical ozone production, using an artificial light source. Our results are thus indicative of the ozone formation potential for a sampled ambient air mixture, including full VOC complexity, i.e. independent of characterization of individual organic compounds. Ground level measurements were performed as part of the PROPHET-AMOS 2016 field campaign, at a site located within a Northern Michigan forest that has typically low NOx abundance, but high isoprene and terpenoid loadings. As the ambient NOx concentrations were low during the campaign, experiments were performed in which NO was artificially added to the sampled ambient air mixture, to quantify changes in the potential ozone production rate as a function of NOx, and hence the ozone forming characteristics of the ambient air. Preliminarily results from these experiments are presented, and indicate that while ozone production increases with added NO, significant variation was observed for a given NO addition, reflecting differences in the ambient VOC chemical reactivity and ozone formation tendency.

Characteristics of ozone vertical profile observed in the boundary layer around Beijing in autumn.

PubMed

Ma, Zhiqiang; Zhang, Xiaoling; Xu, Jing; Zhao, Xiujuan; Meng, Wei

2011-01-01

In the autumn of 2008, the vertical profiles of ozone and meteorological parameters in the low troposphere (0-1000 m) were observed at two sites around Beijing, specifically urban Nanjiao and rural Shangdianzi. At night and early morning, the lower troposphere divided into two stratified layers due to temperature inversion. Ozone in the lower layer showed a large gradient due to the titration of NO. Air flow from the southwest brought ozone-rich air to Beijing, and the ozone profiles were marked by a continuous increase in the residual layer at night. The accumulated ozone in the upper layer played an important role in the next day's surface peak ozone concentration, and caused a rapid increase in surface ozone in the morning. Wind direction shear and wind speed shear exhibited different influences on ozone profiles and resulted in different surface ozone concentrations in Beijing.

Variability of winter and summer surface ozone in Mexico City on the intraseasonal timescale

NASA Astrophysics Data System (ADS)

Barrett, Bradford S.; Raga, Graciela B.

2016-12-01

Surface ozone concentrations in Mexico City frequently exceed the Mexican standard and have proven difficult to forecast due to changes in meteorological conditions at its tropical location. The Madden-Julian Oscillation (MJO) is largely responsible for intraseasonal variability in the tropics. Circulation patterns in the lower and upper troposphere and precipitation are associated with the oscillation as it progresses eastward around the planet. It is typically described by phases (labeled 1 through 8), which correspond to the broad longitudinal location of the active component of the oscillation with enhanced precipitation. In this study we evaluate the intraseasonal variability of winter and summer surface ozone concentrations in Mexico City, which was investigated over the period 1986-2014 to determine if there is a modulation by the MJO that would aid in the forecast of high-pollution episodes. Over 1 000 000 hourly observations of surface ozone from five stations around the metropolitan area were standardized and then binned by active phase of the MJO, with phase determined using the real-time multivariate MJO index. Highest winter ozone concentrations were found in Mexico City on days when the MJO was active and in phase 2 (over the Indian Ocean), and highest summer ozone concentrations were found on days when the MJO was active and in phase 6 (over the western Pacific Ocean). Lowest winter ozone concentrations were found during active MJO phase 8 (over the eastern Pacific Ocean), and lowest summer ozone concentrations were found during active MJO phase 1 (over the Atlantic Ocean). Anomalies of reanalysis-based cloud cover and UV-B radiation supported the observed variability in surface ozone in both summer and winter: MJO phases with highest ozone concentration had largest positive UV-B radiation anomalies and lowest cloud-cover fraction, while phases with lowest ozone concentration had largest negative UV-B radiation anomalies and highest cloud-cover fraction. Furthermore, geopotential height anomalies at 250 hPa favoring reduced cloudiness, and thus elevated surface ozone, were found in both seasons during MJO phases with above-normal ozone concentrations. Similar height anomalies at 250 hPa favoring enhanced cloudiness, and thus reduced surface ozone, were found in both seasons during MJO phases with below-normal ozone concentrations. These anomalies confirm a physical pathway for MJO modulation of surface ozone via modulation of the upper troposphere.

Biodegradability of DBP precursors after drinking water ozonation.

PubMed

de Vera, Glen Andrew; Keller, Jurg; Gernjak, Wolfgang; Weinberg, Howard; Farré, Maria José

2016-12-01

Ozonation is known to generate biodegradable organic matter, which is typically reduced by biological filtration to avoid bacterial regrowth in distribution systems. Post-chlorination generates halogenated disinfection byproducts (DBPs) but little is known about the biodegradability of their precursors. This study determined the effect of ozonation and biofiltration conditions, specifically ozone exposure and empty bed contact time (EBCT), on the control of DBP formation potentials in drinking water. Ozone exposure was varied through addition of H 2 O 2 during ozonation at 1 mgO 3 /mgDOC followed by biological filtration using either activated carbon (BAC) or anthracite. Ozonation led to a 10% decrease in dissolved organic carbon (DOC), without further improvement from H 2 O 2 addition. Raising H 2 O 2 concentrations from 0 to 2 mmol/mmolO 3 resulted in increased DBP formation potentials during post-chlorination of the ozonated water (target Cl 2 residual after 24 h = 1-2 mg/L) as follows: 4 trihalomethanes (THM4, 37%), 8 haloacetic acids (HAA8, 44%), chloral hydrate (CH, 107%), 2 haloketones (HK2, 97%), 4 haloacetonitriles (HAN4, 33%), trichloroacetamide (TCAM, 43%), and adsorbable organic halogen (AOX, 27%), but a decrease in the concentrations of 2 trihalonitromethanes (THNM2, 43%). Coupling ozonation with biofiltration prior to chlorination effectively lowered the formation potentials of all DBPs including CH, HK2, and THNM2, all of which increased after ozonation. The dynamics of DBP formation potentials during BAC filtration at different EBCTs followed first-order reaction kinetics. Minimum steady-state concentrations were attained at an EBCT of about 10-20 min, depending on the DBP species. The rate of reduction in DBP formation potentials varied among individual species before reaching their minimum concentrations. CH, HK2, and THNM2 had the highest rate constants of between 0.5 and 0.6 min -1 followed by HAN4 (0.4 min -1 ), THM4 (0.3 min -1 ), HAA8 (0.2 min -1 ), and AOX (0.1 min -1 ). At an EBCT of 15 min, the reduction in formation potential for most DBPs was less than 50% but was higher than 70% for CH, HK2, and THNM2. The formation of bromine-containing DBPs increased with increasing EBCT, most likely due to an increase in Br - /DOC ratio. Overall, this study demonstrated that the combination of ozonation and biofiltration is an effective approach to mitigate DBP formation during drinking water treatment. Copyright © 2016 Elsevier Ltd. All rights reserved.

An Overview of the SOLVE-THESEO 2000 Campaign

NASA Technical Reports Server (NTRS)

Newman, Paul A.; Harris, Neil R. P.; Adriani, Alberto; Amanatidis, Georgios T.; Anderson, James G.; Braathen, Geir O.; Brune, William H.; Carslaw, Kenneth S.; Craig, Michael T.; DeCola, Philip E.

2001-01-01

Between November 1999 and April 2000, two major field experiments, the SAGE III Ozone Loss and Validation Experiment (SOLVE) and the Third European Stratospheric Experiment on Ozone (THESEO 2000), collaborated to form the largest field campaign yet mounted to study Arctic ozone loss. This international campaign involved more than 500 scientists from over 20 countries spread across the high and mid-latitudes of the northern hemisphere. The main scientific aims of SOLVE-THESEO 2000 were to study (a) the processes leading to ozone loss in the Arctic vortex and (b) the effect on ozone amounts over northern mid-latitudes. The campaign included satellites, heavy lift balloon launches, 6 different aircraft, ground stations, and scores of ozone-sonde. Campaign activities were principally conducted in 3 intensive measurement phases centered on early December 1999, late January 2000, and early March 2000. Observations made during the campaign showed that temperatures were unusually cold in the polar lower stratosphere over the course of the 1999-2000 winter. These cold temperatures resulted in the formation of extensive polar stratospheric clouds (PSCs) across the Arctic. Heterogeneous chemical reactions on the surfaces of the PSC particles produced high levels of reactive chlorine within the polar vortex by early January. This reactive chlorine catalytically destroyed about 60% of the ozone in a layer near 20 km between late January and mid-March 2000.

Oxidation of sulfamethoxazole (SMX) by chlorine, ozone and permanganate--a comparative study.

PubMed

Gao, Shanshan; Zhao, Zhiwei; Xu, Yongpeng; Tian, Jiayu; Qi, Hong; Lin, Wei; Cui, Fuyi

2014-06-15

Sulfamethoxazole (SMX), a typical sulfonamide antibiotic, has been widely detected in secondary wastewater effluents and surface waters. In this work we investigated the oxidative degradation of SMX by commonly used oxidants of chlorine, ozone and permanganate. Chlorine and ozone were shown to be more effective for the removal of SMX (0.05-5.0mg/L), as compared with permanganate. Higher pH enhanced the oxidation of SMX by ozone and permanganate, but decreased the removal by chlorine. Moreover, the ozonation of SMX was significantly influenced by the presence of humic acid (HA), which exhibited negligible influence on the oxidation by chlorine and permanganate. Fairly lower mineralization of SMX occurred during the oxidation reactions, with the highest dissolved organic carbon (DOC) removal of 13% (for ozone). By using LC-MS/MS, 7, 5 and 5 oxidation products were identified for chlorine, ozone and permanganate and possible transformation pathways were proposed. It was shown that different oxidants shared some common pathways, such as the cleavage of SN bond, the hydroxylation of the benzene ring, etc. On the other hand, each of the oxidants also exhibited exclusive degradation mechanisms, leading to the formation of different transformation products (TPs). This work may provide useful information for the selection of oxidants in water treatment processes. Copyright © 2014 Elsevier B.V. All rights reserved.

Wintertime vertical variations in particulate matter (PM) and precursor concentrations in the San Joaquin Valley during the California Regional Coarse PM/Fine PM Air Quality Study.

PubMed

Brown, Steven G; Roberts, Paul T; McCarthy, Michael C; Lurmann, Frederick W; Hyslop, Nicole P

2006-09-01

Air quality monitoring was conducted at a rural site with a tower in the middle of California's San Joaquin Valley (SJV) and at elevated sites in the foothills and mountains surrounding the SJV for the California Regional PM10/ PM2.5 Air Quality Study. Measurements at the surface and n a tower at 90 m were collected in Angiola, CA, from December 2000 through February 2001 and included hourly black carbon (BC), particle counts from optical particle counters, nitric oxide, ozone, temperature, relative humidity, wind speed, and direction. Boundary site measurements were made primarily using 24-hr integrated particulate matter (PM) samples. These measurements were used to understand the vertical variations of PM and PM precursors, the effect of stratification in the winter on concentrations and chemistry aloft and at the surface, and the impact of aloft-versus-surface transport on PM concentrations. Vertical variations of concentrations differed among individual species. The stratification may be important to atmospheric chemistry processes, particularly nighttime nitrate formation aloft, because NO2 appeared to be oxidized by ozone in the stratified aloft layer. Additionally, increases in accumulation-mode particle concentrations in the aloft layer during a fine PM (PM2.5) episode corresponded with increases in aloft nitrate, demonstrating the likelihood of an aloft nighttime nitrate formation mechanism. Evidence of local transport at the surface and regional transport aloft was found; transport processes also varied among the species. The distribution of BC appeared to be regional, and BC was often uniformly mixed vertically. Overall, the combination of time-resolved tower and surface measurements provided important insight into PM stratification, formation, and transport.

Ozone reaction with interior building materials: Influence of diurnal ozone variation, temperature and humidity

NASA Astrophysics Data System (ADS)

Rim, Donghyun; Gall, Elliott T.; Maddalena, Randy L.; Nazaroff, William W.

2016-01-01

Elevated tropospheric ozone concentrations are associated with increased morbidity and mortality. Indoor ozone chemistry affects human exposure to ozone and reaction products that also may adversely affect health and comfort. Reactive uptake of ozone has been characterized for many building materials; however, scant information is available on how diurnal variation of ambient ozone influences ozone reaction with indoor surfaces. The primary objective of this study is to investigate ozone-surface reactions in response to a diurnally varying ozone exposure for three common building materials: ceiling tile, painted drywall, and carpet tile. A secondary objective is to examine the effects of air temperature and humidity. A third goal is to explore how conditioning of materials in an occupied office building might influence subsequent ozone-surface reactions. Experiments were performed at bench-scale with inlet ozone concentrations varied to simulate daytime (ozone elevated) and nighttime (ozone-free in these experiments) periods. To simulate office conditions, experiments were conducted at two temperatures (22 °C and 28 °C) and three relative humidity values (25%, 50%, 75%). Effects of indoor surface exposures were examined by placing material samples in an occupied office and repeating bench-scale characterization after exposure periods of 1 and 2 months. Deposition velocities were observed to be highest during the initial hour of ozone exposure with slow decrease in the subsequent hours of simulated daytime conditions. Daily-average ozone reaction probabilities for fresh materials are in the respective ranges of (1.7-2.7) × 10-5, (2.8-4.7) × 10-5, and (3.0-4.5) × 10-5 for ceiling tile, painted drywall, and carpet tile. The reaction probability decreases by 7%-47% across the three test materials after two 8-h periods of ozone exposure. Measurements with the samples from an occupied office reveal that deposition velocity can decrease or increase with time. Influence of temperature and humidity on ozone-surface reactivity was not strong.

The effect of ozone and open air factor on surface-attached and biofilm environmental Listeria monocytogenes.

PubMed

Nicholas, R; Dunton, P; Tatham, A; Fielding, L

2013-08-01

The effects of gaseous ozone and open air factor (OAF) on environmental Listeria monocytogenes attached to three common food contact surfaces were investigated. Listeria monocytogenes on different food contact surfaces was treated with ozone and OAF. Microbiological counts, scanning electron microscopy (SEM) and atomic force microscopy (AFM) were performed. Ozone at 10 ppm gave <1-log reduction when L. monocytogenes was attached to stainless steel, while 45 ppm gave a log reduction of 3.41. OAF gave better log reductions than 10 ppm ozone, but lower log reductions than 45 ppm. Significant differences were found between surfaces. Biofilm organisms were significantly more resistant than those surface attached on stainless steel. SEM and AFM demonstrated different membrane and cell surface modifications following ozone or OAF treatment. The strain used demonstrated higher resistance to ozone than previous studies. This may be due to the fact that it was isolated from a food manufacturing premises that used oxidizing disinfectants. OAF was more effective at reducing the levels of the organism than an ozone concentration of 10 ppm. Pathogen management strategies must account for resistance of environmental strains when validating cleaning and disinfection. OAF has shown potential for surface decontamination compared with ozone. SEM and AFM are valuable tools for determining mechanisms of action of antimicrobial agents. © 2013 The Society for Applied Microbiology.

Evaluation of Day and Nighttime Lower Tropospheric Ozone from Air Quality Models using TES and Ozonesondes

NASA Astrophysics Data System (ADS)

Osterman, G. B.; Neu, J. L.; Eldering, A.; Pinder, R. W.; Tang, Y.; McQueen, J.

2012-12-01

At night, ozone can be transported long distances above the surface inversion layer without chemical destruction or deposition. As the boundary layer breaks up in the morning, this nocturnal ozone can be mixed down to the surface and rapidly increase ozone concentrations at a rate that can rival chemical ozone production. Most regional scale models that are used for air quality forecasts and ozone source attribution do not adequately capture nighttime ozone concentrations and transport. We combine ozone profile data from the NASA Earth Observing System (EOS) Tropospheric Emission Spectrometer (TES) and other sensors, ozonesonde data collected during the INTEX Ozonesonde Network Study (IONS), EPA AirNow ground station ozone data, the Community Multi-Scale Air Quality (CMAQ) model, and the National Air Quality Forecast Capability (NAQFC) model to examine air quality events during August 2006. We present both aggregated statistics and case-study analyses that assess the relationship between the models' ability to reproduce surface air quality events and their ability to capture the vertical distribution of ozone both during the day and at night. We perform the comparisons looking at the geospatial dependence in the differences between the measurements and models under different surface ozone conditions.

Bromide's effect on DBP formation, speciation, and control; Part 1: Ozonation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shukairy, H.M.; Summers, R.S.; Miltner, R.J.

1994-06-01

The effect of variable ozone dosage and bromide concentration on the formation of organic disinfection by-products (DBPs) and bromate were evaluated. Low ozone dosages resulted in oxidation of organic precursors, yielding decreases in the formation potential for total trihalomethanes (THMs), six haloacetic acids (HAAs), and total organic halide (TOX). Increasing the ozone dosage oxidized bromide to bromate, decreasing the bromide for incorporation into DBPs. Bromate concentrations were linearly correlated with ozone residuals. Changes in the bromine incorporation factors n and n[prime] reflected differences in the resulting speciation of THMs and HAAs, respectively. Because TOX measurements based on chloride equivalence maymore » underestimate the halogenated DBP yield for high-bromide waters, a procedure is described whereby bromide and bromate concentrations were used to correct the TOX measurement.« less

Total ozone and surface temperature correlations during 1972 - 1981

NASA Technical Reports Server (NTRS)

Parsons, C. L.

1983-01-01

Ten years of Dobson spectrophotometer total ozone measurements and surface temperature observations were used to construct monthly mean values of the two parameters. The variability of both parameters is greatest in the months of January and February. Indeed, in January there is an apparent correlation between high total ozone values and abnormally low surface temperatures. However, the correlation does not hold in February. By reviewing the history of stratospheric warmings during this period, it is argued that the ozone and surface temperature correlation is influenced by the advection or lack of advection of ozone rich arctic air resulting from sudden stratospheric warmings.

Disinfection of fresh chicken breast fillets with in-package atmospheric cold plasma: effect of treatment voltage and time

USDA-ARS?s Scientific Manuscript database

Effects of treatment voltage and time of in-package atmospheric cold plasma (ACP) were studied on ozone formation, microbiological quality, surface color, and pH of fresh chicken fillets. Samples were sealed in food trays in air, treated with a dielectric-barrier-discharge (DBD) ACP system, and stor...

Options and limitations for bromate control during ozonation of wastewater.

PubMed

Soltermann, Fabian; Abegglen, Christian; Tschui, Manfred; Stahel, Sandro; von Gunten, Urs

2017-06-01

Wastewater treatment plants (WWTPs) are important point sources for micropollutants, which are harmful to freshwater organisms. Ozonation of wastewater is a powerful option to abate micropollutants, but may result in the formation of the potentially toxic oxidation by-product bromate in bromide-containing wastewaters. This study investigates options to reduce bromate formation during wastewater ozonation by (i) reducing the bromide concentration of the wastewater, (ii) lowering the ozone dose during wastewater treatment and (iii) adding hydrogen peroxide to limit the lifetime of ozone and quench the intermediates of the bromate formation pathway. Two examples demonstrate that a high share of bromide in wastewater can originate from single point sources (e.g., municipal waste incinerators or landfills). The identification of major point sources requires laborious sampling campaigns, but may facilitate the reduction of the bromide load significantly. To reduce the bromate formation by lowering the ozone dose interferes with the aim to abate micropollutants. Therefore, an additional treatment is necessary to ensure the elimination of micropollutants. Experiments at a pilot-plant illustrate that a combined treatment (ozone/powdered activated carbon) allows to eliminate micropollutants with low bromate yields. Furthermore, the addition of hydrogen peroxide was investigated at bench-scale. The bromate yields could be reduced by ∼50% and 65% for a hydrogen peroxide dose of 5 and 10 mg L -1 , respectively. In conclusion, there are options to reduce the bromate formation during wastewater ozonation, however, they are not simple with sometimes limited efficiency. Copyright © 2017 Elsevier Ltd. All rights reserved.

OZONE BYPRODUCT FORMATION

EPA Science Inventory

The use of ozone for water treatment has been increasing as ozone has great potential for degrading water pollutants and inactivating viruses, Giardia cysts, and Cryptosporidium oocysts. Although it appears that ozone generates less undesirable disinfection by-products (DBPs) th...

Potential of select intermediate-volatility organic compounds and consumer products for secondary organic aerosol and ozone formation under relevant urban conditions

NASA Astrophysics Data System (ADS)

Li, Weihua; Li, Lijie; Chen, Chia-li; Kacarab, Mary; Peng, Weihan; Price, Derek; Xu, Jin; Cocker, David R.

2018-04-01

Emissions of certain low vapor pressure-volatile organic compounds (LVP-VOCs) are considered exempt to volatile organic compounds (VOC) regulations due to their low evaporation rates. However, these compounds may still play a role in ambient secondary organic aerosol (SOA) and ozone formation. The LVP-VOCs selected for this work are categorized as intermediate-volatility organic compounds (IVOCs) according to their vapor pressures and molecular formulas. In this study, the evaporation rates of 14 select IVOCs are investigated with half of them losing more than 95% of their mass in less than one month. Further, SOA and ozone formation are presented from 11 select IVOCs and 5 IVOC-containing generic consumer products under atmospherically relevant conditions using varying radical sources (NOx and/or H2O2) and a surrogate reactive organic gas (ROG) mixture. Benzyl alcohol (0.41), n-heptadecane (0.38), and diethylene glycol monobutyl ether (0.16) are determined to have SOA yields greater than 0.1 in the presence of NOx and a surrogate urban hydrocarbon mixture. IVOCs also influence ozone formation from the surrogate urban mixture by impacting radical levels and NOx availability. The addition of lab created generic consumer products has a weak influence on ozone formation from the surrogate mixture but strongly affects SOA formation. The overall SOA and ozone formation of the generic consumer products could not be explained solely by the results of the pure IVOC experiments.

Photochemical ozone formation from petroleum refinery emissions

NASA Astrophysics Data System (ADS)

Sexton, Ken; Westberg, Hal

Atmospheric emissions from the Marathon oil refinery at Robinson, Illinois were investigated during June and July 1977. Surface and aerial measurements were used to provide an integrated, three dimensional monitoring network. Concentrations of ozone, oxides of nitrogen, sulfur dioxide, methane, carbon dioxide, individual non-methane hydrocarbons and halocarbons were recorded on a routine basis. In addition, meteorological parameters such as wind speed, wind direction, solar radiation and mixing height were also measured. The field monitoring study focused on three major areas: (1) characterization of gaseous components within the refinery effluent, especially nonmethane hydrocarbons and nitrogen oxides; (2) natural sunlight bag irradiation experiments to examine ozone forming potential of refinery emissions and (3) aerial measurements of changes in plume chemistry during the first six to eight hours of transport. Results indicate levels of hydrocarbons and nitrogen oxides were elevated downwind of the refinery. Concentrations within the effluent exceeded background values by as much as 300- and 10-fold, respectively. Irradiations of captured refinery emissions suggest excess photochemical ozone can be produced in the first 6 h, with amounts varying according to NMHC/NO x, ratios and initial NMHC concentrations. Real-time measurements on board the aircraft documented instances of ozone buildup in the refinery plume as it drifted downwind.

78 FR 11119 - Air Quality: Revision to Definition of Volatile Organic Compounds-Exclusion of trans

Federal Register 2010, 2011, 2012, 2013, 2014

2013-02-15

... tropospheric ozone formation. In the ``Rules and Regulations'' section of this Federal Register, we are making... compound makes a negligible contribution to tropospheric ozone formation.\\1\\ We are publishing a direct... standards for ozone under title I of the Clean Air Act (CAA). This proposed revision would add trans 1...

Retrieval of Surface Ozone from UV-MFRSR Irradiances using Deep Learning

NASA Astrophysics Data System (ADS)

Chen, M.; Sun, Z.; Davis, J.; Zempila, M.; Liu, C.; Gao, W.

2017-12-01

High concentration of surface ozone is harmful to humans and plants. USDA UV-B Monitoring and Research Program (UVMRP) uses Ultraviolet (UV) version of Multi-Filter Rotating Shadowband Radiometer (UV-MFRSR) to measure direct, diffuse, and total irradiances every three minutes at seven UV channels (i.e. 300, 305, 311, 317, 325, 332, and 368 nm channels with 2 nm full width at half maximum). Based on the wavelength dependency of aerosol optical depths, there have been plenty of literatures exploring retrieval methods of total column ozone from UV-MFRSR measurements. However, few has explored the retrieval of surface ozone. The total column ozone is the integral of the multiplication of ozone concentration (varying by height and time) and cross section (varying by wavelength and temperature) over height. Because of the distinctive values of ozone cross section in the UV region, the irradiances at seven UV channels have the potential to resolve the ozone concentration at multiple vertical layers. If the UV irradiances at multiple time points are considered together, the uncertainty or the vertical resolution of ozone concentrations can be further improved. In this study, the surface ozone amounts at the UVMRP station located at Billings, Oklahoma are estimated from the adjacent (i.e. within 200 miles) US Environmental Protection Agency (EPA) surface ozone observations using the spatial analysis technique. Then, the (direct normal) irradiances of UVMRP at one or more time points as inputs and the corresponding estimated surface ozone from EPA as outputs are fed into a pre-trained (dense) deep neural network (DNN) to explore the hidden non-linear relationship between them. This process could improve our understanding of their physical/mathematical relationship. Finally, the optimized DNN is tested with the preserved 5% of the dataset, which are not used during training, to verify the relationship.

Catalytic ozonation of dimethyl phthalate and chlorination disinfection by-product precursors over Ru/AC.

PubMed

Wang, Jianbing; Zhou, Yunrui; Zhu, Wanpeng; He, Xuwen

2009-07-15

Catalytic ozonation of dimethyl phthalate (DMP) in aqueous solution (5mg/L) under various reactions was performed to examine the effect of catalyst dosage, catalyst particle size, ozone dosage, and gas flow rate on the mineralization of DMP. The mineralization of DMP can be achieved via ozonation and the presence of Ru/AC could greatly accelerate the mineralization rate of DMP in ozonation process. In the continuous experiment of the Ru/AC catalyzed ozonation of DMP, total organic carbon (TOC) removals were kept stable around 75% during 42 h reaction. No leaching of ruthenium was observed in the treated water samples. The treatment of natural water using Ru/AC+O(3), Ru/AC+O(2) and ozonation alone was studied. In the Ru/AC+O(3) process, TOC removals, the reductions of the haloacetic acid formation potentials (HAAFPs), and the reductions of the trihalomethane formation potentials (THMFPs) of 11 water samples were 22-44%, 39-61% and 50-65%, respectively. Ru/AC+O(3) process was much more effective than ozonation alone for TOC removal and the reduction of disinfection by-product formation potential (DBPFP) in the treatment of natural water. It is a promising water treatment technology.

The formation of ozone and UV radiation from high-power pulsed electric discharges

NASA Astrophysics Data System (ADS)

Piskarev, I. M.; Ushkanov, V. A.; Selemir, V. D.; Spirov, G. M.; Malevannaya Pikar', I. A.; Zuimach, E. A.

2008-09-01

High-power electric discharges with pulse energies of from 0.15 J to 4 kJ were studied. The yields of UV photons and ozone were found to be approximately equal, which led us to conclude that discharge conditions under which UV radiation and ozone fully destroyed each other were possible. If ozone formation was suppressed, as when a negative volume charge was created in the spark gap region, the flux of UV photons reached 3 × 1023 photons/(cm2 s).

Influence of power supply on the generation of ozone and degradation of phenol in a surface discharge reactor

NASA Astrophysics Data System (ADS)

Zhao, Yan; Shang, Kefeng; Duan, Lijuan; Li, Yue; An, Jiutao; Zhang, Chunyang; Lu, Na; Li, Jie; Wu, Yan

2013-03-01

A surface Dielectric Barrier Discharge (DBD) reactor was utilized to degrade phenol in water. Different power supplies applied to the DBD reactor affect the discharge modes, the formation of chemically active species and thus the removal efficiency of pollutants. It is thus important to select an optimized power supply for the DBD reactor. In this paper, the influence of the types of power supplies including alternate current (AC) and bipolar pulsed power supply on the ozone generation in a surface discharge reactor was measured. It was found that compared with bipolar pulsed power supply, higher energy efficiency of O3 generation was obtained when DBD reactor was supplied with 50Hz AC power supply. The highest O3 generation was approximate 4 mg kJ-1 moreover, COD removal efficiency of phenol wastewater reached 52.3% after 3 h treatment under an AC peak voltage of 2.6 kV.

Field measurements of the ambient ozone formation potential in Beijing during winter

NASA Astrophysics Data System (ADS)

Crilley, Leigh; Kramer, Louisa; Thomson, Steven; Lee, James; Squires, Freya; Bloss, William

2017-04-01

The air quality issues in Beijing have been well-documented, and the severe air pollution levels result in a unique chemical mix in the urban boundary layer, both in terms of concentration and composition. As many of the atmospheric chemical process are non-linear and interlinked, this makes predictions difficult for species formed in atmosphere, such as ozone, requiring field measurements to understand these processes in order to guide mitigation efforts. To investigate the ozone formation potential of ambient air, we employed a custom built instrument to measure in near real time the potential for in situ ozone production, using an artificial light source. Our results are thus indicative of the ozone formation potential for the sampled ambient air mixture. Measurements were performed as part of the Air Pollution and Human Health (APHH) field campaign in November / December 2016 at a suburban site in central Beijing. We also conducted experiments to examine the ozone production sensitivity to NOx. We will present preliminarily results from ambient sampling and NOx experiments demonstrating changes in the ozone production potential during clean and haze periods in Beijing.

Atlas of TOMS ozone data collected during the Genesis of Atlantic Lows Experiment (GALE), 1986

NASA Technical Reports Server (NTRS)

Larko, David E.; Uccellini, Louis W.; Krueger, Arlin J.

1986-01-01

Data from the TOMS (Total Ozone Mapping Spectrometer) instrument aboard the Nimbus-7 satellite were collected daily in real time during the GALE (Genesis of Atlantic Lows Experiment) from January 15 through March 15, l986. The TOMS ozone data values were processed into GEMPAK format and transferred from the Goddard Space Flight Center to GALE operations in Raleigh-Durham, NC, in as little as three hours for use, in part, to direct aircraft research flights recording in situ measurements of ozone and water vapor in areas of interest. Once in GEMPAK format, the ozone values were processed into gridded form using the Barnes objective analysis scheme and contour plots of the ozone created. This atlas provides objectively analyzed contour plots of the ozone for each of the sixty days of GALE as well as four-panel presentations of the ozone analysis combined on the basis of GALE Intensive Observing Periods (IOP's).

Using Ozone Lidar to Investigate Sources of High Ozone Concentrations in the Western United States

NASA Astrophysics Data System (ADS)

Senff, C. J.; Langford, A. O.; Alvarez, R. J.; Brewer, Wm. A.; Banta, R. M.; Marchbanks, R. D.; Sandberg, S. P.; Weickmann, A. M.; Holloway, J. S.; Williams, E. J.

2016-06-01

We have used NOAA's Tunable Optical Profiler for Aerosol and oZone (TOPAZ) ozone lidar to investigate the sources of high surface ozone concentrations in two different regions of the western United States (US): the Uintah Basin in northeast Utah and Clark County in southern Nevada, which includes the city of Las Vegas. The Uintah Basin is a booming oil and gas producing region that often suffers from very high wintertime ozone concentrations. Clark County experiences violations of the US ozone standard primarily in spring and early summer despite a lack of any major local pollution sources. TOPAZ lidar observations, in conjunction with surface in situ measurements and model results, provided strong evidence that the high wintertime ozone concentrations in the Uintah Basin are primarily driven by local emissions associated with oil and gas exploration, whereas the Clark County ozone exceedances are often caused by ozone-rich air that is transported from the lower stratosphere all the way down to the earth's surface.

Why do Models Overestimate Surface Ozone in the Southeastern United States?

NASA Astrophysics Data System (ADS)

Travis, K.; Jacob, D.; Fisher, J. A.; Kim, S.; Marais, E. A.; Zhu, L.; Yu, K.; Miller, C. E.; Yantosca, R.; Payer Sulprizio, M.; Thompson, A. M.; Wennberg, P. O.; Crounse, J.; St Clair, J. M.; Cohen, R. C.; Laughner, J.; Dibb, J. E.; Hall, S. R.; Ullmann, K.; Wolfe, G.; Pollack, I. B.; Peischl, J.; Neuman, J. A.; Zhou, X.

2016-12-01

Ozone pollution in the Southeast US involves complex chemistry driven by emissions of anthropogenic nitrogen oxide radicals (NOx = NO + NO2) and biogenic isoprene. Model estimates of surface ozone concentrations tend to be biased high in the region and this is of concern for designing effective emission control strategies to meet air quality standards. We use detailed chemical observations from the SEAC4RS aircraft campaign in August and September 2013, interpreted with the GEOS-Chem chemical transport model at 0.25°×0.3125° horizontal resolution, to better understand the factors controlling surface ozone in the Southeast US. We find that the National Emission Inventory (NEI) for NO­x from the US Environmental Protection Agency (EPA) is too high in the Southeast and nationally by a factor of 2. This finding is based on SEAC4RS observations of NOx and its oxidation products, surface network observations of nitrate wet deposition fluxes, and OMI satellite observations of tropospheric NO2 columns. Upper tropospheric NO2 from lightning makes a large contribution to the satellite observations that must be accounted for when using these data to estimate surface NOx emissions. We find that only half of isoprene oxidation proceeds by the high-NOx pathway to produce ozone; this fraction is only moderately sensitive to changes in NOx emissions because isoprene and NOx emissions are spatially segregated. GEOS-Chem with reduced NOx emissions provides an unbiased simulation of ozone observations from the aircraft, and reproduces the observed ozone production efficiency in the boundary layer as derived from a regression of ozone and NOx oxidation products. However, the model is still biased high by 8±13 ppb relative to observed surface ozone in the Southeast US. Ozonesondes launched during midday hours show a 7 ppb ozone decrease from 1.5 km to the surface that GEOS-Chem does not capture. This may be caused by excessively dry conditions in the model, representing another factor important in the simulation of surface ozone.

Responses of surface ozone air quality to anthropogenic nitrogen deposition in the Northern Hemisphere

NASA Astrophysics Data System (ADS)

Zhao, Yuanhong; Zhang, Lin; Tai, Amos P. K.; Chen, Youfan; Pan, Yuepeng

2017-08-01

Human activities have substantially increased atmospheric deposition of reactive nitrogen to the Earth's surface, inducing unintentional effects on ecosystems with complex environmental and climate consequences. One consequence remaining unexplored is how surface air quality might respond to the enhanced nitrogen deposition through surface-atmosphere exchange. Here we combine a chemical transport model (GEOS-Chem) and a global land model (Community Land Model, CLM) to address this issue with a focus on ozone pollution in the Northern Hemisphere. We consider three processes that are important for surface ozone and can be perturbed by the addition of atmospheric deposited nitrogen - namely, emissions of biogenic volatile organic compounds (VOCs), ozone dry deposition, and soil nitrogen oxide (NOx) emissions. We find that present-day anthropogenic nitrogen deposition (65 Tg N a-1 to the land), through enhancing plant growth (represented as increases in vegetation leaf area index, LAI, in the model), could increase surface ozone from increased biogenic VOC emissions (e.g., a 6.6 Tg increase in isoprene emission), but it could also decrease ozone due to higher ozone dry deposition velocities (up to 0.02-0.04 cm s-1 increases). Meanwhile, deposited anthropogenic nitrogen to soil enhances soil NOx emissions. The overall effect on summer mean surface ozone concentrations shows general increases over the globe (up to 1.5-2.3 ppbv over the western US and South Asia), except for some regions with high anthropogenic NOx emissions (0.5-1.0 ppbv decreases over the eastern US, western Europe, and North China). We compare the surface ozone changes with those driven by the past 20-year climate and historical land use changes. We find that the impacts from anthropogenic nitrogen deposition can be comparable to the climate- and land-use-driven surface ozone changes at regional scales and partly offset the surface ozone reductions due to land use changes reported in previous studies. Our study emphasizes the complexity of biosphere-atmosphere interactions, which can have important implications for future air quality prediction.

Meteorologically-adjusted trend analysis of surface observed ozone at three monitoring sites in Delhi, India: 2007-2011

NASA Astrophysics Data System (ADS)

Biswas, J.; Farooqui, Z.; Guttikunda, S. K.

2012-12-01

It is well known that meteorological parameters have significant impact on surface ozone concentrations. Therefore it is important to remove the effects of meteorology on ozone concentrations to correctly estimate long-term trends in ozone levels due to the alterations in precursor emissions. This is important for the development of effectual control strategies. In this study surface observed ozone trends in New Delhi are analyzed using Komogorov-Zurbenko (KZ) filter, US EPA ozone adjustment due to weather approach and the classification and regression tree method. The statistical models are applied to the ozone data at three observational sites in New Delhi metropolitan areas, 1) Income Tax Office (ITO) 2) Sirifort and 3) Delhi College of Engineering (DCE). The ITO site is located adjacent to a traffic crossing, Sirifort is an urban site and the DCE site is located in a residential area. The ITO site is also influenced by local industrial emissions. DCE has higher ozone levels than the other two sites. It was found that ITO has lowest ozone concentrations amongst the three sites due to ozone titrating due to industrial and on-road mobile NOx emissions. The statistical methods employed can assess ozone trends at these sites with a high degree of confidence and the results can be used to gauge the effectiveness of control strategies on surface ozone levels in New Delhi.

Surface ozone variability at Kislovodsk Observatory

NASA Technical Reports Server (NTRS)

Elansky, Nikolay F.; Makarov, Oleg V.; Senik, Irina A.

1994-01-01

The results of the surface ozone observations at the Observatory 'Kislovodsk', situated in the North Caucasus at the altitude 2070 m a.s.l., are given. The observatory is in the background conditions and the variations of the surface ozone are determined by the natural dynamic and photochemical processes. The mean value of the concentration and its seasonal variations are very near to those obtained at the high-mountain stations in Alps. The daily variations have the features, which remain stable during all warm period of the year (April-October). These features, including the minimum of the surface ozone at noon, are formed by the mountain-valley circulation. The significant variations of the surface ozone are connected with the unstationary lee waves.

Impact of Surface Emissions to the Zonal Variability of Tropical Tropospheric Ozone and Carbon Monoxide for November 2004

NASA Technical Reports Server (NTRS)

Bowman, K. W.; Jones, D.; Logan, J.; Worden, H.; Boersma, F.; Chang, R.; Kulawik, S.; Osterman, G.; Worden, J.

2008-01-01

The chemical and dynamical processes governing the zonal variability of tropical tropospheric ozone and carbon monoxide are investigated for November 2004 using satellite observations, in-situ measurements, and chemical transport models in conjunction with inverse-estimated surface emissions. Vertical ozone profile estimates from the Tropospheric Emission Spectrometer (TES) and ozone sonde measurements from the Southern Hemisphere Additional Ozonesondes (SHADOZ) network show the so called zonal 'wave-one' pattern, which is characterized by peak ozone concentrations (70-80 ppb) centered over the Atlantic, as well as elevated concentrations of ozone over Indonesia and Australia (60-70 ppb) in the lower troposphere. Observational evidence from TES CO vertical profiles and Ozone Monitoring Instrument (OMI) NO2 columns point to regional surface emissions as an important contributor to the elevated ozone over Indonesia. This contribution is investigated with the GEOS-Chem chemistry and transport model using surface emission estimates derived from an optimal inverse model, which was constrained by TES and Measurements Of Pollution In The Troposphere (MOPITT) CO profiles (Jones et al., 2007). These a posteriori estimates, which were over a factor of 2 greater than climatological emissions, reduced differences between GEOS-Chem and TES ozone observations by 30-40% and led to changes in GEOS-Chem upper tropospheric ozone of up to 40% over Indonesia. The remaining residual differences can be explained in part by upper tropospheric ozone produced from lightning NOx in the South Atlantic. Furthermore, model simulations from GEOS-Chem indicate that ozone over Indonesian/Australian is more sensitive to changes in surface emissions of NOx than ozone over the tropical Atlantic.

Lower tropospheric ozone and aerosol measurements at a coastal mountain site in Central California

NASA Astrophysics Data System (ADS)

Post, A.; Faloona, I. C.; Lighthall, D.; Wexler, A. S.; Cliff, S. S.; Conley, S. A.; Zhao, Y.

2013-12-01

Increasing concern over the impacts of exogenous air pollution in California's Central Valley has prompted the establishment of a coastal, high altitude monitoring site at the Chews Ridge Observatory (1550 m) approximately 30 km east of Point Sur in Monterey County, operated by the Monterey Institute for Research in Astronomy. Eighteen months of ozone and aerosol measurements are presented in the context of long-range transport and its potential impact on surface air quality in the southern San Joaquin Valley. Moreover, several ozone surveys have been conducted by aircraft upwind, over the Pacific Ocean, and downwind, over the Central Valley, to characterize horizontal and vertical transport across the coastal mountains. Diurnal variations present at Chews Ridge indicate the formation of a convective boundary layer on the ridge during the daytime leading to a 6-8 ppb decrease in ozone accompanied by a rise in specific humidity of 2-3 g/kg due to coupling with the forest. During the nighttime, the sampled air masses are representative of free tropospheric conditions which have not been significantly influenced by either local emissions nor convective coupling to the surface. The maximum daily 8-hour average ozone concentration at Chews Ridge is used in lagged correlation analysis with two sites in the San Joaquin Valley, Fresno and Arvin, to de-emphasize the influence of locally produced, diurnally cycled ozone. The correlation coefficients (~0.60) peak between 9-21 hour lag and tend to decorrelate completely within 4-5 days. These and other analyses along with data provided by the aircraft sampling are used to provide a deeper understanding of ozone transport into the San Joaquin Valley. Aerosol size is measured with a scanning mobility particle sizer and composition is analyzed with an 8-stage rotating drum impactor whose substrates are characterized by X-ray fluorescence. Various elemental ratios and back trajectory calculations are used to infer the temporal patterns of influence that long range transport has on California air quality.

Effect of duty-cycles on the air plasma gas-phase of dielectric barrier discharges

NASA Astrophysics Data System (ADS)

Barni, R.; Biganzoli, I.; Dell'Orto, E. C.; Riccardi, C.

2015-10-01

An experimental investigation concerning the effects of a duty-cycle in the supply of a dielectric barrier discharge in atmospheric pressure air has been performed. Electrical characteristics of the discharge have been measured, focusing mainly on the statistical properties of the current filaments and on dielectric surface charging, both affected by the frequent repetition of breakdown imposed by the duty-cycle. Information on the gas-phase composition was gathered too. In particular, a strong enhancement in the ozone formation rate is observed when suitable long pauses separate the active discharge phases. A simulation of the chemical kinetics in the gas-phase, based on a simplified discharge modeling, is briefly described in order to shed light on the observed increase in ozone production. The effect of a duty-cycle on surface modification of polymeric films in order to increase their wettability has been investigated too.

Global Ozone and Reactive Nitrogen : Composition, Chemistry and Sources

NASA Technical Reports Server (NTRS)

Sing, Hanwant B.; Bradshaw, J.; Davis, D.; Gregory, G.; Talbot, R.

1994-01-01

Ozone plays a central role in the chemistry of the atmosphere both as an ultraviolet shield and as a source of hydroxyl radicals (OH), a potent initiator of atmospheric chemistry. There is evidence to suggest that the ozone abundance in the troposphere (0-10 km) has doubled since the industrial revolution and continues to increase to date. The principle reason for this increase is thought to be the increasing emissions of nitrogen oxides (NO(x)) from anthropogenic activities. Although NO(x) is highly reactive and its products such as HN03 are easily removed by deposition, it now appears that its chemistry is quite complex and it can be transported over long distances via its conversion to a variety of nitrates and penetrates. The sources of atmospheric NO(x) include free tropospheric sources such as lightning and subsonic aircraft, as well as surface emissions which are transported to the free troposphere via convective processes. Recent experimental and theoretical studies have tried to unravel the chemistry of reactive nitrogen species, its sources, and their role in ozone formation. In this presentation we shall describe the results from these studies.

Formation of assimilable organic carbon during oxidation of natural waters with ozone, chlorine dioxide, chlorine, permanganate, and ferrate.

PubMed

Ramseier, Maaike K; Peter, Andreas; Traber, Jacqueline; von Gunten, Urs

2011-02-01

Five oxidants, ozone, chlorine dioxide, chlorine, permanganate, and ferrate were studied with regard to the formation of assimilable organic carbon (AOC) and oxalate in absence and presence of cyanobacteria in lake water matrices. Ozone and ferrate formed significant amounts of AOC, i.e. more than 100 μg/L AOC were formed with 4.6 mg/L ozone and ferrate in water with 3.8 mg/L dissolved organic carbon. In the same water samples chlorine dioxide, chlorine, and permanganate produced no or only limited AOC. When cyanobacterial cells (Aphanizomenon gracile) were added to the water, an AOC increase was detected with ozone, permanganate, and ferrate, probably due to cell lysis. This was confirmed by the increase of extracellular geosmin, a substance found in the selected cyanobacterial cells. AOC formation by chlorine and chlorine dioxide was not affected by the presence of the cells. The formation of oxalate upon oxidation was found to be a linear function of the oxidant consumption for all five oxidants. The following molar yields were measured in three different water matrices based on oxidant consumed: 2.4-4.4% for ozone, 1.0-2.8% for chlorine dioxide and chlorine, 1.1-1.2% for ferrate, and 11-16% for permanganate. Furthermore, oxalate was formed in similar concentrations as trihalomethanes during chlorination (yield ∼ 1% based on chlorine consumed). Oxalate formation kinetics and stoichiometry did not correspond to the AOC formation. Therefore, oxalate cannot be used as a surrogate for AOC formation during oxidative water treatment. Copyright © 2010 Elsevier Ltd. All rights reserved.

Children's Models of the Ozone Layer and Ozone Depletion.

ERIC Educational Resources Information Center

Christidou, Vasilia; Koulaidis, Vasilis

1996-01-01

The views of 40 primary students on ozone and its depletion were recorded through individual, semi-structured interviews. The data analysis resulted in the formation of a limited number of models concerning the distribution and role of ozone in the atmosphere, the depletion process, and the consequences of ozone depletion. Identifies five target…

Sensitivity of volatile organic compounds (VOCs) and ozone to land surface processes and vegetation distributions in California

NASA Astrophysics Data System (ADS)

Zhao, C.; Huang, M.; Fast, J. D.; Berg, L. K.; Qian, Y.; Guenther, A. B.; Gu, D.; Shrivastava, M. B.; Liu, Y.; Walters, S.; Jin, J.

2014-12-01

Current climate models still have large uncertainties in estimating biogenic trace gases, which can significantly affect secondary organic aerosol (SOA) formation and ultimately aerosol radiative forcing. These uncertainties result from many factors, including coupling strategy between biogenic emissions and land-surface schemes and specification of vegetation types, both of which can affect the simulated near-surface fluxes of biogenic volatile organic compounds (VOCs). In this study, sensitivity experiments are conducted using the Weather Research and Forecasting model with chemistry (WRF-Chem) to examine the sensitivity of simulated VOCs and ozone to land surface processes and vegetation distributions in California. The measurements collected during the California Nexus of Air Quality and Climate Experiment (CalNex) and the Carbonaceous Aerosol and Radiative Effects Study (CARES) conducted during May and June of 2010 provide a good opportunity to evaluate the simulations. First, the biogenic VOC emissions in the WRF-Chem simulations with the two land surface schemes, Noah and CLM4, are estimated by the Model of Emissions of Gases and Aerosols from Nature version one (MEGANv1), which has been publicly released and widely used with WRF-Chem. The impacts of land surface processes on estimating biogenic VOC emissions and simulating VOCs and ozone are investigated. Second, in this study, a newer version of MEGAN (MEGANv2.1) is coupled with CLM4 as part of WRF-Chem to examine the sensitivity of biogenic VOC emissions to the MEGAN schemes used and determine the importance of using a consistent vegetation map between a land surface scheme and the biogenic VOC emission scheme. Specifically, MEGANv2.1 is embedded into the CLM4 scheme and shares a consistent vegetation map for estimating biogenic VOC emissions. This is unlike MEGANv1 in WRF-Chem that uses a standalone vegetation map that differs from what is used in land surface schemes. Furthermore, we examine the impact of vegetation distribution on simulating VOCs and ozone by comparing coupled WRF-Chem-CLM-MEGANv2.1 simulations using multiple vegetation maps.

Tropospheric ozone in the western Pacific Rim: Analysis of satellite and surface-based observations along with comprehensive 3-D model simulations

NASA Technical Reports Server (NTRS)

Young, Sun-Woo; Carmichael, Gregory R.

1994-01-01

Tropospheric ozone production and transport in mid-latitude eastern Asia is studied. Data analysis of surface-based ozone measurements in Japan and satellite-based tropospheric column measurements of the entire western Pacific Rim are combined with results from three-dimensional model simulations to investigate the diurnal, seasonal and long-term variations of ozone in this region. Surface ozone measurements from Japan show distinct seasonal variation with a spring peak and summer minimum. Satellite studies of the entire tropospheric column of ozone show high concentrations in both the spring and summer seasons. Finally, preliminary model simulation studies show good agreement with observed values.

Isotope Effect in Ozone Formation: Assessing the Relationship Between Photon Energy and Stabilization

NASA Astrophysics Data System (ADS)

Gardner, D. A.; Chakraborty, S.; Thiemens, M. H.

2016-12-01

While it has been found that the isotopic fractionation of oxygen during processes such as evaporation or precipitation happens mass-dependently (i.e. δ17O = 0.52δ18O), it was discovered in the 1980's that during ozone (O3) formation, fractionation occurs mass-independently (i.e. δ17O = δ18O). The purpose of this series of photolysis experiments was to assess the relationship between incoming photon energy and anomalous oxygen enrichment during the formation of ozone from molecular oxygen, a topic that has not yet been explored in detail, to our knowledge. A UV lamp emitting wavelengths of 184.9 and 253.7 nm was used to photolyze molecular oxygen in a vacuum chamber to form ozone. The ozone was separated from unreacted oxygen by trapping ozone with liquid nitrogen in the reaction chamber finger. After the untrapped oxygen was evacuated, the ozone was collected in a sample tube with molecular sieve, which allows the ozone to break down to molecular oxygen. In these experiments, mass-spectroscopy was performed on molecular oxygen to measure the isotopic composition (δ17O and δ18O). A limited number of experiments were performed using two different collection methods: collection immediately following formation and collection at the end of photon exposure, allowing a certain amount of ozone to dissociate and recycle. We compared the enrichments of against in ozone from the two above mentioned cases. In the former case, the enrichment in δ17O and δ18O follow a linear relationship of 0.92 (normalized to starting composition), consistent with literature data. Whereas for the latter case, the measured slope value was 0.83. The individual δ17O and δ18O values were also relatively higher compared to the first case. Differences for these two cases may arise due to the additional contribution from ozone dissociation (follow a nearly mass-dependent slope, i.e. 0.5) in the second case. More experiments are underway in an attempt to understand the stabilization step of ozone formation (i.e. energy dependence) and associated isotope effect. Results from different photon energies (e.g. 116.5, 121.6, and 123.6 nm) from different UV lamps will be presented in the meeting.

Long-term variation of Surface Ozone, NO2, temperature and relative humidity on crop yield over Andhra Pradesh (AP), India

NASA Astrophysics Data System (ADS)

Arunachalam, M. S.; Obili, Manjula; Srimurali, M.

2016-07-01

Long-term variation of Surface Ozone, NO2, Temperature, Relative humidity and crop yield datasets over thirteen districts of Andhra Pradesh(AP) has been studied with the help of OMI, MODIS, AIRS, ERA-Interim re-analysis and Directorate of Economics and Statistics (DES) of AP. Inter comparison of crop yield loss estimates according to exposure metrics such as AOT40 (accumulated ozone exposure over a threshold of 40) and non-linear variation of surface temperature for twenty and eighteen varieties of two major crop growing seasons namely, kharif (April-September) and rabi (October-March), respectively has been made. Study is carried to establish a new crop-yield-exposure relationship for different crop cultivars of AP. Both ozone and temperature are showing a correlation coefficient of 0.66 and 0.87 with relative humidity; and 0.72 and 0.80 with NO2. Alleviation of high surface ozone results in high food security and improves the economy thereby reduces the induced warming of the troposphere caused by ozone. Keywords: Surface Ozone, NO2, Temperature, Relative humidity, Crop yield, AOT 40.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Newchurch, M.

The objectives of this research were to: (1) examine empirically the aerosol effect on Umkehr ozone profiles using SAGE II aerosol and ozone data; (2) examine theoretically the aerosol effect on Umkehr ozone profiles; (3) examine the differences between SAGE II ozone profiles and both old- and new-format Umkehr ozone profiles for ozone-trend information; (4) reexamine SAGE I-Umkehr ozone differences with the most recent version of SAGE I data; and (5) contribute to the SAGE II science team.

Aviation-attributable ozone as a driver for changes in mortality related to air quality and skin cancer

NASA Astrophysics Data System (ADS)

Eastham, Sebastian D.; Barrett, Steven R. H.

2016-11-01

Aviation is a significant source of tropospheric ozone, which is a critical UV blocking agent, an indirect precursor to the formation of particulate matter, and a respiratory health hazard. To date, investigations of human health impacts related to aviation emissions have focused on particulate matter, and no global estimate yet exists of the combined health impact of aviation due to ozone, particulate matter and UV exposure changes. We use a coupled tropospheric-stratospheric chemical-transport model with a global aviation emissions inventory to estimate the total impact of aviation on all three risk factors. We find that surface ozone due to aviation emissions is maximized during hemispheric winter due to the greater wintertime chemical lifetime of ozone, but that a smaller enhancement of 0.5 ppbv occurs during summertime. This summertime increase results in an estimated 6,800 premature mortalities per year due to ozone exposure, over three times greater than previous estimates. During the winter maximum, interaction with high background NOx concentrations results in enhanced production of nitrate aerosol and increased annual average exposure to particulate matter. This ozone perturbation is shown to be the driving mechanism behind an additional 9,200 premature mortalities due to exposure to particulate matter. However, the increase in tropospheric ozone is also found to result in 400 fewer mortalities due to melanoma skin cancer in 2006. This is the first estimate of global melanoma mortality due to aviation, and the first estimate of skin cancer mortality impacts due to aviation using a global chemical transport model.

Impact of chemical lateral boundary conditions in a regional air quality forecast model on surface ozone predictions during stratospheric intrusions

NASA Astrophysics Data System (ADS)

Pendlebury, Diane; Gravel, Sylvie; Moran, Michael D.; Lupu, Alexandru

2018-02-01

A regional air quality forecast model, GEM-MACH, is used to examine the conditions under which a limited-area air quality model can accurately forecast near-surface ozone concentrations during stratospheric intrusions. Periods in 2010 and 2014 with known stratospheric intrusions over North America were modelled using four different ozone lateral boundary conditions obtained from a seasonal climatology, a dynamically-interpolated monthly climatology, global air quality forecasts, and global air quality reanalyses. It is shown that the mean bias and correlation in surface ozone over the course of a season can be improved by using time-varying ozone lateral boundary conditions, particularly through the correct assignment of stratospheric vs. tropospheric ozone along the western lateral boundary (for North America). Part of the improvement in surface ozone forecasts results from improvements in the characterization of near-surface ozone along the lateral boundaries that then directly impact surface locations near the boundaries. However, there is an additional benefit from the correct characterization of the location of the tropopause along the western lateral boundary such that the model can correctly simulate stratospheric intrusions and their associated exchange of ozone from stratosphere to troposphere. Over a three-month period in spring 2010, the mean bias was seen to improve by as much as 5 ppbv and the correlation by 0.1 depending on location, and on the form of the chemical lateral boundary condition.

Products of BVOC oxidation: ozone and organic aerosols

NASA Astrophysics Data System (ADS)

Wildt, Jürgen; Andres, Stefanie; Carriero, Giulia; Ehn, Mikael; Fares, Silvano; Hoffmann, Thorsten; Hacker, Lina; Kiendler-Scharr, Astrid; Kleist, Einhard; Paoletti, Elena; Pullinen, Iida; Rohrer, Franz; Rudich, Yinon; Springer, Monika; Tillmann, Ralf; Wahner, Andreas; Wu, Cheng; Mentel, Thomas

2015-04-01

Biogenic Volatile Organic Compounds (BVOC) are important precursors in photochemical O3 and secondary organic aerosol (SOA) formation. We conducted a series of laboratory experiments with OH-induced oxidation of monoterpenes to elucidate pathways and efficiencies of O3 and SOA formation. At high NOx conditions ([BVOC] / [NOx] < 7 ppbC / ppb) photochemical ozone formation was observed. For -pinene as individual BVOC as well as for the monoterpene mixes emitted from different plant species we observed increasing ozone formation with increasing [NOX]. Between 2 and 3 O3-molecules were formed from 1 monoterpene when ozone formation was BVOC limited. Under such high NOX conditions, new particle formation was suppressed. Increasing [BVOC] / [NOX] ratios caused increasing efficiency of new particle formation indicating that peroxy radicals are the key intermediates in both, photochemical ozone- and new particle formation. The classical chemistry of peroxy radicals is well established (e.g. Master Chemical Mechanism). Peroxy radicals are produced by addition of molecular oxygen to the alkyl radical formed after OH attack at the BVOC. They either react with NO which leads to ozone formation or they react with other peroxy radicals and form chemically stable products (hydroperoxides, alkoholes and ketones). Much less knowledge exists on such reactions for Highly Oxidized Peroxy Radicals, (HOPR). Such HOPR were observed during ozonolysis of several volatiles and, in case of monoterpenes as precursors, they can contain more than 12 Oxygen atoms (Mentel et al., 2015). Although the OH-initiated formation of HOPR is yet not fully understood, their basic gas phase reactions seem to follow classical photochemical rules. In reactions with NO they can act as precursor for O3 and in reactions with other HOPR or with classical less oxidized peroxy radicals they can form highly oxidized stable products and alkoxy radicals. In addition, HOPR-HOPR reactions lead to the formation of dimers that, in case of monoterpenes as reactants, consist of a skeleton with 20 carbon atoms. These dimers seem to play a major role in new particle formation and their existence may explain the observations of Wildt et al. (2014) who found power law dependence with an exponent approaching -2 between new particle formation and ozone formation. The monomer products of HOPR-HOPR reactions play a dominant role in SOA mass formation because their vapour pressures are low enough to allow condensation on pre-existing particulate matter (Ehn et al., 2014). Furthermore, the minor impacts of NOX on particle mass formation (Wildt et al., 2014) are explainable by similar yields of alkoxy radicals in HOPR-HOPR and HOPR-NO reactions, respectively.

Climate Change Impacts on Projections of Excess Mortality at 2030 using Spatially-Varying Ozone-Temperature Risk Surfaces

PubMed Central

Wilson, Ander; Reich, Brian J.; Nolte, Christopher G.; Spero, Tanya L.; Hubbell, Bryan; Rappold, Ana G.

2017-01-01

We project the change in ozone-related mortality burden attributable to changes in climate between a historical (1995–2005) and near-future (2025–2035) time period while incorporating a nonlinear and synergistic effect of ozone and temperature on mortality. We simulate air quality from climate projections varying only biogenic emissions and holding anthropogenic emissions constant, thus attributing changes in ozone only to changes in climate and independent of changes in air pollutant emissions. We estimate nonlinear, spatially-varying, ozone-temperature risk surfaces for 94 US urban areas using observed data. Using the risk surfaces and climate projections we estimate daily mortality attributable to ozone exceeding 40 ppb (moderate level) and 75 ppb (US ozone NAAQS) for each time period. The average increases in city-specific median April-October ozone and temperature between time periods are 1.02 ppb and 1.94°F; however, the results varied by region. Increases in ozone due to climate change result in an increase in ozone-mortality burden. Mortality attributed to ozone exceeding 40 ppb increases by 7.7% (1.6%, 14.2%). Mortality attributed to ozone exceeding 75 ppb increases by 14.2% (1.6%, 28.9%). The absolute increase in excess ozone mortality is larger for changes in moderate ozone levels, reflecting the larger number of days with moderate ozone levels. PMID:27005744

The TOAR database on observations of surface ozone (and more)

NASA Astrophysics Data System (ADS)

Schultz, M. G.; Schröder, S.; Cooper, O. R.; Galbally, I. E.; Petropavlovskikh, I. V.; von Schneidemesser, E.; Tanimoto, H.; Elshorbany, Y. F.; Naja, M. K.; Seguel, R. J.

2017-12-01

In support of the first Tropospheric Ozone Assessment Report (TOAR) a relational database of global surface ozone observations has been developed and populated with hourly measurement data and enhanced metadata. A comprehensive suite of ozone data products including standard statistics, health and vegetation impact metrics, and trend information, are made available through a common data portal and a web interface. These data form the basis of the TOAR analyses focusing on human health, vegetation, and climate relevant ozone issues. Cooperation among many data centers and individual researchers worldwide made it possible to build the world's largest collection of in-situ hourly surface ozone data covering the period from 1970 to 2015. By combining the data from almost 10,000 measurement sites around the world with global metadata information, new analyses of surface ozone have become possible, such as the first globally consistent characterisations of measurement sites as either urban or rural/remote. Exploitation of these global metadata allows for new insights into the global distribution, and seasonal and long-term changes of tropospheric ozone and they enable TOAR to perform the first, globally consistent analysis of present-day ozone concentrations and recent ozone changes with relevance to health, agriculture, and climate. This presentation will provide a summary of the TOAR surface observations database including recent additions of ozone precursor and meteorological data. We will demonstrate how the database can be accessed and the data can be used, and we will discuss its limitations and the potential for closing some of teh remaining data gaps.

Evaluating the effects of climate change on summertime ozone using a relative response factor approach for policymakers.

PubMed

Avise, Jeremy; Abraham, Rodrigo Gonzalez; Chung, Serena H; Chen, Jack; Lamb, Brian; Salathé, Eric P; Zhang, Yongxin; Nolte, Christopher G; Loughlin, Daniel H; Guenther, Alex; Wiedinmyer, Christine; Duhl, Tiffany

2012-09-01

The impact of climate change on surface-level ozone is examined through a multiscale modeling effort that linked global and regional climate models to drive air quality model simulations. Results are quantified in terms of the relative response factor (RRF(E)), which estimates the relative change in peak ozone concentration for a given change in pollutant emissions (the subscript E is added to RRF to remind the reader that the RRF is due to emission changes only). A matrix of model simulations was conducted to examine the individual and combined effects offuture anthropogenic emissions, biogenic emissions, and climate on the RRF(E). For each member in the matrix of simulations the warmest and coolest summers were modeled for the present-day (1995-2004) and future (2045-2054) decades. A climate adjustment factor (CAF(C) or CAF(CB) when biogenic emissions are allowed to change with the future climate) was defined as the ratio of the average daily maximum 8-hr ozone simulated under a future climate to that simulated under the present-day climate, and a climate-adjusted RRF(EC) was calculated (RRF(EC) = RRF(E) x CAF(C)). In general, RRF(EC) > RRF(E), which suggests additional emission controls will be required to achieve the same reduction in ozone that would have been achieved in the absence of climate change. Changes in biogenic emissions generally have a smaller impact on the RRF(E) than does future climate change itself The direction of the biogenic effect appears closely linked to organic-nitrate chemistry and whether ozone formation is limited by volatile organic compounds (VOC) or oxides of nitrogen (NO(x) = NO + NO2). Regions that are generally NO(x) limited show a decrease in ozone and RRF(EC), while VOC-limited regions show an increase in ozone and RRF(EC). Comparing results to a previous study using different climate assumptions and models showed large variability in the CAF(CB). We present a methodology for adjusting the RRF to account for the influence of climate change on ozone. The findings of this work suggest that in some geographic regions, climate change has the potential to negate decreases in surface ozone concentrations that would otherwise be achieved through ozone mitigation strategies. In regions of high biogenic VOC emissions relative to anthropogenic NO(x) emissions, the impact of climate change is somewhat reduced, while the opposite is true in regions of high anthropogenic NO(x) emissions relative to biogenic VOC emissions. Further, different future climate realizations are shown to impact ozone in different ways.

Identifying controlling factors of ground-level ozone levels over southwestern Taiwan using a decision tree

NASA Astrophysics Data System (ADS)

Chu, Hone-Jay; Lin, Chuan-Yao; Liau, Churn-Jung; Kuo, Yi-Ming

2012-12-01

Kaohsiung City and the suburban region of southwestern Taiwan have suffered from severe air pollution since becoming the largest center of heavy industry in Taiwan. The complex process of ozone (O3) formation and its precursor compounds (the volatile organic compounds (VOCs) and nitrogen oxide (NOx) emissions), accompanied by meteorological conditions, make controlling ozone difficult. Using a decision tree is especially appropriate for analyzing time series data that contain ozone levels and meteorological and explanatory variables for ozone formation. Results show that dominant variables such as temperature, wind speed, VOCs, and NOx can play vital roles in describing ozone variations among observations. That temperature and wind speed are highly correlated with ozone levels indicates that these meteorological conditions largely affect ozone variability. The results also demonstrate that spatial heterogeneity of ozone patterns are in coastal and inland areas caused by sea-land breeze and pollutant sources during high ozone episodes over southwestern Taiwan. This study used a decision tree to obtain quantitative insight into spatial distributions of precursor compound emissions and effects of meteorological conditions on ozone levels that are useful for refining monitoring plans and developing management strategies.

Improve observation-based ground-level ozone spatial distribution by compositing satellite and surface observations: A simulation experiment

NASA Astrophysics Data System (ADS)

Zhang, Yuzhong; Wang, Yuhang; Crawford, James; Cheng, Ye; Li, Jianfeng

2018-05-01

Obtaining the full spatial coverage of daily surface ozone fields is challenging because of the sparsity of the surface monitoring network and the difficulty in direct satellite retrievals of surface ozone. We propose an indirect satellite retrieval framework to utilize the information from satellite-measured column densities of tropospheric NO2 and CH2O, which are sensitive to the lower troposphere, to derive surface ozone fields. The method is applicable to upcoming geostationary satellites with high-quality NO2 and CH2O measurements. To prove the concept, we conduct a simulation experiment using a 3-D chemical transport model for July 2011 over the eastern US. The results show that a second order regression using both NO2 and CH2O column densities can be an effective predictor for daily maximum 8-h average ozone. Furthermore, this indirect retrieval approach is shown to be complementary to spatial interpolation of surface observations, especially in regions where the surface sites are sparse. Combining column observations of NO2 and CH2O with surface site measurements leads to an improved representation of surface ozone over simple kriging, increasing the R2 value from 0.53 to 0.64 at a surface site distance of 252 km. The improvements are even more significant with larger surface site distances. The simulation experiment suggests that the indirect satellite retrieval technique can potentially be a useful tool to derive the full spatial coverage of daily surface ozone fields if satellite observation uncertainty is moderate.

Plasmachemical and heterogeneous processes in ozonizers with oxygen activation by a dielectric barrier discharge

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mankelevich, Yu. A., E-mail: ymankelevich@mics.msu.su; Voronina, E. N.; Poroykov, A. Yu.

Plasmachemical and heterogeneous processes of generation and loss of ozone in the atmosphericpressure dielectric barrier discharge in oxygen are studied theoretically. Plasmachemical and electronic kinetics in the stage of development and decay of a single plasma filament (microdischarge) are calculated numerically with and without allowance for the effects of ozone vibrational excitation and high initial ozone concentration. The developed analytical approach is applied to determine the output ozone concentration taking into account ozone heterogeneous losses on the Al{sub 2}O{sub 3} dielectric surface. Using the results of quantummechanical calculations by the method of density functional theory, a multistage catalytic mechanism ofmore » heterogeneous ozone loss based on the initial passivation of a pure Al{sub 2}O{sub 3} surface by ozone and the subsequent interaction of O{sub 3} molecules with the passivated surface is proposed. It is shown that the conversion reaction 2O{sub 3} → 3O{sub 2} of a gas-phase ozone molecule with a physically adsorbed ozone molecule can result in the saturation of the maximum achievable ozone concentration at high specific energy depositions, the nonstationarity of the output ozone concentration, and its dependence on the prehistory of ozonizer operation.« less

Surface ozone at Nam Co in the inland Tibetan Plateau: variation, synthesis comparison and regional representativeness

NASA Astrophysics Data System (ADS)

Yin, Xiufeng; Kang, Shichang; de Foy, Benjamin; Cong, Zhiyuan; Luo, Jiali; Zhang, Lang; Ma, Yaoming; Zhang, Guoshuai; Rupakheti, Dipesh; Zhang, Qianggong

2017-09-01

Ozone is an important pollutant and greenhouse gas, and tropospheric ozone variations are generally associated with both natural and anthropogenic processes. As one of the most pristine and inaccessible regions in the world, the Tibetan Plateau has been considered as an ideal region for studying processes of the background atmosphere. Due to the vast area of the Tibetan Plateau, sites in the southern, northern and central regions exhibit different patterns of variation in surface ozone. Here, we present continuous measurements of surface ozone mixing ratios at Nam Co Station over a period of ˜ 5 years (January 2011 to October 2015), which is a background site in the inland Tibetan Plateau. An average surface ozone mixing ratio of 47.6 ± 11.6 ppb (mean ± standard deviation) was recorded, and a large annual cycle was observed with maximum ozone mixing ratios in the spring and minimum ratios during the winter. The diurnal cycle is characterized by a minimum in the early morning and a maximum in the late afternoon. Nam Co Station represents a background region where surface ozone receives negligible local anthropogenic emissions inputs, and the anthropogenic contribution from South Asia in spring and China in summer may affect Nam Co Station occasionally. Surface ozone at Nam Co Station is mainly dominated by natural processes involving photochemical reactions, vertical mixing and downward transport of stratospheric air mass. Model results indicate that the study site is affected differently by the surrounding areas in different seasons: air masses from the southern Tibetan Plateau contribute to the high ozone levels in the spring, and enhanced ozone levels in the summer are associated with air masses from the northern Tibetan Plateau. By comparing measurements at Nam Co Station with those from other sites on the Tibetan Plateau, we aim to expand the understanding of ozone cycles and transport processes over the Tibetan Plateau. This work may provide a reference for future model simulations.

a Study on the Physical and Chemical Properties of Stratospheric Aerosols.

NASA Astrophysics Data System (ADS)

Tabazadeh, Azadeh

The physical and chemical properties of stratospheric aerosols under background and perturbed conditions are discussed. First, a multi-component aerosol physical chemistry model was developed to study the composition and reactivity of stratospheric aerosols. The compositions are predicted from an equilibrium assumption between the condensed-and gas-phases, and they are calculated as a function of ambient temperature, relative humidity, and the total mass of nitric acid and sulfuric acid present per unit volume of air. The water and solute activity parameters in the aerosol model are derived from various laboratory sources, and the set of equilibrium equations are solved using a unique numerical scheme. The aerosol model is applied to study the formation of nitric acid-containing aerosols in the stratosphere. Also, the equilibrium compositions are used to estimate the extent of aqueous phase processing of chlorine species in the aerosol solutions. This processing can contribute to the depletion of the stratospheric ozone layer, especially after major volcanic eruptions where sulfate aerosols are more abundant. Second, a surface chemistry model was constructed that includes Langmuir trace-gas adsorption and desorption, Brunauer, Emmett and Teller adsorption of water vapor, surface poisoning, solvation and diffusion of molecules on the surface, chemical activation and reaction of adsorbates, and product desorption or reaction. This model is used to study the effects of relative humidity and other physical parameters on the efficiency of heterogeneous chemical processes which occur on the surfaces of solid polar stratospheric clouds. These heterogeneous chemical processes are responsible for the formation of the "ozone hole", can contribute to global ozone depletion, and may have tropospheric significance. Finally, a fluid dynamics and thermodynamics model of volcanic eruption columns was used to develop a scheme for predicting the extent of HCl removal from volcanic plumes. If most of the volcanically emitted chlorine stays in the upper atmosphere, the chlorine concentration in the stratosphere could increase by a factor of 2 to 10, leading to severe global ozone depletions. However, model results indicate that HCl is efficiently scavenged from volcanic plumes by supercooled water droplets, which form as the plume lofts and cools. HCl dissolution in these drops, followed by rainout, prevents substantial injections of chlorine into the stratosphere.

Vertical ozone characteristics in urban boundary layer in Beijing.

PubMed

Ma, Zhiqiang; Xu, Honghui; Meng, Wei; Zhang, Xiaoling; Xu, Jing; Liu, Quan; Wang, Yuesi

2013-07-01

Vertical ozone and meteorological parameters were measured by tethered balloon in the boundary layer in the summer of 2009 in Beijing, China. A total of 77 tethersonde soundings were taken during the 27-day campaign. The surface ozone concentrations measured by ozonesondes and TEI 49C showed good agreement, albeit with temporal difference between the two instruments. Two case studies of nocturnal secondary ozone maxima are discussed in detail. The development of the low-level jet played a critical role leading to the observed ozone peak concentrations in nocturnal boundary layer (NBL). The maximum of surface ozone was 161.7 ppbv during the campaign, which could be attributed to abundant precursors storage near surface layer at nighttime. Vertical distribution of ozone was also measured utilizing conventional continuous analyzers on 325-m meteorological observation tower. The results showed the NBL height was between 47 and 280 m, which were consistent with the balloon data. Southerly air flow could bring ozone-rich air to Beijing, and the ozone concentrations exceeded the China's hourly ozone standard (approximately 100 ppb) above 600 m for more than 12 h.

Ozone assisted oxidation of gaseous PCDD/Fs over CNTs-containing composite catalysts at low temperature.

PubMed

Wang, Qiulin; Tang, Minghui; Peng, Yaqi; Du, Cuicui; Lu, Shengyong

2018-05-01

Ozone assisted carbon nanotubes (CNTs) supported vanadium oxide/titanium dioxide (V/Ti-CNTs) or vanadium oxide-manganese oxide/titanium dioxide (V-Mn/Ti-CNTs) catalysts towards gaseous PCDD/Fs (polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans) catalytic oxidations at low temperature (150 °C) were investigated. The removal efficiency (RE) and decomposition efficiency (DE) of PCDD/Fs achieved with V-Mn/Ti-CNTs alone were 95% and 45% at 150 °C under a space velocity (SV) of 14000 h -1 ; yet, these values reached 99% and 91% when catalyst and low concentration (50 ppm) ozone were used in combined. The ozone promotion effect on catalytic activity was further enhanced with the addition of manganese oxide (MnO x ) and CNTs. Adding MnO x and CNTs in V/Ti catalysts facilitated the ozone decomposition (creating more active species on catalyst surface), thus, improved ozone utilization (demanding relatively lower ozone addition concentration). On the other hand, this study threw light upon ozone promotion mechanism based on the comparison of catalyst properties (i.e. components, surface area, surface acidity, redox ability and oxidation state) before and after ozone treatment. The experimental results indicate that a synergistic effect exists between catalyst and ozone: ozone is captured and decomposed on catalyst surface; meanwhile, the catalyst properties are changed by ozone in return. Reactive oxygen species from ozone decomposition and the accompanied catalyst properties optimization are crucial reasons for catalyst activation at low temperature. Copyright © 2018 Elsevier Ltd. All rights reserved.

Interfaces of electrical contacts in organic semiconductor devices

NASA Astrophysics Data System (ADS)

Demirkan, Korhan

Progress in organic semiconductor devices relies on better understanding of interfaces as well as material development. The engineering of interfaces that exhibit low resistance, low operating voltage and long-term stability to minimize device degradation is one of the crucial requirements. Photoelectron spectroscopy is a powerful technique to study the metal-semiconductor interfaces, allowing: (i) elucidation of the energy levels of the semiconductor and the contacts that determine Schottky barrier height, (ii) inspection of electrical interactions (such as charge transfer, dipole formation, formation of induced density of states or formation of polaron/bi-polaron states) that effect the energy level alignment, (iii) determination of interfacial chemistry, and (iv) estimation of interface morphology. In this thesis, we have used photoelectron spectroscopy extensively for detailed analysis of the metal organic semiconductor interfaces. In this study, we demonstrate the use of photoelectron spectroscopy for construction of energy level diagrams and display some results related to chemical tailoring of materials for engineering interfaces with lowered Schottky barriers. Following our work on the energy level alignment of poly(p-phenyene vinylene) based organic semiconductors on various substrates [Au, indium tin oxide, Si (with native oxide) and Al (with native oxide)], we tested controlling the energy level alignment by using polar self assembled molecules (SAMs). Photoelectron spectroscopy showed that, by introducing SAMs on the Au surface, we successfully changed the effective work function of Au surface. We found that in this case, the change in the effective work function of the metal surface was not reflected as a shift in the energy levels of the organic semiconductor, as opposed to the results achieved with different substrate materials. To investigate the chemical interactions at the metal/organic interface, we studied the metallization of poly(2-methoxy-5,2'-ethyl-hexyloxy-phenylene vinylene) (MEH-PPV), polystyrene (PS) and ozone treated polystyrene (PS-O3) surfaces by thermal deposition of aluminum. Photoelectron spectroscopy showed the degree of chemical interaction between Al and each polymer, for MEH-PPV, the chemical interactions were mainly through the C-O present in the side chain of the polymer structure. The chemical interaction of Al with polystyrene was less significant, but it showed a dramatic increase after ozone treatment of the polystyrene surface (due to the formation of exposed oxygen sites). Formation of metal oxide and metal-organic compound is detected during the Al metallization of MEH-PPV and ozone-treated PS surfaces. Our results showed that the condensation of Al on polymer surfaces is highly dependent on surface reactivity. Enormous differences were observed for the condensation coefficient of Al on PS and PS-O3 surfaces. For the inert PS surface, results showed that Al atoms poorly wet the polymer surface and form distributed clusters at the surface. Results on reactive polymer surfaces suggest morphology reminiscent of a Stranski-Krastanov-type growth and high contact area. Many studies have shown that the insertion of a thin interlayer of the oxide or fluoride of alkali or alkaline metals between the low work function electrode and the organic semiconductor layers dramatically lowers the onset voltage and increases the efficiency compared to identical devices without the insulating layer. Various modes have been suggested for the mechanism of device performance enhancement. We have investigated the chemical and electrical interaction of (i) LiF with MEH-PPV, (ii) Al with MEH-PPV in the presence of a thin LiF layer at the interface, and finally (iii) the interaction of Al with LiF. AFM and XPS data showed that LiF forms island on the surface. Our data in agreement with various existing models suggested the (i) alteration in the electronic properties under applied bias, (ii) doping of the organic semiconductor, (iii) formation of metal alloy (Au-Li). In addition to the possible electrical modifications at the interface suggested previously, our data also suggest a change in the film growth on LiF modified surfaces.

Trends in surface ozone concentrations at Arosa (Switzerland)

NASA Astrophysics Data System (ADS)

Staehelin, Johannes; Thudium, Juerg; Buehler, Ralph; Volz-Thomas, Andreas; Graber, Werner

During the years 1989-1991, ozone was measured at four sites around Arosa (Switzerland). One of these sites was identical with that, where surface ozone was measured in the 1950s (Götz and Volz, 1951; Perl, 1965). Comparison of both old and recent data indicates that surface ozone concentrations at Arosa have increased by a factor of approximately 2.2. The increase shows a seasonal variation with a relative increase of more than a factor of three in December and January. The results are discussed in the context of measurements made at other times, locations and altitudes. The comparison indicates that the increase in ozone levels at Arosa has most likely occured between the fifties and today. The measurements additionally suggest that photochemical ozone production in the free troposphere has significantly contributed to the observed ozone trends in winter.

Apparatus and process for the surface treatment of carbon fibers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Paulauskas, Felix Leonard; Ozcan, Soydan; Naskar, Amit K.

A method for surface treating a carbon-containing material in which carbon-containing material is reacted with decomposing ozone in a reactor (e.g., a hollow tube reactor), wherein a concentration of ozone is maintained throughout the reactor by appropriate selection of at least processing temperature, gas stream flow rate, reactor dimensions, ozone concentration entering the reactor, and position of one or more ozone inlets (ports) in the reactor, wherein the method produces a surface-oxidized carbon or carbon-containing material, preferably having a surface atomic oxygen content of at least 15%. The resulting surface-oxidized carbon material and solid composites made therefrom are also described.

The microbial killing capacity of aqueous and gaseous ozone on different surfaces contaminated with dairy cattle manure

PubMed Central

Lowe, James

2018-01-01

A high reactivity and leaving no harmful residues make ozone an effective disinfectant for farm hygiene and biosecurity. Our objectives were therefore to (1) characterize the killing capacity of aqueous and gaseous ozone at different operational conditions on dairy cattle manure-based pathogens (MBP) contaminated different surfaces (plastic, metal, nylon, rubber, and wood); (2) determine the effect of microbial load on the killing capacity of aqueous ozone. In a crossover design, 14 strips of each material were randomly assigned into 3 groups, treatment (n = 6), positive-control (n = 6), and negative-control (n = 2). The strips were soaked in dairy cattle manure with an inoculum level of 107–108 for 60 minutes. The treatment strips were exposed to aqueous ozone of 2, 4, and 9 ppm and gaseous ozone of 1and 9 ppm for 2, 4, and 8 minutes exposure. 3M™ Petrifilm™ rapid aerobic count plate and plate reader were used for bacterial culture. On smooth surfaces, plastic and metal, aqueous ozone at 4 ppm reduced MBP to a safe level (≥5-log10) within 2 minutes (6.1 and 5.1-log10, respectively). However, gaseous ozone at 9 ppm for 4 minutes inactivated 3.3-log10 of MBP. Aqueous ozone of 9 ppm is sufficient to reduce MBP to a safe level, 6.0 and 5.4- log10, on nylon and rubber surfaces within 2 and 8 minutes, respectively. On complex surfaces, wood, both aqueous and gaseous ozone at up to 9 ppm were unable to reduce MBP to a safe level (3.6 and 0.8-log10, respectively). The bacterial load was a strong predictor for reduction in MBP (P<0.0001, R2 = 0.72). We conclude that aqueous ozone of 4 and 9 ppm for 2 minutes may provide an efficient method to reduce MBP to a safe level on smooth and moderately rough surfaces, respectively. However, ozone alone may not an adequate means of controlling MBP on complex surfaces. PMID:29758045

Influence of Mountains on Arctic Tropospheric Ozone

NASA Astrophysics Data System (ADS)

Whiteway, J. A.; Seabrook, J.

2015-12-01

Tropospheric ozone was measured above Ellesmere Island in the Canadian Arctic during spring using a differential absorption lidar (DIAL). Analysis of the observations revealed that mountains had a significant effect on the vertical distribution of ozone. Ozone depletion events were observed when air that had spent significant time near to the frozen surface of the Arctic Ocean reached Eureka. This air arrived at Eureka by flowing over the surrounding mountains. Surface level ozone depletion events were not observed during periods when mountains blocked the flow of air from over the sea ice. In the case of blocking there was an enhancement in the amount of ozone near the surface as air from the mid troposphere descended in the lee of the mountains. Three case studies will be presented.

Influence of local meteorology and NO2 conditions on ground-level ozone concentrations in the eastern part of Texas, USA.

PubMed

Gorai, A K; Tuluri, F; Tchounwou, P B; Ambinakudige, S

2015-02-01

The influence of local climatic factors on ground-level ozone concentrations is an area of increasing interest to air quality management in regards to future climate change. This study presents an analysis on the role of temperature, wind speed, wind direction, and NO 2 level on ground-level ozone concentrations over the region of Eastern Texas, USA. Ozone concentrations at the ground level depend on the formation and dispersion processes. Formation process mainly depends on the precursor sources, whereas, the dispersion of ozone depends on meteorological factors. Study results showed that the spatial mean of ground-level ozone concentrations was highly dependent on the spatial mean of NO 2 concentrations. However, spatial distributions of NO 2 and ozone concentrations were not uniformed throughout the study period due to uneven wind speeds and wind directions. Wind speed and wind direction also played a significant role in the dispersion of ozone. Temperature profile in the area rarely had any effects on the ozone concentrations due to low spatial variations.

Influence of local meteorology and NO2 conditions on ground-level ozone concentrations in the eastern part of Texas, USA

PubMed Central

Gorai, A. K.; Tuluri, F.; Tchounwou, P. B.; Ambinakudige, S.

2014-01-01

The influence of local climatic factors on ground-level ozone concentrations is an area of increasing interest to air quality management in regards to future climate change. This study presents an analysis on the role of temperature, wind speed, wind direction, and NO2 level on ground-level ozone concentrations over the region of Eastern Texas, USA. Ozone concentrations at the ground level depend on the formation and dispersion processes. Formation process mainly depends on the precursor sources, whereas, the dispersion of ozone depends on meteorological factors. Study results showed that the spatial mean of ground-level ozone concentrations was highly dependent on the spatial mean of NO2 concentrations. However, spatial distributions of NO2 and ozone concentrations were not uniformed throughout the study period due to uneven wind speeds and wind directions. Wind speed and wind direction also played a significant role in the dispersion of ozone. Temperature profile in the area rarely had any effects on the ozone concentrations due to low spatial variations. PMID:25755687

Ultrahigh vacuum and low-temperature cleaning of oxide surfaces using a low-concentration ozone beam

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pratt, A.; Department of Physics, University of York, Heslington, York YO10 5DD; Graziosi, P.

We present a novel method of delivering a low-concentration (<15%) ozone beam to an ultra-high vacuum environment for the purpose of cleaning and dosing experimental samples through oxidation processing. The system described is safe, low-cost, and practical and overcomes the limitations of ozone transport in the molecular flow environment of high or ultrahigh vacuum whilst circumventing the use of pure ozone gas which is potentially highly explosive. The effectiveness of this method in removing surface contamination is demonstrated through comparison of high-temperature annealing of a simple oxide (MgO) in ozone and oxygen environments as monitored using quadrupole mass spectroscopy andmore » Auger electron spectroscopy. Additionally, we demonstrate the potential of ozone for obtaining clean complex oxide surfaces without the need for high-temperature annealing which may significantly alter surface structure.« less

Field responses of Prunus serotina and Asclepias syriaca to ozone around southern Lake Michigan.

PubMed

Bennett, J P; Jepsen, E A; Roth, J A

2006-07-01

Higher ozone concentrations east of southern Lake Michigan compared to west of the lake were used to test hypotheses about injury and growth effects on two plant species. We measured approximately 1000 black cherry trees and over 3000 milkweed stems from 1999 to 2001 for this purpose. Black cherry branch elongation and milkweed growth and pod formation were significantly higher west of Lake Michigan while ozone injury was greater east of Lake Michigan. Using classification and regression tree (CART) analyses we determined that departures from normal precipitation, soil nitrogen and ozone exposure/peak hourly concentrations were the most important variables affecting cherry branch elongation, and milkweed stem height and pod formation. The effects of ozone were not consistently comparable with the effects of soil nutrients, weather, insect or disease injury, and depended on species. Ozone SUM06 exposures greater than 13 ppm-h decreased cherry branch elongation 18%; peak 1-h exposures greater than 93 ppb reduced milkweed stem height 13%; and peak 1-h concentrations greater than 98 ppb reduced pod formation 11% in milkweed.

THE EMERGING RELATIONSHIP BETWEEN GROUND LEVEL OZONE AND LANDSCAPE CHARACTERISTICS

EPA Science Inventory

One of the most serious environmental health problems facing our society is that of poor air quality caused primarily by the formation of ground level ozone. Although natural ozone is beneficial in the upper atmosphere as a filter for ultraviolet radiation, ground- level ozone is...

Impacts of seasonal and regional variability in biogenic VOC emissions on surface ozone in the Pearl River Delta region, China

DOE Office of Scientific and Technical Information (OSTI.GOV)

Situ, S.; Guenther, Alex B.; Wang, X. J.

In this study, the BVOC emissions in November 2010 over the Pearl River Delta (PRD) region in southern China have been estimated by the latest version of a Biogenic Volatile Organic Compound (BVOC) emission model (MEGAN v2.1). The evaluation of MEGAN performance at a representative forest site within this region indicates MEGAN can estimate BVOC emissions reasonably well in this region except overestimating isoprene emission in autumn for reasons that are discussed in this manuscript. Along with the output from MEGAN, the Weather Research and Forecasting model with chemistry (WRF-Chem) is used to estimate the impacts of BVOC emissions onmore » surface ozone in the PRD region. The results show BVOC emissions increase the daytime ozone peak by *3 ppb on average, and the max hourly impacts of BVOC emissions on the daytime ozone peak is 24.8 ppb. Surface ozone mixing ratios in the central area of Guangzhou- Foshan and the western Jiangmen are most sensitive to BVOC emissions BVOCs from outside and central PRD influence the central area of Guangzhou-Foshan and the western Jiangmen significantly while BVOCs from rural PRD mainly influence the western Jiangmen. The impacts of BVOC emissions on surface ozone differ in different PRD cities, and the impact varies in different seasons. Foshan and Jiangmen being most affected in autumn, result in 6.0 ppb and 5.5 ppb increases in surface ozone concentrations, while Guangzhou and Huizhou become more affected in summer. Three additional experiments concerning the sensitivity of surface ozone to MEGAN input variables show that surface ozone is more sensitive to landcover change, followed by emission factors and meteorology.« less

Space-Based Diagnosis of Surface Ozone Sensitivity to Anthropogenic Emissions

NASA Technical Reports Server (NTRS)

Martin, Randall V.; Fiore, Arlene M.; VanDonkelaar, Aaron

2004-01-01

We present a novel capability in satellite remote sensing with implications for air pollution control strategy. We show that the ratio of formaldehyde columns to tropospheric nitrogen dioxide columns is an indicator of the relative sensitivity of surface ozone to emissions of nitrogen oxides (NO(x) = NO + NO2) and volatile organic compounds (VOCs). The diagnosis from these space-based observations is highly consistent with current understanding of surface ozone chemistry based on in situ observations. The satellite-derived ratios indicate that surface ozone is more sensitive to emissions of NO(x) than of VOCs throughout most continental regions of the Northern Hemisphere during summer. Exceptions include Los Angeles and industrial areas of Germany. A seasonal transition occurs in the fall when surface ozone becomes less sensitive to NOx and more sensitive to VOCs.

A revised linear ozone photochemistry parameterization for use in transport and general circulation models: multi-annual simulations

NASA Astrophysics Data System (ADS)

Cariolle, D.; Teyssèdre, H.

2007-01-01

This article describes the validation of a linear parameterization of the ozone photochemistry for use in upper tropospheric and stratospheric studies. The present work extends a previously developed scheme by improving the 2D model used to derive the coefficients of the parameterization. The chemical reaction rates are updated from a compilation that includes recent laboratory works. Furthermore, the polar ozone destruction due to heterogeneous reactions at the surface of the polar stratospheric clouds is taken into account as a function of the stratospheric temperature and the total chlorine content. Two versions of the parameterization are tested. The first one only requires the resolution of a continuity equation for the time evolution of the ozone mixing ratio, the second one uses one additional equation for a cold tracer. The parameterization has been introduced into the chemical transport model MOCAGE. The model is integrated with wind and temperature fields from the ECMWF operational analyses over the period 2000-2004. Overall, the results show a very good agreement between the modelled ozone distribution and the Total Ozone Mapping Spectrometer (TOMS) satellite data and the "in-situ" vertical soundings. During the course of the integration the model does not show any drift and the biases are generally small. The model also reproduces fairly well the polar ozone variability, with notably the formation of "ozone holes" in the southern hemisphere with amplitudes and seasonal evolutions that follow the dynamics and time evolution of the polar vortex. The introduction of the cold tracer further improves the model simulation by allowing additional ozone destruction inside air masses exported from the high to the mid-latitudes, and by maintaining low ozone contents inside the polar vortex of the southern hemisphere over longer periods in spring time. It is concluded that for the study of climatic scenarios or the assimilation of ozone data, the present parameterization gives an interesting alternative to the introduction of detailed and computationally costly chemical schemes into general circulation models.

A revised global ozone dry deposition estimate based on a new two-layer parameterisation for air-sea exchange and the multi-year MACC composition reanalysis

NASA Astrophysics Data System (ADS)

Luhar, Ashok K.; Woodhouse, Matthew T.; Galbally, Ian E.

2018-03-01

Dry deposition at the Earth's surface is an important sink of atmospheric ozone. Currently, dry deposition of ozone to the ocean surface in atmospheric chemistry models has the largest uncertainty compared to deposition to other surface types, with implications for global tropospheric ozone budget and associated radiative forcing. Most global models assume that the dominant term of surface resistance in the parameterisation of ozone dry deposition velocity at the oceanic surface is constant. There have been recent mechanistic parameterisations for air-sea exchange that account for the simultaneous waterside processes of ozone solubility, molecular diffusion, turbulent transfer, and first-order chemical reaction of ozone with dissolved iodide and other compounds, but there are questions about their performance and consistency. We present a new two-layer parameterisation scheme for the oceanic surface resistance by making the following realistic assumptions: (a) the thickness of the top water layer is of the order of a reaction-diffusion length scale (a few micrometres) within which ozone loss is dominated by chemical reaction and the influence of waterside turbulent transfer is negligible; (b) in the water layer below, both chemical reaction and waterside turbulent transfer act together and are accounted for; and (c) chemical reactivity is present through the depth of the oceanic mixing layer. The new parameterisation has been evaluated against dry deposition velocities from recent open-ocean measurements. It is found that the inclusion of only the aqueous iodide-ozone reaction satisfactorily describes the measurements. In order to better quantify the global dry deposition loss and its interannual variability, modelled 3-hourly ozone deposition velocities are combined with the 3-hourly MACC (Monitoring Atmospheric Composition and Climate) reanalysis ozone for the years 2003-2012. The resulting ozone dry deposition is found to be 98.4 ± 30.0 Tg O3 yr-1 for the ocean and 722.8 ± 87.3 Tg O3 yr-1 globally. The new estimate of the ocean component is approximately a third of the current model estimates. This reduction corresponds to an approximately 20 % decrease in the total global ozone dry deposition, which (with all other components being unchanged) is equivalent to an increase of approximately 5 % in the modelled tropospheric ozone burden and a similar increase in tropospheric ozone lifetime.

Improvements to the WRF-Chem 3.5.1 model for quasi-hemispheric simulations of aerosols and ozone in the Arctic

DOE PAGES

Marelle, Louis; Raut, Jean-Christophe; Law, Kathy S.; ...

2017-01-01

In this study, the WRF-Chem regional model is updated to improve simulated short-lived pollutants (e.g., aerosols, ozone) in the Arctic. Specifically, we include in WRF-Chem 3.5.1 (with SAPRC-99 gas-phase chemistry and MOSAIC aerosols) (1) a correction to the sedimentation of aerosols, (2) dimethyl sulfide (DMS) oceanic emissions and gas-phase chemistry, (3) an improved representation of the dry deposition of trace gases over seasonal snow, and (4) an UV-albedo dependence on snow and ice cover for photolysis calculations. We also (5) correct the representation of surface temperatures over melting ice in the Noah Land Surface Model and (6) couple and further test the recent KF-CuP (Kain–Fritsch +more » Cumulus Potential) cumulus parameterization that includes the effect of cumulus clouds on aerosols and trace gases. The updated model is used to perform quasi-hemispheric simulations of aerosols and ozone, which are evaluated against surface measurements of black carbon (BC), sulfate, and ozone as well as airborne measurements of BC in the Arctic. The updated model shows significant improvements in terms of seasonal aerosol cycles at the surface and root mean square errors (RMSEs) for surface ozone, aerosols, and BC aloft, compared to the base version of the model and to previous large-scale evaluations of WRF-Chem in the Arctic. These improvements are mostly due to the inclusion of cumulus effects on aerosols and trace gases in KF-CuP (improved RMSE for surface BC and BC profiles, surface sulfate, and surface ozone), the improved surface temperatures over sea ice (surface ozone, BC, and sulfate), and the updated trace gas deposition and UV albedo over snow and ice (improved RMSE and correlation for surface ozone). DMS emissions and chemistry improve surface sulfate at all Arctic sites except Zeppelin, and correcting aerosol sedimentation has little influence on aerosols except in the upper troposphere.« less

Improvements to the WRF-Chem 3.5.1 model for quasi-hemispheric simulations of aerosols and ozone in the Arctic

DOE Office of Scientific and Technical Information (OSTI.GOV)

Marelle, Louis; Raut, Jean-Christophe; Law, Kathy S.

In this study, the WRF-Chem regional model is updated to improve simulated short-lived pollutants (e.g., aerosols, ozone) in the Arctic. Specifically, we include in WRF-Chem 3.5.1 (with SAPRC-99 gas-phase chemistry and MOSAIC aerosols) (1) a correction to the sedimentation of aerosols, (2) dimethyl sulfide (DMS) oceanic emissions and gas-phase chemistry, (3) an improved representation of the dry deposition of trace gases over seasonal snow, and (4) an UV-albedo dependence on snow and ice cover for photolysis calculations. We also (5) correct the representation of surface temperatures over melting ice in the Noah Land Surface Model and (6) couple and further test the recent KF-CuP (Kain–Fritsch +more » Cumulus Potential) cumulus parameterization that includes the effect of cumulus clouds on aerosols and trace gases. The updated model is used to perform quasi-hemispheric simulations of aerosols and ozone, which are evaluated against surface measurements of black carbon (BC), sulfate, and ozone as well as airborne measurements of BC in the Arctic. The updated model shows significant improvements in terms of seasonal aerosol cycles at the surface and root mean square errors (RMSEs) for surface ozone, aerosols, and BC aloft, compared to the base version of the model and to previous large-scale evaluations of WRF-Chem in the Arctic. These improvements are mostly due to the inclusion of cumulus effects on aerosols and trace gases in KF-CuP (improved RMSE for surface BC and BC profiles, surface sulfate, and surface ozone), the improved surface temperatures over sea ice (surface ozone, BC, and sulfate), and the updated trace gas deposition and UV albedo over snow and ice (improved RMSE and correlation for surface ozone). DMS emissions and chemistry improve surface sulfate at all Arctic sites except Zeppelin, and correcting aerosol sedimentation has little influence on aerosols except in the upper troposphere.« less

Improvements to the WRF-Chem 3.5.1 model for quasi-hemispheric simulations of aerosols and ozone in the Arctic

NASA Astrophysics Data System (ADS)

Marelle, Louis; Raut, Jean-Christophe; Law, Kathy S.; Berg, Larry K.; Fast, Jerome D.; Easter, Richard C.; Shrivastava, Manish; Thomas, Jennie L.

2017-10-01

In this study, the WRF-Chem regional model is updated to improve simulated short-lived pollutants (e.g., aerosols, ozone) in the Arctic. Specifically, we include in WRF-Chem 3.5.1 (with SAPRC-99 gas-phase chemistry and MOSAIC aerosols) (1) a correction to the sedimentation of aerosols, (2) dimethyl sulfide (DMS) oceanic emissions and gas-phase chemistry, (3) an improved representation of the dry deposition of trace gases over seasonal snow, and (4) an UV-albedo dependence on snow and ice cover for photolysis calculations. We also (5) correct the representation of surface temperatures over melting ice in the Noah Land Surface Model and (6) couple and further test the recent KF-CuP (Kain-Fritsch + Cumulus Potential) cumulus parameterization that includes the effect of cumulus clouds on aerosols and trace gases. The updated model is used to perform quasi-hemispheric simulations of aerosols and ozone, which are evaluated against surface measurements of black carbon (BC), sulfate, and ozone as well as airborne measurements of BC in the Arctic. The updated model shows significant improvements in terms of seasonal aerosol cycles at the surface and root mean square errors (RMSEs) for surface ozone, aerosols, and BC aloft, compared to the base version of the model and to previous large-scale evaluations of WRF-Chem in the Arctic. These improvements are mostly due to the inclusion of cumulus effects on aerosols and trace gases in KF-CuP (improved RMSE for surface BC and BC profiles, surface sulfate, and surface ozone), the improved surface temperatures over sea ice (surface ozone, BC, and sulfate), and the updated trace gas deposition and UV albedo over snow and ice (improved RMSE and correlation for surface ozone). DMS emissions and chemistry improve surface sulfate at all Arctic sites except Zeppelin, and correcting aerosol sedimentation has little influence on aerosols except in the upper troposphere.

An evaluation of the regional acid deposition model surface module for ozone uptake at three sites in the San Joaquin Valley of California

NASA Technical Reports Server (NTRS)

Massman, W. J.; Pederson, J.; Delany, A.; Grantz, D.; Hertog, G. Den; Neumann, H. H.; Oncley, S. P.; Pearson, R., Jr.; Shaw, R. H.

1994-01-01

Plants and soils act as major sinks for the destruction of tropospheric ozone, especially during daylight hours when plant stomata open and are thought to provide the dominant pathway for the uptake of ozone. The present study, part of the California Ozone Deposition Experiment, compares predictions of the regional acid deposition model ozone surface conductance module with surface conductance data derived from eddy covariance measurements of ozone flux taken at a grape, a cotton, and a grassland site in the San Joaquin Valley of California during the summer of 1991. Results indicate that the model (which was developed to provide long-term large-area estimates for the eastern United States) significantly overpredicts the surface conductance at all times of the day for at least two important types of plant cover of the San Joaquin Valley and that it incorrectly partitions the ozone flux between transpiring and nontranspiring components of the surface at the third site. Consequently, the model either overpredicts or inaccurately represents the observed deposition velocities. Other results indicate that the presence of dew does not reduce the rate of ozone deposition, contradicting to model assumptions, and that model assumptions involving the dependency of stomata upon environmental temperature are unnecessary. The effects of measurement errors and biases, arising from the presence of the roughness sublayer and possible photochemical reactions, are also discussed. A simpler model for ozone surface deposition (at least for the San Joaquin Valley) is proposed and evaluated.

Analysis of European ozone trends in the period 1995-2014

NASA Astrophysics Data System (ADS)

Yan, Yingying; Pozzer, Andrea; Ojha, Narendra; Lin, Jintai; Lelieveld, Jos

2018-04-01

Surface-based measurements from the EMEP and Airbase networks are used to estimate the changes in surface ozone levels during the 1995-2014 period over Europe. We find significant ozone enhancements (0.20-0.59 µg m-3 yr-1 for the annual means; P-value < 0.01 according to an F-test) over the European suburban and urban stations during 1995-2012 based on the Airbase sites. For European background ozone observed at EMEP sites, it is shown that a significantly decreasing trend in the 95th percentile ozone concentrations has occurred, especially at noon (0.9 µg m-3 yr-1; P-value < 0.01), while the 5th percentile ozone concentrations continued to increase with a trend of 0.3 µg m-3 yr-1 (P-value < 0.01) during the study period. With the help of numerical simulations performed with the global chemistry-climate model EMAC, the importance of anthropogenic emissions changes in determining these changes over background sites are investigated. The EMAC model is found to successfully capture the observed temporal variability in mean ozone concentrations, as well as the contrast in the trends of 95th and 5th percentile ozone over Europe. Sensitivity simulations and statistical analysis show that a decrease in European anthropogenic emissions had contrasting effects on surface ozone trends between the 95th and 5th percentile levels and that background ozone levels have been influenced by hemispheric transport, while climate variability generally regulated the inter-annual variations of surface ozone in Europe.

Evaluating a Space-Based Indicator of Surface Ozone-NOx-VOC Sensitivity Over Midlatitude Source Regions and Application to Decadal Trends

NASA Astrophysics Data System (ADS)

Jin, Xiaomeng; Fiore, Arlene M.; Murray, Lee T.; Valin, Lukas C.; Lamsal, Lok N.; Duncan, Bryan; Folkert Boersma, K.; De Smedt, Isabelle; Abad, Gonzalo Gonzalez; Chance, Kelly; Tonnesen, Gail S.

2017-10-01

Determining effective strategies for mitigating surface ozone (O3) pollution requires knowledge of the relative ambient concentrations of its precursors, NOx, and VOCs. The space-based tropospheric column ratio of formaldehyde to NO2 (FNR) has been used as an indicator to identify NOx-limited versus NOx-saturated O3 formation regimes. Quantitative use of this indicator ratio is subject to three major uncertainties: (1) the split between NOx-limited and NOx-saturated conditions may shift in space and time, (2) the ratio of the vertically integrated column may not represent the near-surface environment, and (3) satellite products contain errors. We use the GEOS-Chem global chemical transport model to evaluate the quantitative utility of FNR observed from the Ozone Monitoring Instrument over three northern midlatitude source regions. We find that FNR in the model surface layer is a robust predictor of the simulated near-surface O3 production regime. Extending this surface-based predictor to a column-based FNR requires accounting for differences in the HCHO and NO2 vertical profiles. We compare four combinations of two OMI HCHO and NO2 retrievals with modeled FNR. The spatial and temporal correlations between the modeled and satellite-derived FNR vary with the choice of NO2 product, while the mean offset depends on the choice of HCHO product. Space-based FNR indicates that the spring transition to NOx-limited regimes has shifted at least a month earlier over major cities (e.g., New York, London, and Seoul) between 2005 and 2015. This increase in NOx sensitivity implies that NOx emission controls will improve O3 air quality more now than it would have a decade ago.

Evaluating a Space-Based Indicator of Surface Ozone-NO x -VOC Sensitivity Over Midlatitude Source Regions and Application to Decadal Trends.

PubMed

Jin, Xiaomeng; Fiore, Arlene M; Murray, Lee T; Valin, Lukas C; Lamsal, Lok N; Duncan, Bryan; Boersma, K Folkert; De Smedt, Isabelle; Abad, Gonzalo Gonzalez; Chance, Kelly; Tonnesen, Gail S

2017-10-16

Determining effective strategies for mitigating surface ozone (O 3 ) pollution requires knowledge of the relative ambient concentrations of its precursors, NO x , and VOCs. The space-based tropospheric column ratio of formaldehyde to NO 2 (FNR) has been used as an indicator to identify NO x -limited versus NO x -saturated O 3 formation regimes. Quantitative use of this indicator ratio is subject to three major uncertainties: (1) the split between NO x -limited and NO x -saturated conditions may shift in space and time, (2) the ratio of the vertically integrated column may not represent the near-surface environment, and (3) satellite products contain errors. We use the GEOS-Chem global chemical transport model to evaluate the quantitative utility of FNR observed from the Ozone Monitoring Instrument over three northern midlatitude source regions. We find that FNR in the model surface layer is a robust predictor of the simulated near-surface O 3 production regime. Extending this surface-based predictor to a column-based FNR requires accounting for differences in the HCHO and NO 2 vertical profiles. We compare four combinations of two OMI HCHO and NO 2 retrievals with modeled FNR. The spatial and temporal correlations between the modeled and satellite-derived FNR vary with the choice of NO 2 product, while the mean offset depends on the choice of HCHO product. Space-based FNR indicates that the spring transition to NO x -limited regimes has shifted at least a month earlier over major cities (e.g., New York, London, and Seoul) between 2005 and 2015. This increase in NO x sensitivity implies that NO x emission controls will improve O 3 air quality more now than it would have a decade ago.

An Elevated Reservoir of Air Pollutants over the Mid-Atlantic States During the 2011 DISCOVER-AQ Campaign: Airborne Measurements and Numerical Simulations

NASA Technical Reports Server (NTRS)

He, Hao; Loughner, Christopher P.; Stehr, Jeffrey W.; Arkinson, Heather L.; Brent, Lacey C.; Follette-Cook, Melanie B.; Tzortziou, Maria A.; Pickering, Kenneth E.; Thompson, Anne M.; Martins, Douglas K.;

Transboundary Contributions To Surface Ozone In California's Central Valley

NASA Astrophysics Data System (ADS)

Post, A.; Faloona, I. C.; Conley, S. A.; Lighthall, D.

2014-12-01

Rising concern over the impacts of exogenous air pollution in California's Central Valley has prompted the establishment of a coastal, high altitude monitoring site at the Chews Ridge Observatory (1550 m) approximately 30 km east of Point Sur in Monterey County, under the auspices of the Monterey Institute for Research in Astronomy. Two and a half years of continuous ozone data are presented in the context of long-range transport and its potential impact on surface air quality in the San Joaquin Valley (SJV). Past attempts to quantify the impact of transboundary ozone on surface levels have relied on uncertain model estimates, or have been limited to weekly ozonesonde data. Here, we present an observationally derived quantification of the contribution of free tropospheric ozone to surface sites in the San Joaquin Valley throughout three ozone seasons (June through September, 2012-2014). The diurnal ozone patterns at Chews Ridge, and their correlations with ozone aloft over the Valley, have been presented previously. Furthermore, reanalysis data of geopotential heights indicate consistent flow from Chews Ridge to the East, directly over the SJV. In a related airborne project we quantify the vertical exchange, or entrainment, rate over the Southern SJV from a series of focused flights measuring ozone concentrations during peak photochemical hours in conjunction with local meteorological data to quantify an ozone budget for the area. By applying the entrainment rates observed in that study here we are able to quantify the seasonal contributions of free tropospheric ozone measured at Chews Ridge to surface sites in the San Joaquin Valley, and compare prior model estimates to our observationally derived values.

Stratospheric Intrusion-Influenced Ozone Air Quality Exceedences Investigated in MERRA-2

NASA Technical Reports Server (NTRS)

Knowland, K. Emma; Ott, Lesley; Duncan, Bryan; Wargan, Krzysztof

2017-01-01

Ozone near the surface is harmful to human health and is a result of the photochemical reaction with both man-made and natural precursor pollutant sources. Therefore, in order to reduce near surface ozone concentrations, communities must reduce anthropogenic pollution sources. However, the injection of stratospheric ozone into the troposphere, known as a stratospheric intrusion, can also lead to concentrations of ground-level ozone exceeding air quality standards. Stratospheric intrusions are dynamical atmospheric features, however, these intrusions have been misrepresented in models and reanalyses until recently, as the features of a stratospheric intrusion are best identified in horizontal resolutions of approximately 50 km or smaller. NASA's Modern-Era Retrospective Analysis for Research and Applications Version-2 (MERRA-2) reanalysis is a publicly-available high-resolution dataset (50 km) with assimilated ozone that characterizes stratospheric ozone on the same spatiotemporal resolution as the meteorology. We show that stratospheric intrusions that impact surface air quality are well represented in the MERRA-2 reanalysis. This is demonstrated through a case study analysis of stratospheric intrusion events which were identified by the United States Environmental Protection Agency (EPA) to impact surface ozone air quality in spring 2012 in Colorado. The stratospheric intrusions are identified in MERRA-2 by the folding of the dynamical tropopause under the jet stream and subsequent isentropic descent of dry, O3-rich stratospheric air towards the surface where ozone air quality exceedences were observed. The MERRA-2 reanalysis can support air quality agencies for more rapid identification of the impact of stratospheric air on ground-level ozone.

Ozone Transport Aloft Drives Surface Ozone Maxima Across the Mojave Desert

NASA Astrophysics Data System (ADS)

VanCuren, R. A.

2014-12-01

A persistent layer of polluted air in the lower free troposphere over the Mojave Desert (California and Nevada) drives spring and summer surface ozone maxima as deep afternoon mixing delivers ozone and ozone precursors to surface measurement sites 200 km or more downwind of the mountains that separate the deserts from the heavily populated coastal areas of California. Pollutants in this elevated layer derive from California source regions (the Los Angeles megacity region and the intensive agricultural region of the San Joaquin Valley), and from long-range transport from Asia. Recognition of this poorly studied persistent layer explains and expands the significance of previously published reports of ozone and other pollutants observed in and over the Mojave Desert, resolves an apparent paradox in the timing of ozone peaks due to transport from the upwind basins, and provides a new perspective on the long-range downwind impacts of megacity pollution plumes.

Ozone sensitivity in hybrid poplar correlates with insensitivity to both salicylic acid and jasmonic acid. The role of programmed cell death in lesion formation.

PubMed

Koch, J R; Creelman, R A; Eshita, S M; Seskar, M; Mullet, J E; Davis, K R

2000-06-01

Our earlier studies demonstrated that the ozone-sensitive hybrid poplar clone NE-388 displays an attenuated level of ozone-, wound-, and phytopathogen-induced defense gene expression. To determine if this reduced gene activation involves signal transduction pathways dependent on salicylic acid (SA) and/or jasmonic acid (JA), we compared the responses of NE-388 and an ozone-tolerant clone, NE-245, to these signal molecules. JA levels increased in both clones in response to ozone, but only minimal increases in SA levels were measured for either clone. Treatment with SA and methyl jasmonate induced defense gene expression only in NE-245, indicating that NE-388 is insensitive to these signal molecules. DNA fragmentation, an indicator of programmed cell death (PCD), was detected in NE-245 treated with either ozone or an avirulent phytopathogen, but was not detected in NE-388. We conclude that these clones undergo two distinct mechanisms of ozone-induced lesion formation. In NE-388, lesions appear to be due to toxic cell death resulting from a limited ability to perceive and subsequently activate SA- and/or JA-mediated antioxidant defense responses. In NE-245, SA-dependent PCD precedes lesion formation via a process related to the PCD pathway activated by phytopathogenic bacteria. These results support the hypothesis that ozone triggers a hypersensitive response.

Ozone Sensitivity in Hybrid Poplar Correlates with Insensitivity to Both Salicylic Acid and Jasmonic Acid. The Role of Programmed Cell Death in Lesion Formation1

PubMed Central

Koch, Jennifer Riehl; Creelman, Robert A.; Eshita, Steven M.; Seskar, Mirjana; Mullet, John E.; Davis, Keith R.

2000-01-01

Our earlier studies demonstrated that the ozone-sensitive hybrid poplar clone NE-388 displays an attenuated level of ozone-, wound-, and phytopathogen-induced defense gene expression. To determine if this reduced gene activation involves signal transduction pathways dependent on salicylic acid (SA) and/or jasmonic acid (JA), we compared the responses of NE-388 and an ozone-tolerant clone, NE-245, to these signal molecules. JA levels increased in both clones in response to ozone, but only minimal increases in SA levels were measured for either clone. Treatment with SA and methyl jasmonate induced defense gene expression only in NE-245, indicating that NE-388 is insensitive to these signal molecules. DNA fragmentation, an indicator of programmed cell death (PCD), was detected in NE-245 treated with either ozone or an avirulent phytopathogen, but was not detected in NE-388. We conclude that these clones undergo two distinct mechanisms of ozone-induced lesion formation. In NE-388, lesions appear to be due to toxic cell death resulting from a limited ability to perceive and subsequently activate SA- and/or JA-mediated antioxidant defense responses. In NE-245, SA-dependent PCD precedes lesion formation via a process related to the PCD pathway activated by phytopathogenic bacteria. These results support the hypothesis that ozone triggers a hypersensitive response. PMID:10859179

Using Tropospheric Ozone Profiles and Surface Data (2004 - 2012) to Determine Background Ozone Levels in Houston, Texas

NASA Astrophysics Data System (ADS)

Spychala, M. D.; Morris, G. A.; Lefer, B. L.; Rappenglueck, B.; Cohan, D. S.; zhou, W.

2012-12-01

The Tropospheric Ozone Pollution Project (TOPP) at Rice University (2004 - 2006) and the University of Houston (2006 - present) has gathered > 400 profiles of ozone, temperature, pressure, and relative humidity, and > 250 of those also have wind speed and wind direction near the core of the City of Houston, Texas. Houston continues to be plagued with difficulty in coming into compliance with EPA National Ambient Air Quality Standards (NAAQS) due to a combination of its geographic location, large commuter population, significant petrochemical and energy production, and favorable weather patterns. An outstanding question remains the relative partitioning of ozone between local and remote, anthropogenic and natural sources. In this presentation, we use TOPP ozone profiles to determine a "background" ozone concentration and compare this measure with surface monitor "background" ozone as determined from upwind and downwind Continuous Air Monitoring Stations (CAMS) in an effort to further our understanding of this partitioning. For periods studied with the Community Multiscale Air Quality (CMAQ) Model, we also compare the sonde and surface "background" ozone with that suggested by the model.

Evaluating the Vertical Distribution of Ozone and its Relationship to Pollution Events in Air Quality Models using Satellite Data

NASA Astrophysics Data System (ADS)

Osterman, G. B.; Neu, J. L.; Eldering, A.; Pinder, R. W.; Tang, Y.; McQueen, J.

2014-12-01

Most regional scale models that are used for air quality forecasts and ozone source attribution do not adequately capture the distribution of ozone in the mid- and upper troposphere, but it is unclear how this shortcoming relates to their ability to simulate surface ozone. We combine ozone profile data from the NASA Earth Observing System (EOS) Tropospheric Emission Spectrometer (TES) and a new joint product from TES and the Ozone Monitoring Instrument along with ozonesonde measurements and EPA AirNow ground station ozone data to examine air quality events during August 2006 in the Community Multi-Scale Air Quality (CMAQ) and National Air Quality Forecast Capability (NAQFC) models. We present both aggregated statistics and case-study analyses with the goal of assessing the relationship between the models' ability to reproduce surface air quality events and their ability to capture the vertical distribution of ozone. We find that the models lack the mid-tropospheric ozone variability seen in TES and the ozonesonde data, and discuss the conditions under which this variability appears to be important for surface air quality.

Surface Ozone Measured at GLOBE Schools in the Czech Republic: A Demonstration of the Importance of Student Contribution to the Larger Science Picture

NASA Technical Reports Server (NTRS)

Pippin, Margaret R.; Creilson, John K.; Henderson, Bryana L.; Ladd, Irene H.; Fishman, Jack; Votapkova, Dana; Krpcova, Ilona

2008-01-01

GLOBE (Global Learning and Observations to Benefit the Environment) is a worldwide hands-on, primary and secondary school-based education and science program, developed to give students a chance to perform real science by making measurements, analyzing data, and participating in research in collaboration with scientists. As part of the GLOBE Surface Ozone Protocol and with the assistance of the TEREZA Association in the Czech Republic, schools in the Czech Republic have been making and reporting daily measurements of surface ozone and surface meteorological data since 2001. Using a hand-held ozone monitor developed for GLOBE, students at several Czech schools have generated multiyear data records of surface ozone from 2001 to 2005. Analysis of the data shows surface ozone levels were anomalously high during the summer of 2003 relative to other summers. These findings are consistent with measurements by the European Environment Agency that highlights the summer of 2003 as having exceptionally long-lasting and spatially extensive episodes of high surface ozone, especially during the first half of August. Further analysis of the summer s prevailing meteorology shows not only that it was one of the hottest on record, a finding also seen in the student data, but the conditions for production of ozone were ideal. Findings such as these increase student, teacher, and scientist confidence in the utility of the GLOBE data for engaging budding scientists in the collection, analysis, and eventual interpretation of the data for inquiry-based education.

Atomic layer deposition of Al{sub 2}O{sub 3} for single electron transistors utilizing Pt oxidation and reduction

DOE Office of Scientific and Technical Information (OSTI.GOV)

McConnell, Michael S., E-mail: mmcconn5@nd.edu; Schneider, Louisa C.; Karbasian, Golnaz

This work describes the fabrication of single electron transistors using electron beam lithography and atomic layer deposition to form nanoscale tunnel transparent junctions of alumina (Al{sub 2}O{sub 3}) on platinum nanowires using either water or ozone as the oxygen precursor and trimethylaluminum as the aluminum precursor. Using room temperature, low frequency conductance measurements between the source and drain, it was found that devices fabricated using water had higher conductance than devices fabricated with ozone. Subsequent annealing caused both water- and ozone-based devices to increase in conductance by more than 2 orders of magnitude. Furthermore, comparison of devices at low temperaturesmore » (∼4 K) showed that annealed devices displayed much closer to the ideal behavior (i.e., constant differential conductance) outside of the Coulomb blockade region and that untreated devices showed nonlinear behavior outside of the Coulomb blockade region (i.e., an increase in differential conductance with source-drain voltage bias). Transmission electron microscopy cross-sectional images showed that annealing did not significantly change device geometry, but energy dispersive x-ray spectroscopy showed an unusually large amount of oxygen in the bottom platinum layer. This suggests that the atomic layer deposition process results in the formation of a thin platinum surface oxide, which either decomposes or is reduced during the anneal step, resulting in a tunnel barrier without the in-series native oxide contribution. Furthermore, the difference between ozone- and water-based devices suggests that ozone promotes atomic layer deposition nucleation by oxidizing the surface but that water relies on physisorption of the precursors. To test this theory, devices were exposed to forming gas at room temperature, which also reduces platinum oxide, and a decrease in resistance was observed, as expected.« less

The effects of ultra-thin cerium fluoride film as the anode buffer layer on the electrical characteristics of organic light emitting diodes

NASA Astrophysics Data System (ADS)

Lu, Hsin-Wei; Tsai, Cheng-Che; Hong, Cheng-Shong; Kao, Po-Ching; Juang, Yung-Der; Chu, Sheng-Yuan

2016-11-01

In this study, the efficiency of organic light-emitting diodes (OLEDs) was enhanced by depositing a CeF3film as an ultra-thin buffer layer between the indium tin oxide (ITO) electrode and α-naphthylphenylbiphenyldiamine (NPB) hole transport layer, with the structure configuration ITO/CeF3 (0.5, 1, and 1.5 nm)/α-naphthylphenylbiphenyl diamine (NPB) (40 nm)/tris(8-hydroxyquinoline) aluminum (Alq3) (60 nm)/lithium fluoride (LiF) (1 nm)/Al (150 nm). The enhancement mechanism was systematically investigated via several approaches. The X-ray photoelectron spectroscopy and ultraviolet photoelectron spectroscopy results revealed the formation of the UV-ozone treated CeF3 film. The work function increased from 4.8 eV (standard ITO electrode) to 5.22 eV (0.5-nm-thick UV-ozone treated CeF3 film deposited on the ITO electrode). The surface roughness of the UV-ozone treated CeF3 film was smoother than that of the standard ITO electrode. Further, the UV-ozone treated CeF3 film increased both the surface energy and polarity, as determined from contact angle measurements. In addition, admittance spectroscopy measurements showed an increased capacitance and conductance of the OLEDs. Accordingly, the turn-on voltage decreased from 4.2 V to 3.6 V at 1 mA/cm2, the luminance increased from 7588 cd/m2 to 24760 cd/m2, and the current efficiency increased from 3.2 cd/A to 3.8 cd/A when the 0.5-nm-thick UV-ozone treated CeF3 film was inserted into the OLEDs.

Role of photoexcited nitrogen dioxide chemistry on ozone formation and emission control strategy over the Pearl River Delta, China

EPA Science Inventory

A new hydroxyl radical formation pathway via photo-excited nitrogen dioxide chemistry is incorporated into a chemistry-only box model as well as a 3D air quality model to examine its potential role on ozone formation and emission control strategy over the Pearl River Delta region...

Surface energy changes produced by ultraviolet-ozone irradiation of poly(methylmethacrylate), polycarbone and polytetrafluoroethylene

NASA Technical Reports Server (NTRS)

Ponter, A. B.; Jones, W. R., Jr.; Jansen, R. H.

1994-01-01

Contact angles of water and methylene iodide were measured as a function of UV/O3 treatment time for three polymers: poly(methylmethacrylate) (PMMA), polycarbonate, and polytetrafluoroethylene (PTFE). Surface roughnesses were also measured. Surface free energies were then calculated using relationships developed by Kaelble and Neumann. The surface energy of polycarbonate was found to increase (60 percent) during UV/O3 treatment. However, calculations on PMMA were hampered by the formation of a water soluble surface product. On PTFE surfaces, the UV/O3 treatment etched the surface causing large increases in surface roughness, rendering contact angle measurements impossible. It is concluded that care must be taken in interpreting contact angle measurements and surface energy calculations on UV/O3 treated polymer surfaces.

Soil Moisture-Atmosphere Feedbacks on Atmospheric Tracers: The Effects of Soil Moisture on Precipitation and Near-Surface Chemistry

NASA Astrophysics Data System (ADS)

Tawfik, Ahmed B.

The atmospheric component is described by rapid fluctuations in typical state variables, such as temperature and water vapor, on timescales of hours to days and the land component evolves on daily to yearly timescales. This dissertation examines the connection between soil moisture and atmospheric tracers under varying degrees of soil moisture-atmosphere coupling. Land-atmosphere coupling is defined over the United States using a regional climate model. A newly examined soil moisture-precipitation feedback is identified for winter months extending the previous summer feedback to colder temperature climates. This feedback is driven by the freezing and thawing of soil moisture, leading to coupled land-atmosphere conditions near the freezing line. Soil moisture can also affect the composition of the troposphere through modifying biogenic emissions of isoprene (C5H8). A novel first-order Taylor series decomposition indicates that isoprene emissions are jointly driven by temperature and soil moisture in models. These compounds are important precursors for ozone formation, an air pollutant and a short-lived forcing agent for climate. A mechanistic description of commonly observed relationships between ground-level ozone and meteorology is presented using the concept of soil moisture-temperature coupling regimes. The extent of surface drying was found to be a better predictor of ozone concentrations than temperature or humidity for the Eastern U.S. This relationship is evaluated in a coupled regional chemistry-climate model under several land-atmosphere coupling and isoprene emissions cases. The coupled chemistry-climate model can reproduce the observed soil moisture-temperature coupling pattern, yet modeled ozone is insensitive to changes in meteorology due to the balance between isoprene and the primary atmospheric oxidant, the hydroxyl radical (OH). Overall, this work highlights the importance of soil moisture-atmosphere coupling for previously neglected cold climate regimes, controlling isoprene emissions variability, and providing a processed-based description of observed ozone-meteorology relationships. From the perspective of ozone air quality, the lack of sensitivity of ozone to meteorology suggests a systematic deficiency in chemistry models in high isoprene emission regions. This shortcoming must be addressed to better estimate tropospheric ozone radiative forcing and to understanding how ozone air quality may respond to future warming.

Using Ozone To Clean and Passivate Oxygen-Handling Hardware

NASA Technical Reports Server (NTRS)

Torrance, Paul; Biesinger, Paul

2009-01-01

A proposed method of cleaning, passivating, and verifying the cleanliness of oxygen-handling hardware would extend the established art of cleaning by use of ozone. As used here, "cleaning" signifies ridding all exposed surfaces of combustible (in particular, carbon-based) contaminants. The method calls for exposing the surfaces of the hardware to ozone while monitoring the ozone effluent for carbon dioxide. The ozone would passivate the hardware while oxidizing carbon-based residues, converting the carbon in them to carbon dioxide. The exposure to ozone would be continued until no more carbon dioxide was detected, signifying that cleaning and passivation were complete.

Efficiency of activated carbon to transform ozone into *OH radicals: influence of operational parameters.

PubMed

Sánchez-Polo, M; von Gunten, U; Rivera-Utrilla, J

2005-09-01

Based on previous findings (Jans, U., Hoigné, J., 1998. Ozone Sci. Eng. 20, 67-87), the activity of activated carbon for the transformation of ozone into *OH radicals including the influence of operational parameters (carbon dose, ozone dose, carbon-type and carbon treatment time) was quantified. The ozone decomposition constant (k(D)) was increased by the presence of activated carbon in the system and depending on the type of activated carbon added, the ratio of the concentrations of *OH radicals and ozone, the R(ct) value ([*OH]/[O3]), was increased by a factor 3-5. The results obtained show that the surface chemical and textural characteristics of the activated carbon determines its activity for the transformation of ozone into *OH radicals. The most efficient carbons in this process are those with high basicity and large surface area. The obtained results show that the interaction between ozone and pyrrol groups present on the surface of activated carbon increase the concentration of O2*- radicals in the system, enhancing ozone transformation into *OH radicals. The activity of activated carbon decreases for extended ozone exposures. This may indicate that activated carbon does not really act as a catalyst but rather as a conventional initiator or promoter for the ozone transformation into *OH radicals. Ozonation of Lake Zurich water ([O3] = 1 mg/L) in presence of activated carbon (0.5 g/L) lead to an increase in the k(D) and R(ct) value by a factor of 10 and 39, respectively, thereby favouring the removal of ozone-resistant contaminants. Moreover, the presence of activated carbon during ozonation of Lake Zurich water led to a 40% reduction in the content of dissolved organic carbon during the first 60 min of treatment. The adsorption of low concentrations of dissolved organic matter (DOM) on activated carbon surfaces did not modify its capacity to initiate/promote ozone transformation into *OH radicals.

Field responses of Prunus serotina and Asclepias syriaca to ozone around southern Lake Michigan

USGS Publications Warehouse

Bennett, J.P.; Jepsen, E.A.; Roth, J.A.

2006-01-01

Higher ozone concentrations east of southern Lake Michigan compared to west of the lake were used to test hypotheses about injury and growth effects on two plant species. We measured approximately 1000 black cherry trees and over 3000 milkweed stems from 1999 to 2001 for this purpose. Black cherry branch elongation and milkweed growth and pod formation were significantly higher west of Lake Michigan while ozone injury was greater east of Lake Michigan. Using classification and regression tree (CART) analyses we determined that departures from normal precipitation, soil nitrogen and ozone exposure/peak hourly concentrations were the most important variables affecting cherry branch elongation, and milkweed stem height and pod formation. The effects of ozone were not consistently comparable with the effects of soil nutrients, weather, insect or disease injury, and depended on species. Ozone SUM06 exposures greater than 13 ppm-h decreased cherry branch elongation 18%; peak 1-h exposures greater than 93 ppb reduced milkweed stem height 13%; and peak 1-h concentrations greater than 98 ppb reduced pod formation 11% in milkweed. Decreased cherry branch elongation, milkweed stem height and pod production, and foliar injury on both species occurred at sites around southern Lake Michigan at ozone exposures of 13 SUM06 ppm-h and 93a??98 ppb peak hourly.

Isoprene Emissions and Ozone Formation in Urban Conditions: A Case Study in the City of Rio de Janeiro.

PubMed

da Silva, Cleyton Martins; Corrêa, Sergio Machado; Arbilla, Graciela

2018-01-01

The potential role of isoprene oxidative processes, as well as the possible impact of air pollution on isoprene emissions, are more important in tropical cities, surrounded by rainforests. In this study, the contribution of isoprene to ozone formation was determined considering different scenarios, mainly volatile organic compounds/NO x (VOC/NO x ) ratios, and typical atmospheric conditions for the city of Rio de Janeiro, where more than 36% of the urbanized area is covered by vegetation. Ozone isopleths and incremental reactivity coefficients (IR) were evaluated to understand the direct contribution of isoprene to ground-level ozone formation and the negative impact of anthropogenic NO x emissions on the natural atmospheric balance. Although isoprene accounted for only 2.7% of the total VOC mass, excluding the isoprene concentration from the model reduced the maximum ozone value by 14.1%. The calculated IR coefficient (grams of O 3 formed per gram of added isoprene) was 2.2 for a VOC/NO x ratio of 8.86.

The impacts of ozonation on oil sands process-affected water biodegradability and biofilm formation characteristics in bioreactors.

PubMed

Hwang, Geelsu; Dong, Tao; Islam, Md Sahinoor; Sheng, Zhiya; Pérez-Estrada, Leónidas A; Liu, Yang; Gamal El-Din, Mohamed

2013-02-01

To examine the effects of the ozonation process (as an oxidation treatment for water and wastewater treatment applications) on microbial biofilm formation and biodegradability of organic compounds present in oil sands process-affected water (OSPW), biofilm reactors were operated continuously for 6weeks. Two types of biofilm substrate materials: polyethylene (PE) and polyvinylchloride (PVC), and two types of OSPW-fresh and ozonated OSPWs-were tested. Endogenous microorganisms, in OSPW, quickly formed biofilms in the reactors. Without ozonation, the bioreactor (using endogenous microorganisms) removed 13.8% of the total acid-extractable organics (TAO) and 18.5% of the parent naphthenic acids (NAs) from fresh OSPW. The combined ozonation and biodegradation process removed 87.2% of the OSPW TAO and over 99% of the OSPW parent NAs. Further UPLC/HRMS analysis showed that NA biodegradability decreased as the NA cyclization number increased. Microbial biofilm formation was found to depend on the biofilm substrate type. Copyright © 2012 Elsevier Ltd. All rights reserved.

Why do Models Overestimate Surface Ozone in the Southeastern United States?

NASA Technical Reports Server (NTRS)

Travis, Katherine R.; Jacob, Daniel J.; Fisher, Jenny A.; Kim, Patrick S.; Marais, Eloise A.; Zhu, Lei; Yu, Karen; Miller, Christopher C.; Yantosca, Robert M.; Sulprizio, Melissa P.;

Why do models overestimate surface ozone in the Southeast United States?

NASA Astrophysics Data System (ADS)

Travis, Katherine R.; Jacob, Daniel J.; Fisher, Jenny A.; Kim, Patrick S.; Marais, Eloise A.; Zhu, Lei; Yu, Karen; Miller, Christopher C.; Yantosca, Robert M.; Sulprizio, Melissa P.; Thompson, Anne M.; Wennberg, Paul O.; Crounse, John D.; St. Clair, Jason M.; Cohen, Ronald C.; Laughner, Joshua L.; Dibb, Jack E.; Hall, Samuel R.; Ullmann, Kirk; Wolfe, Glenn M.; Pollack, Illana B.; Peischl, Jeff; Neuman, Jonathan A.; Zhou, Xianliang

2016-11-01

Ozone pollution in the Southeast US involves complex chemistry driven by emissions of anthropogenic nitrogen oxide radicals (NOx ≡ NO + NO2) and biogenic isoprene. Model estimates of surface ozone concentrations tend to be biased high in the region and this is of concern for designing effective emission control strategies to meet air quality standards. We use detailed chemical observations from the SEAC4RS aircraft campaign in August and September 2013, interpreted with the GEOS-Chem chemical transport model at 0.25° × 0.3125° horizontal resolution, to better understand the factors controlling surface ozone in the Southeast US. We find that the National Emission Inventory (NEI) for NOx from the US Environmental Protection Agency (EPA) is too high. This finding is based on SEAC4RS observations of NOx and its oxidation products, surface network observations of nitrate wet deposition fluxes, and OMI satellite observations of tropospheric NO2 columns. Our results indicate that NEI NOx emissions from mobile and industrial sources must be reduced by 30-60 %, dependent on the assumption of the contribution by soil NOx emissions. Upper-tropospheric NO2 from lightning makes a large contribution to satellite observations of tropospheric NO2 that must be accounted for when using these data to estimate surface NOx emissions. We find that only half of isoprene oxidation proceeds by the high-NOx pathway to produce ozone; this fraction is only moderately sensitive to changes in NOx emissions because isoprene and NOx emissions are spatially segregated. GEOS-Chem with reduced NOx emissions provides an unbiased simulation of ozone observations from the aircraft and reproduces the observed ozone production efficiency in the boundary layer as derived from a regression of ozone and NOx oxidation products. However, the model is still biased high by 6 ± 14 ppb relative to observed surface ozone in the Southeast US. Ozonesondes launched during midday hours show a 7 ppb ozone decrease from 1.5 km to the surface that GEOS-Chem does not capture. This bias may reflect a combination of excessive vertical mixing and net ozone production in the model boundary layer.

Why do Models Overestimate Surface Ozone in the Southeastern United States?

PubMed

Travis, Katherine R; Jacob, Daniel J; Fisher, Jenny A; Kim, Patrick S; Marais, Eloise A; Zhu, Lei; Yu, Karen; Miller, Christopher C; Yantosca, Robert M; Sulprizio, Melissa P; Thompson, Anne M; Wennberg, Paul O; Crounse, John D; St Clair, Jason M; Cohen, Ronald C; Laughner, Joshua L; Dibb, Jack E; Hall, Samuel R; Ullmann, Kirk; Wolfe, Glenn M; Pollack, Illana B; Peischl, Jeff; Neuman, Jonathan A; Zhou, Xianliang

2016-01-01

Ozone pollution in the Southeast US involves complex chemistry driven by emissions of anthropogenic nitrogen oxide radicals (NO x ≡ NO + NO 2 ) and biogenic isoprene. Model estimates of surface ozone concentrations tend to be biased high in the region and this is of concern for designing effective emission control strategies to meet air quality standards. We use detailed chemical observations from the SEAC 4 RS aircraft campaign in August and September 2013, interpreted with the GEOS-Chem chemical transport model at 0.25°×0.3125° horizontal resolution, to better understand the factors controlling surface ozone in the Southeast US. We find that the National Emission Inventory (NEI) for NO x from the US Environmental Protection Agency (EPA) is too high. This finding is based on SEAC 4 RS observations of NO x and its oxidation products, surface network observations of nitrate wet deposition fluxes, and OMI satellite observations of tropospheric NO 2 columns. Our results indicate that NEI NO x emissions from mobile and industrial sources must be reduced by 30-60%, dependent on the assumption of the contribution by soil NO x emissions. Upper tropospheric NO 2 from lightning makes a large contribution to satellite observations of tropospheric NO 2 that must be accounted for when using these data to estimate surface NO x emissions. We find that only half of isoprene oxidation proceeds by the high-NO x pathway to produce ozone; this fraction is only moderately sensitive to changes in NO x emissions because isoprene and NO x emissions are spatially segregated. GEOS-Chem with reduced NO x emissions provides an unbiased simulation of ozone observations from the aircraft, and reproduces the observed ozone production efficiency in the boundary layer as derived from a regression of ozone and NO x oxidation products. However, the model is still biased high by 8±13 ppb relative to observed surface ozone in the Southeast US. Ozonesondes launched during midday hours show a 7 ppb ozone decrease from 1.5 km to the surface that GEOS-Chem does not capture. This bias may reflect a combination of excessive vertical mixing and net ozone production in the model boundary layer.

Why do Models Overestimate Surface Ozone in the Southeastern United States?

PubMed Central

Travis, Katherine R.; Jacob, Daniel J.; Fisher, Jenny A.; Kim, Patrick S.; Marais, Eloise A.; Zhu, Lei; Yu, Karen; Miller, Christopher C.; Yantosca, Robert M.; Sulprizio, Melissa P.; Thompson, Anne M.; Wennberg, Paul O.; Crounse, John D.; St Clair, Jason M.; Cohen, Ronald C.; Laughner, Joshua L.; Dibb, Jack E.; Hall, Samuel R.; Ullmann, Kirk; Wolfe, Glenn M.; Pollack, Illana B.; Peischl, Jeff; Neuman, Jonathan A.; Zhou, Xianliang

2018-01-01

Ozone pollution in the Southeast US involves complex chemistry driven by emissions of anthropogenic nitrogen oxide radicals (NOx ≡ NO + NO2) and biogenic isoprene. Model estimates of surface ozone concentrations tend to be biased high in the region and this is of concern for designing effective emission control strategies to meet air quality standards. We use detailed chemical observations from the SEAC4RS aircraft campaign in August and September 2013, interpreted with the GEOS-Chem chemical transport model at 0.25°×0.3125° horizontal resolution, to better understand the factors controlling surface ozone in the Southeast US. We find that the National Emission Inventory (NEI) for NOx from the US Environmental Protection Agency (EPA) is too high. This finding is based on SEAC4RS observations of NOx and its oxidation products, surface network observations of nitrate wet deposition fluxes, and OMI satellite observations of tropospheric NO2 columns. Our results indicate that NEI NOx emissions from mobile and industrial sources must be reduced by 30–60%, dependent on the assumption of the contribution by soil NOx emissions. Upper tropospheric NO2 from lightning makes a large contribution to satellite observations of tropospheric NO2 that must be accounted for when using these data to estimate surface NOx emissions. We find that only half of isoprene oxidation proceeds by the high-NOx pathway to produce ozone; this fraction is only moderately sensitive to changes in NOx emissions because isoprene and NOx emissions are spatially segregated. GEOS-Chem with reduced NOx emissions provides an unbiased simulation of ozone observations from the aircraft, and reproduces the observed ozone production efficiency in the boundary layer as derived from a regression of ozone and NOx oxidation products. However, the model is still biased high by 8±13 ppb relative to observed surface ozone in the Southeast US. Ozonesondes launched during midday hours show a 7 ppb ozone decrease from 1.5 km to the surface that GEOS-Chem does not capture. This bias may reflect a combination of excessive vertical mixing and net ozone production in the model boundary layer. PMID:29619045

N-nitrosodimethylamine (NDMA) formation during ozonation of N,N-dimethylhydrazine compounds: Reaction kinetics, mechanisms, and implications for NDMA formation control.

PubMed

Lim, Sungeun; Lee, Woongbae; Na, Soyoung; Shin, Jaedon; Lee, Yunho

2016-11-15

Compounds with N,N-dimethylhydrazine moieties ((CH 3 ) 2 N-N-) form N-nitrosodimethylamine (NDMA) during ozonation, but the relevant reaction chemistry is hitherto poorly understood. This study investigated the reaction kinetics and mechanisms of NDMA formation during ozonation of unsymmetrical dimethylhydrazine (UDMH) and daminozide (DMZ) as structural model N,N-dimethylhydrazine compounds. The reaction of ozone with these NDMA precursor compounds was fast, and k O3 at pH 7 was 2 × 10 6  M -1  s -1 for UDMH and 5 × 10 5  M -1  s -1 for DMZ. Molar NDMA yields (i.e., Δ[NDMA]/Δ[precursor] × 100) were 84% and 100% for UDMH and DMZ, respectively, determined at molar ozone dose ratio ([O 3 ] 0 /[precursor] 0 ) of ≥4 in the presence of tert-butanol as hydroxyl radical (OH) scavenger. The molar NDMA yields decreased significantly in the absence of tert-butanol, indicating OH formation and its subsequent reaction with the parent precursors forming negligible NDMA. The k OH at pH 7 was 4.9 × 10 9  M -1  s -1 and 3.4 × 10 9  M -1  s -1 for UDMH and DMZ, respectively. Reaction mechanisms are proposed in which an ozone adduct is formed at the nitrogen next to N,N-dimethylamine which decomposes via homolytic and heterolytic cleavages of the -N + -O-O-O - bond, forming NDMA as a final product. The heterolytic cleavage pathway explains the significant OH formation via radical intermediates. Overall, significant NDMA formation was found to be unavoidable during ozonation or even O 3 /H 2 O 2 treatment of waters containing N,N-dimethylhydrazine compounds due to their rapid reaction with ozone forming NDMA with high yield. Thus, source control or pre-treatment of N,N-dimethylhydrazine precursors and post-treatment of NDMA are proposed as the mitigation options. Copyright © 2016 Elsevier Ltd. All rights reserved.

Surface ozone seasonality under global change: Influence from dry deposition and isoprene emissions at northern mid-latitudes

NASA Astrophysics Data System (ADS)

Clifton, O.; Paulot, F.; Fiore, A. M.; Horowitz, L. W.; Malyshev, S.; Shevliakova, E.; Correa, G. J. P.; Lin, M.

2017-12-01

Identifying the contributions of nonlinear chemistry and transport to observed surface ozone seasonal cycles over land using global models relies on an accurate representation of ozone uptake by vegetation (dry deposition). It is well established that in the absence of ozone precursor emission changes, a warming climate will increase surface ozone in polluted regions, and that a rise in temperature-dependent isoprene emissions would exacerbate this "climate penalty". However, the influence of changes in ozone dry deposition, expected to evolve with climate and land use, is often overlooked in air quality projections. With a new scheme that represents dry deposition within the NOAA GFDL dynamic vegetation land model (LM3) coupled to the NOAA GFDL atmospheric chemistry-climate model (AM3), we simulate the impact of 21st century climate and land use on ozone dry deposition and isoprene emissions. This dry deposition parameterization is a version of the Wesely scheme, but uses parameters explicitly calculated by LM3 that respond to climate and land use (e.g., stomatal conductance, canopy interception of water, leaf area index). The parameterization includes a nonstomatal deposition dependence on humidity. We evaluate climatological present-day seasonal cycles of ozone deposition velocities and abundances with those observed at northern mid-latitude sites. With a set of 2010s and 2090s decadal simulations under a high climate warming scenario (RCP8.5) and a sensitivity simulation with well-mixed greenhouse gases following RCP8.5 but air pollutants held at 2010 levels (RCP8.5_WMGG), we examine changes in surface ozone seasonal cycles. We build on our previous findings, which indicate that strong reductions in anthropogenic NOx emissions under RCP8.5 cause the surface ozone seasonal cycle over the NE USA to reverse, shifting from a summer peak at present to a winter peak by 2100. Under RCP8.5_WMGG, we parse the separate effects of climate and land use on ozone dry deposition vs. isoprene emissions to quantify the impact of each process on surface ozone seasonal cycles and compare to the changes induced by declining anthropogenic NOx emissions (RCP8.5).

California Baseline Ozone Transport Study (CABOTS): Ozonesonde Measurements

NASA Astrophysics Data System (ADS)

Eiserloh, A. J., Jr.; Chiao, S.; Spitze, J.; Cauley, S.; Clark, J.; Roberts, M.

2016-12-01

Because the EPA recently lowered the ambient air quality standard for the 8-hr average of ozone (O3) to70 ppbv, California must continue to achieve significant reductions in ozone precursor emissions and prepare for new State Implementation Plans (SIP) to demonstrate how ground-level ambient ozone will be reduced below the new health-based standard. Prior studies suggest that background levels of ozone traveling across the Pacific Ocean can significantly influence surface ozone throughout California, particularly during the spring. Evidence has been presented indicating that background levels of ozone continue to increase in the western United States over the recent few decades, implying more ozone exceedances in the future. To better understand the contributions of the external natural and anthropogenic pollution sources as well as atmospheric processes for surface ozone concentrations in California during the spring and summer months, the California Baseline Ozone Transport Study (CABOTS) has been established. One major goal of CABOTS is to implement near daily ozonesonde measurements along the California Coast to quantify background ozone aloft before entering the State during high ozone season. CABOTS has been ongoing from May through August of 2016 launching ozonesondes from Bodega Bay and Half Moon Bay, California. The temporal progression of ozonesonde measurements and subsequent analysis of the data will be discussed with a focus on the contribution of background ozone to surface ozone sites inland as well as likely origins of layers aloft. Comparisons of current ozonesondes versus prior ozonesonde studies of California will also be performed. A few selected cases of high ozone layers moving onshore from different sources will be discussed as well.

Surface and Tropospheric Ozone Profile Variability (1999-2014) at the TOLNet Site of Table Mountain, California

NASA Astrophysics Data System (ADS)

Granados-Muñoz, M. J.; Leblanc, T.

2015-12-01

Ozone in the lower troposphere acts as an air pollutant affecting human health and vegetation. Tropospheric ozone sources and variability are not yet fully identified or understood and recent studies reveal the importance of increasing the number of tropospheric ozone profiling stations and long term measurements. As part of the international monitoring network NDACC, and the U.S.-based network TOLNet, a differential absorption lidar has been performing tropospheric ozone measurements (3-20 km) at the JPL Table Mountain Facility (TMF, California) since 1999, and surface measurements have been performed since 2013 with a UV photometric analyzer. Because of the site's geolocation and high elevation, background tropospheric ozone, unaffected by the boundary layer dynamics and local anthropogenic emissions of ozone precursors, is usually expected. However, transboundary ozone contributions such as stratospheric intrusions and Asian pollution episodes are frequently detected. In this study, a statistical analysis of the 14-year lidar profiles and the 2.5-year surface data is presented. Seasonal, interannual and diurnal variability and its possible causes (e.g. El Nino/La Nina events, North American Monsoon) are investigated. Together with the high elevation surface data gathered at TMF, surface data from ARB stations nearby are analyzed to understand the lowermost tropospheric ozone variability component. The frequency of stratospheric intrusions and Asian pollution episodes reaching the Western U.S. is also examined in an attempt to understand the relative contribution of each process to the observed variability throughout the troposphere. The Table Mountain surface and lidar measurements are expected to contribute significantly to the emerging system of global air quality observations, and to the improvement of global and regional data assimilation and modeling.

78 FR 44485 - Implementation of the 2008 National Ambient Air Quality Standards for Ozone: State Implementation...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-07-24

...] Implementation of the 2008 National Ambient Air Quality Standards for Ozone: State Implementation Plan... Rule Regarding ``Implementation of the 2008 National Ambient Air Quality Standards for Ozone: State... ground-level ozone formation. B. What should I consider as I prepare my comments for the EPA? 1...

Preliminary SEM Observations on the Surface of Elastomeric Impression Materials after Immersion or Ozone Disinfection

PubMed Central

Prombonas, Anthony; Yannikakis, Stavros; Karampotsos, Thanasis; Katsarou, Martha-Spyridoula; Drakoulis, Nikolaos

2016-01-01

Introduction Surface integrity of dental elastomeric impression materials that are subjected to disinfection is of major importance for the quality of the final prosthetic restorations. Aim The aim of this qualitative Scanning Electronic Microscopy (SEM) study was to reveal the effects of immersion or ozone disinfection on the surface of four dental elastomeric impression materials. Materials and Methods Four dental elastomeric impression material brands were used (two vinyl polysiloxane silicones, one polyether, and one vinyl polyether silicone). Total of 32 specimens were fabricated, eight from each impression material. Specimens were immersion (0.525% sodium hypochlorite solution or 0.3% benzalkonium chloride solution) or ozone disinfected or served as controls and examined with SEM. Results Surface degradation was observed on several speci-mens disinfected with 0.525% sodium hypochlorite solution. Similar wavy-wrinkling surface structures were observed in almost all specimens, when treated either with 0.3% benzalkonium chloride solution or ozone. Conclusion The SEM images obtained from this study revealed that both immersion disinfectants and ozone show similar impression material surface alterations. Ozone seems to be non-inferior as compared to immersion disinfectants, but superior as to environmental protection. PMID:28208993

Tropospheric ozone in east Asia

DOE Office of Scientific and Technical Information (OSTI.GOV)

Phadnis, M.J.

1996-12-31

An analysis of the observed data for the tropospheric ozone at mid latitudes in east Asia is done. There are three ways by which the tropospheric ozone is calculated, namely: (1) Ozonesonde measurements, (2) Fishman`s method of Residual Ozone and (3) TOMS measurements - an indirect method of calculating tropospheric ozone. In addition the surface ozone values at the network sites in Japan is also considered. The analysis of data is carried out for a period of twelve years from 1979 to 1991. In general it is observed that the tropospheric ozone is more in summer than winter, obviously becausemore » of the larger tropopause height in summer. On an average for the period of the analysis, the ozone values are at a high of about 60 DU (dobson units). While in winter the values go down to around 30 DU. Also a time series analysis shows an increasing trend in the values over the years. The ozonesonde values are correlated more to the TOMS tropospheric ozone values. For the stations analyzed in Japan, the TOMS tropospheric ozone values are generally greater than the ozonesonde values. The analysis of the average monthly surface ozone in Japan shows highs in spring and lows in summer. This can be attributed to movement of pollutant laden fronts towards Japan during spring. The highs for surface ozone are about 50 DU while the lows are around 20 DU.« less

Ozone response to a CO2 doubling - Results from a stratospheric circulation model with heterogeneous chemistry

NASA Technical Reports Server (NTRS)

Pitari, G.; Palermi, S.; Visconti, G.; Prinn, R. G.

1992-01-01

A spectral 3D model of the stratosphere has been used to study the sensitivity of polar ozone with respect to a carbon dioxide increase. The lower stratospheric cooling associated with an imposed CO2 doubling may increase the probability of polar stratospheric cloud (PSC) formation and this affect ozone. The ozone perturbation obtained with the inclusion of a simple parameterization for heterogeneous chemistry on PSCs is compared to that relative to a pure homogeneous chemistry. In both cases the temperature perturbation is determined by a CO2 doubling, while the total chlorine content is kept at the present level. It is shown that the lower temperature may increase the depth and the extension of the ozone hole by extending the area amenable to PSC formation. It may be argued that this effect, coupled with an increasing amount of chlorine, may produce a positive feedback on the ozone destruction.

Interactive Ozone and Methane Chemistry in GISS-E2 Historical and Future Climate Simulations

NASA Technical Reports Server (NTRS)

Shindell, D. T.; Pechony, O.; Voulgarakis, A.; Faluvegi, G.; Nazarenko. L.; Lamarque, J.-F.; Bowman, K.; Milly, G.; Kovari, B.; Ruedy, R.;

Mortality tradeoff between air quality and skin cancer from changes in stratospheric ozone

NASA Astrophysics Data System (ADS)

Eastham, Sebastian D.; Keith, David W.; Barrett, Steven R. H.

2018-03-01

Skin cancer mortality resulting from stratospheric ozone depletion has been widely studied. Similarly, there is a deep body of literature on surface ozone and its health impacts, with modeling and observational studies demonstrating that surface ozone concentrations can be increased when stratospheric air mixes to the Earth’s surface. We offer the first quantitative estimate of the trade-off between these two effects, comparing surface air quality benefits and UV-related harms from stratospheric ozone depletion. Applying an idealized ozone loss term in the stratosphere of a chemistry-transport model for modern-day conditions, we find that each Dobson unit of stratospheric ozone depletion results in a net decrease in the global annual mortality rate of ~40 premature deaths per billion population (d/bn/DU). The impacts are spatially heterogeneous in sign and magnitude, composed of a reduction in premature mortality rate due to ozone exposure of ~80 d/bn/DU concentrated in Southeast Asia, and an increase in skin cancer mortality rate of ~40 d/bn/DU, mostly in Western Europe. This is the first study to quantify air quality benefits of stratospheric ozone depletion, and the first to find that marginal decreases in stratospheric ozone around modern-day values could result in a net reduction in global mortality due to competing health impact pathways. This result, which is subject to significant methodological uncertainty, highlights the need to understand the health and environmental trade-offs involved in policy decisions regarding anthropogenic influences on ozone chemistry over the 21st century.

Immobilization of naringin onto chitosan substrates by using ozone activation.

PubMed

Li, Chung Hsing; Wang, Jing Wei; Ho, Ming Hua; Shih, Jia Lin; Hsiao, Sheng Wen; Thien, Doan Van Hong

2014-03-01

Ozone oxidation can easily produce peroxides containing active free radicals that can be used for the surface modification of biomaterials. This process is highly efficient and nontoxic. In this research, naringin, an HMG-CoA reductase inhibitor that can promote bone formation, was immobilized onto a chitosan film using ozone activation. First, a chitosan film was treated by ozone to produce peroxides; these peroxides were then quantified and their amount was optimized by an iodide assay. For the in vitro delivery of naringin, a chitosan-naringin substrate was immersed in phosphate-buffered saline to quantify the released amount of naringin. It was found that the immobilized naringin was slowly released over the course of two weeks, where its concentration in the medium was controlled by this delivery process. The results of cell culture showed that cell viability and early osteogenic differentiation, as measured by alkaline phosphatase expression, were promoted with the immobilized naringin on chitosan substrates. The expression of osteogenic proteins, including type-I collagen, bone siloprotein, and osteocalcin, were also enhanced. According to the results of Smad1 and Smad6 phosphorylation, immobilized naringin on ozonated chitosan substrates would be able to initiate bone morphogenetic protein-Smad signaling by activating receptor Smad and by suppressing inhibitory Smad. The results in this research demonstrated that the naringin-chitosan substrate produced by biocompatible ozone activation was highly osteoconductive without cytotoxicity. Copyright © 2013 Elsevier B.V. All rights reserved.

Analysis of Strong Wintertime Ozone Events in an Area of Extensive Oil and Gas Extraction

NASA Astrophysics Data System (ADS)

Rappenglück, Bernhard; Ackermann, Luis; Alvarez, Sergio; Golovko, Julia; Buhr, Martin; Field, Robert; Soltis, Jeff; Montague, Derek C.; Hauze, Bill; Scott, Adamson; Risch, Dan; Wilkerson, George; Bush, David; Stoeckenius, Till; Keslar, Cara

2015-04-01

During recent years, elevated ozone (O3) values have been observed repeatedly in the Upper Green River Basin (UGRB), Wyoming during wintertime. This paper presents an analysis of high ozone days in late winter 2011 (1-hour average up to 166 ppbv). Intensive Observational Periods (IOPs) were performed which included comprehensive surface and boundary layer measurements. Low windspeeds in combination with low mixing layer heights (~50 m agl) are essential for accumulation of pollutants. Air masses contain substantial amounts of reactive nitrogen (NOx) and non-methane hydrocarbons (NMHC) emitted from fossil fuel exploration activities in the Pinedale Anticline. On IOP days in the morning hours reactive nitrogen (up to 69%), then aromatics and alkanes (each ~10-15%; mostly ethane and propane) are major contributors to the hydroxyl (OH) reactivity. This time frame largely coincides with lowest NMHC/NOx ratios (~50), reflecting a relatively low NMHC mixture, and a change from a NOx-limited regime towards a NMHC limited regime. OH production on IOP days is mainly due to nitrous acid (HONO). On a 24-hr basis and as determined for a measurement height of 1.80 m above the surface HONO photolysis on IOP days can contribute ~83% to OH production on average, followed by alkene ozonolysis (~9%). Photolysis by ozone and HCHO photolysis contributes about 4% each to hydroxyl formation. High HONO levels (maximum hourly median on IOP days: 1,096 pptv) are favored by a combination of shallow boundary layer conditions and enhanced photolysis rates due to the high albedo of the snow surface. HONO is most likely formed through (i) abundant nitric acid (HNO3) produced in atmospheric oxidation of NOx, deposited onto the snow surface and undergoing photo-enhanced heterogeneous conversion to HONO and (ii) combustion related emission of HONO. HONO production is confined to the lowermost 10 m of the boundary layer. HONO, serves as the most important precursor for OH, strongly enhanced due to the high albedo of the snow cover.

Lidar Measurements of Tropospheric Ozone in the Arctic

NASA Astrophysics Data System (ADS)

Seabrook, Jeffrey; Whiteway, James

2016-06-01

This paper reports on differential absorption lidar (DIAL) measurements of tropospheric ozone in the Canadian Arctic during springtime. Measurements at Eureka Weather Station revealed that mountains have a significant effect on the vertical structure of ozone above Ellesmere Island. Ozone depletion events were observed when air that had spent significant time near to the frozen surface of the Arctic Ocean reached Eureka. This air arrived at Eureka by flowing over the surrounding mountains. Surface level ozone depletions were not observed during periods when the flow of air from over the sea ice was blocked by mountains. In the case of blocking there was an enhancement in the amount of ozone near the surface as air from the mid troposphere descended in the lee of the mountains. Three case studies will be shown in the presentation, while one is described in this paper.

Degradation of trifluoroacetate in oxic and anoxic sediments

USGS Publications Warehouse

Visscher, P.T.; Culbertson, C.W.; Oremland, R.S.

1994-01-01

THE deleterious effect of chlorofluorocarbons on stratospheric ozone has led to international cooperation to end their use. The search for acceptable alternatives has focused on hydrofluorocarbons (HFCs) or hydrochlorofluorocarbons (HCFCs) which are attractive because they have relatively short atmospheric residence times. HFCs and HCFCs are attacked by tropospheric hydroxyl radicals, leading to the formation of trifluoroacetate (TFA). Most of the atmospheric TFA is deposited at the Earth's surface, where it is thought to be highly resistant to bacterial attack. Therefore, use of HCFCs and HFCs may lead to accumulation of TFA in soils, where it could prove toxic or inhibitory to plants and soil microbial communities. Although little is known about the toxicity of TFA, monofluoroacetate, which occurs at low levels in some plants and which is susceptible to slow attack by aerobic soil microbes, is known to be acutely toxic. Here we report that TFA can be rapidly degraded microbially under anoxic and oxic conditions. These results imply that significant microbial sinks exist in nature for the elimination of TFA from the environment. We also show that oxic degradation of TFA leads to the formation of fluoroform, a potential ozone-depleting compound with a much longer atmospheric lifetime than the parent compounds.The deleterious effect of chlorofluorcarbons on stratospheric ozone has led to international cooperation to end their use. The search for acceptable alternatives has focused on hydroflnorocarbons (HFCs) or hydrochloroflnorcarbons (HCFs) which are attractive because they have relatively short atmospheric residence times. HFCs and HCFs are attacked by tropospheric hydroxyl radicals, leading to the formation of trifluoroacetate (TFA). Most of the atmospheric TFA is deposited at the Earth's surface, where it is thought to be highly resistant to bacterial attack. Therefore, use of HCFs and HCFs may lead to accummulation of TFA in soils, where it could prove toxic or inhibitory to plants and soil microbial communities. Although little is known about the toxicity of TFA, monofluoracetate, which occurs at low levels in some plants and which is susceptible to slow attack by aerobic soil microbes, is known to be acutely toxic. Here we report that TFA can be rapidly degraded microbially under anoxic and oxic conditions. These results imply that significant microbial sinks exist in nature for the elimination of TFA from the environment. We also show that oxic degradation of TFA leads to the formation of fluoroform, a potential ozone-depleting compound with a much longer atmospheric lifetime than the parent compounds.

Effects of ozone-vegetation coupling on surface ozone air quality via biogeochemical and meteorological feedbacks

NASA Astrophysics Data System (ADS)

Sadiq, Mehliyar; Tai, Amos P. K.; Lombardozzi, Danica; Martin, Maria Val

2017-02-01

Tropospheric ozone is one of the most hazardous air pollutants as it harms both human health and plant productivity. Foliage uptake of ozone via dry deposition damages photosynthesis and causes stomatal closure. These foliage changes could lead to a cascade of biogeochemical and biogeophysical effects that not only modulate the carbon cycle, regional hydrometeorology and climate, but also cause feedbacks onto surface ozone concentration itself. In this study, we implement a semi-empirical parameterization of ozone damage on vegetation in the Community Earth System Model to enable online ozone-vegetation coupling, so that for the first time ecosystem structure and ozone concentration can coevolve in fully coupled land-atmosphere simulations. With ozone-vegetation coupling, present-day surface ozone is simulated to be higher by up to 4-6 ppbv over Europe, North America and China. Reduced dry deposition velocity following ozone damage contributes to ˜ 40-100 % of those increases, constituting a significant positive biogeochemical feedback on ozone air quality. Enhanced biogenic isoprene emission is found to contribute to most of the remaining increases, and is driven mainly by higher vegetation temperature that results from lower transpiration rate. This isoprene-driven pathway represents an indirect, positive meteorological feedback. The reduction in both dry deposition and transpiration is mostly associated with reduced stomatal conductance following ozone damage, whereas the modification of photosynthesis and further changes in ecosystem productivity are found to play a smaller role in contributing to the ozone-vegetation feedbacks. Our results highlight the need to consider two-way ozone-vegetation coupling in Earth system models to derive a more complete understanding and yield more reliable future predictions of ozone air quality.

LABORATORY AND COMPUTATIONAL INVESTIGATIONS OF THE ATMOSPHERIC CHEMISTRY OF KEY OXIDATION PRODUCTS CONTROLLING TROPOSPHERIC OZONE FORMATION

EPA Science Inventory

Major uncertainties remain in our ability to identify the key reactions and primary oxidation products of volatile hydrocarbons that contribute to ozone formation in the troposphere. To reduce these uncertainties, computational chemistry, mechanistic and process analysis techniqu...

The role of refinery flaring events and bay breezes on a high surface ozone episode during the Houston, Texas DISCOVER-AQ field campaign

NASA Astrophysics Data System (ADS)

Loughner, C.; Follette-Cook, M. B.; Fried, A.; Pickering, K. E.

2015-12-01

The highest observed surface ozone concentrations in the Houston metropolitan area in 2013 occurred on September 25, which coincided with the Texas DISCOVER-AQ (Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relevant to Air Quality) field campaign. Surface ozone was elevated throughout the Houston metropolitan area with maximum 8-hour average ozone peaking along the western shore of Galveston Bay, reaching 124 ppbv, almost 50 ppbv above the current EPA standard of 75 ppbv. The NASA P-3B aircraft observed plumes from refinery flares west and northwest of Galveston Bay that were transported over the water. Continental air pollution from the north was transported into the Houston metropolitan area where it mixed with locally generated emissions. A bay breeze circulation formed causing pollutants that were transported out over the water in the morning to recirculate back inland where they mixed with freshly emitted pollution near the bay breeze convergence zone. The highest surface ozone concentrations were reported near the bay breeze front. This ozone episode will be presented using measurements made during the DISCOVER-AQ field campaign and a CMAQ model simulation with integrated source apportionment, which tracks the contribution of emissions source groups and regions on ozone concentrations.

Formation of halogen-induced secondary organic aerosol (XOA)

NASA Astrophysics Data System (ADS)

Kamilli, Katharina; Ofner, Johannes; Zetzsch, Cornelius; Held, Andreas

2013-04-01

Reactive halogen species (RHS) are very important due to their potential of stratospheric ozone depletion and surface ozone destruction. RHS seem to interact with precursors of secondary organic aerosol (SOA) similarly to common atmospheric oxidants like OH radicals and ozone. The potential interaction of RHS with preformed SOA has recently been studied (Ofner et al., 2012). Although aerosol formation from reaction of RHS with typical SOA precursors was previously studied (e.g. Cai et al., 2006), no data are available on bromine-induced aerosol formation from organic precursors yet. An aerosol smog-chamber was used to examine the halogen-induced secondary organic aerosol (XOA) formation under atmospheric conditions using simulated sunlight. With a concentration of 10 ppb for the organic precursor, 2 ppb for molecular chlorine, and 10 ppb for molecular bromine, the experimental setup is close to ambient conditions. By combined measurements of the aerosol size distribution, ozone and NOx mixing ratios, as well as the decay of the organic precursor, aerosol yields and aerosol growth rates were determined. The decay of the organic precursor was analyzed by capillary gas chromatography coupled with flame-ionization detection (GC-FID) and the aerosol size distribution was measured using a Scanning Mobility Particle Sizer (SMPS). Additionally, with the decay rate of the precursor and the calculated photolysis rates of molecular halogen species, based on the well-known spectrum of the solar simulator, mechanistic details on the XOA formation pathways can be determined. We observed XOA formation even at very low precursor and RHS concentrations with a diameter mode at 10-20 nm and a number concentration up to 1000000 particles cm-3. While the XOA formation from chlorine is very rapid, the interaction of bromine with the organic precursors is about five times slower. The aerosol yield reached maximum values of 0.01 for the reaction of chlorine with α-pinene and 0.0004 for bromine with α-pinene. This work was funded by German Research Foundation (DFG) under grants HE 5214/5-1 and ZE792/5-2. References: Cai, X., and Griffin, R. J.: Secondary aerosol formation from the oxidation of biogenic hydrocarbons by chlorine atoms, J. Geophys. Res., 111, D14206/14201-D14206/14214, 2006. Ofner, J. Balzer, N., Buxmann, J., Grothe, H., Schmitt-Kopplin, Ph., Platt, U., and Zetzsch, C., Halogenation processes of secondary organic aerosol and implications on halogen release mechanisms, Atmos. Chem. Phys. Discuss. 12, 2975-3017, 2012.

Determination of volatile organic compound emissions and ozone formation from spraying solvent-based pesticides.

PubMed

Kumar, Anuj; Howard, Cody J; Derrick, Doniche; Malkina, Irina L; Mitloehner, Frank M; Kleeman, Michael J; Alaimo, Christopher P; Flocchini, Robert G; Green, Peter G

2011-01-01

Large-scale agricultural activities have come under scrutiny for possible contributions to the emission of ozone precursors. The San Joaquin Valley (SJV) of California is an area with intense agricultural activity that exceeds the federal ozone standards for more than 30 to 40 d yr(-1) and the more stringent state standards for more than 100 d yr(-1). Pesticides are used widely in both agricultural and residential subregions of the SJV, but the largest use, by weight of "active ingredient," is in agriculture. The objective of the study was to determine the role of pesticide application on airborne volatile organic compounds (VOC) concentrations and ozone formation in the SJV. The ozone formation from the pesticide formulation sprayed on commercial orchards was studied using two transportable smog chambers at four application sites during the summers of 2007 and 2008. In addition to the direct measurements of ozone formation, airborne VOC concentrations were measured before and after pesticide spraying using canister and sorbent tube sampling techniques. Soil VOC concentrations were also measured to understand the distribution of VOCs between different environmental compartments. Numerous VOCs were detected in the air and soil samples throughout the experiment but higher molecular weight aromatic hydrocarbons were the primary compounds observed in elevated concentrations immediately after pesticide spraying. Measurements indicate that the ozone concentration formed by VOC downwind of the orchard may increase up to 15 ppb after pesticide application, with a return back to prespray levels after 1 to 2 d. by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Deposition velocities and impact of physical properties on ozone removal for building materials

NASA Astrophysics Data System (ADS)

Lin, Chi-Chi; Hsu, Shu-Chen

2015-01-01

This study aims to estimate the ozone deposition velocities of eight commonly used building materials (BMs) which include calcium silicate board (CSB), green calcium silicate board (GCSB), mineral fiber ceiling (MFC), green mineral fiber ceiling (GMFC), gypsum board (GB), green gypsum board (GGB), wooden flooring (WF) and green wooden flooring (GWF). In addition, the impact of physical properties (specific surface area and total pore volume of BM) on ozone removal ability was also explored and discussed. Studies were conducted in a small-scale environmental stainless steel chamber. CSB and GCSB showed the highest ozone deposition velocities, while WF and GWF showed the lowest ozone deposition velocities among test BMs materials. All reaction probabilities were estimated to fall within the order of magnitude of 10-6. Green BMs showed lower reaction probabilities with ozone comparing with non-green BMs except for GGB. Consistent with the trends for deposition velocity, fleecy and porous materials exhibit higher reaction probabilities than smooth, non-porous surfaces. Specific surface area of BM is more closely related to ozone removal than total pore volume of BM with R2 of 0.93 vs. R2 of 0.84. Discussion of Thiele modulus for all test BMs indicates surface reactions are occurring quickly relative to internal diffusion and ozone removal is internal diffusion-limited.

GOME-2 Tropospheric Ozone Profile Retrievals from Joint UV/Visible Measurement

NASA Astrophysics Data System (ADS)

Liu, X.; Zoogman, P.; Chance, K.; Cai, Z.; Nowlan, C. R.; Huang, G.; Gonzalez Abad, G.

2016-12-01

It has been shown from sensitivity studies that adding visible measurements in the Chappuis ozone band to UV measurements in the Hartley/Huggins ozone bands can significantly enhance retrieval sensitivity to lower tropospheric ozone from backscattered solar radiances due to deeper photon penetration in the visible to the surface than in the ultraviolet. The first NASA EVI (Earth Venture Instrument) TEMPO (Tropospheric Emissions: Monitoring of Pollution) instrument is being developed to measure backscattered solar radiation in two channels ( 290-490 and 540-740 nm) and make atmospheric pollution measurements over North America from the Geostationary orbit. However, this retrieval enhancement has yet to be demonstrated from existing measurements due to the weak ozone absorption in the visible and strong interferences from surface reflectance and aerosols and the requirement of accurate radiometric calibration across different spectral channels. We present GOME-2 retrievals from joint UV/visible measurements using the SAO ozone profile retrieval algorithm, to directly explore the retrieval improvement in lower tropospheric ozone from additional visible measurements. To reduce the retrieval interference from surface reflectance, we add characterization of surface spectral reflectance in the visible based on combining EOFs (Empirical Orthogonal Functions) derived from ASTER and other surface reflectance spectra with MODIS BRDF climatology into the ozone profile algorithm. The impacts of various types of aerosols and surface BRDF on the retrievals will be investigated. In addition, we will also perform empirical radiometric calibration of the GOME-2 data based on radiative transfer simulations. We will evaluate the retrieval improvement of joint UV/visible retrieval over the UV retrieval based on fitting quality and validation against ozonesonde observations.

Ozone response to enhanced heterogeneous processing after the eruption of Mt. Pinatubo

NASA Technical Reports Server (NTRS)

Rodriguez, Jose M.; Ko, M. K. W.; Sze, N. D.; Heisey, C. W.; Yue, G. K.; Mccormick, M. P.

1994-01-01

Increases in aerosol loading after the Pinatubo eruption are expected to cause additional ozone depletion. Even though aerosol loadings were highest in the winter of 1991-1992, recent analyses of satellite and ground-based ozone measurements indicate that ozone levels in the winter of 1992-1993 are the lowest recorded in recent years, raising the question of the mechanisms responsible for such behavior. We have incorporated aerosol surface areas derived from the Stratospheric Aerosol and Gas Experiment II (SAGE-II) measurements into our two-dimensional model. Inclusion of heterogeneous chemsitry on these enhanced aerosol surfaces yields maximum ozone reductions during the winter of 1992-1993 in the Northern Hemisphere, consistent with those derived from observations. This delayed behavior is due to the combination of the non-linear nature of the impact of heterogeneous reactions as a function of aerosol surface area, and the long time constants for ozone in the lower stratosphere. If heterogeneous mechanisms are primarily responsible for the low 1992-1993 ozone levels, we expect ozone concentrations to start recovering in 1994.

Air Quality Impacts of Oil and Gas Operations in the Northern Colorado Front Range

NASA Astrophysics Data System (ADS)

Helmig, D.; Thompson, C. R.; Jacques, H.; Smith, K. R.; Terrell, R. M.

2014-12-01

Exceedences of the US EPA National Ambient Air Quality Standard (NAAQS) for surface ozone have been reported from monitoring sites in the Northern Colorado Front Range (NCFR) for more than fifteen years during summer. Comparison of ozone records from the NCFR clearly show that ozone primarily results from regional photochemical daytime production. Recent trend analyses do not show an improvement of surface ozone despite efforts by the State of Colorado to curb ozone precursor emissions. Our review of atmospheric volatile organic compound (VOC) measurements from historic and recent monitoring shows significant spatial increases of atmospheric VOC towards the oil and gas development area in Weld County, NW of the Denver-Boulder metropolitan region. Secondly, analyses of VOC trends and VOC signatures show an overall increase of oil and gas associated VOC relative to other VOC sources. These analyses suggest that oil and gas emissions are playing and increasing role in ozone production in the NCFR and that reductions of oil and gas emissions would be beneficial for lowering surface ozone and attainment of the ozone NAAQS.

Effects of future land use and ecosystem changes on boundary-layer meteorology and air quality

NASA Astrophysics Data System (ADS)

Tai, A. P. K.; Wang, L.; Sadeke, M.

2017-12-01

Land vegetation plays key roles shaping boundary-layer meteorology and air quality via various pathways. Vegetation can directly affect surface ozone via dry deposition and biogenic emissions of volatile organic compounds (VOCs). Transpiration from land plants can also influence surface temperature, soil moisture and boundary-layer mixing depth, thereby indirectly affecting surface ozone. Future changes in the distribution, density and physiology of vegetation are therefore expected to have major ramifications for surface ozone air quality. In our study, we examine two aspects of potential vegetation changes using the Community Earth System Model (CESM) in the fully coupled land-atmosphere configuration, and evaluate their implications on meteorology and air quality: 1) land use change, which alters the distribution of plant functional types and total leaf density; and 2) ozone damage on vegetation, which alters leaf density and physiology (e.g., stomatal resistance). We find that, following the RCP8.5 scenario for 2050, global cropland expansion induces only minor changes in surface ozone in tropical and subtropical regions, but statistically significant changes by up to +4 ppbv in midlatitude North America and East Asia, mostly due to higher surface temperature that enhances biogenic VOC emissions, and reduced dry deposition to a lesser degree. These changes are in turn to driven mostly by meteorological changes that include a shift from latent to sensible heat in the surface energy balance and reduced soil moisture, reflecting not only local responses but also a northward expansion of the Hadley Cell. On the other hand, ozone damage on vegetation driven by rising anthropogenic emissions is shown to induce a further enhancement of ozone by up to +6 ppbv in midlatitude regions by 2050. This reflects a strong localized positive feedback, with severe ozone damage in polluted regions generally inducing stomatal closure, which in turn reduces transpiration, increases surface temperature, and thus enhances biogenic VOC emissions and surface ozone. Our findings demonstrate the importance of considering meteorological responses to vegetation changes in future air quality assessment, and call for greater coordination among land use, ecosystem and air quality management efforts.

The formation and control of emerging disinfection by-products of health concern.

PubMed

Krasner, Stuart W

2009-10-13

When drinking water treatment plants disinfect water, a wide range of disinfection by-products (DBPs) of health and regulatory concern are formed. Recent studies have identified emerging DBPs (e.g. iodinated trihalomethanes (THMs) and acids, haloacetonitriles, halonitromethanes (HNMs), haloacetaldehydes, nitrosamines) that may be more toxic than some of the regulated ones (e.g. chlorine- and bromine-containing THMs and haloacetic acids). Some of these emerging DBPs are associated with impaired drinking water supplies (e.g. impacted by treated wastewater, algae, iodide). In some cases, alternative primary or secondary disinfectants to chlorine (e.g. chloramines, chlorine dioxide, ozone, ultraviolet) that minimize the formation of some of the regulated DBPs may increase the formation of some of the emerging by-products. However, optimization of the various treatment processes and disinfection scenarios can allow plants to control to varying degrees the formation of regulated and emerging DBPs. For example, pre-disinfection with chlorine, chlorine dioxide or ozone can destroy precursors for N-nitrosodimethylamine, which is a chloramine by-product, whereas pre-oxidation with chlorine or ozone can oxidize iodide to iodate and minimize iodinated DBP formation during post-chloramination. Although pre-ozonation may increase the formation of trihaloacetaldehydes or selected HNMs during post-chlorination or chloramination, biofiltration may reduce the formation potential of these by-products.

A network of autonomous surface ozone monitors in Antarctica: technical description and first results

NASA Astrophysics Data System (ADS)

Bauguitte, S. J.; Brough, N.; Frey, M. M.; Jones, A. E.; Roscoe, H. K.; Wolff, E. W.

2009-12-01

Concentrations of surface ozone over polar regions cannot be derived from satellite data so can only be studied from ground-based platforms. To understand the regional picture a carefully-designed network of ground-based monitors is required. Here we report on a network of 10 autonomous ozone monitors that was established around the Weddell Sea sector of coastal Antarctica with a transect up onto the Antarctic Plateau during the International Polar Year. The aim was to measure for a full year, thus gaining a much-improved broader view of boundary layer ozone seasonality at different locations as well as on factors affecting the budget of surface ozone in Antarctica. Of specific interest were the balance between halogen-driven destruction and photochemical production from snow-emitted precursors, as well as the spatial extent of ozone depletion events. Each ozone monitor measured successfully within its predefined duty cycle throughout the year, with some differences in performance dependent on power availability. Here we present technical information and first results from the network.

Impact on short-lived climate forcers increases projected warming due to deforestation.

PubMed

Scott, C E; Monks, S A; Spracklen, D V; Arnold, S R; Forster, P M; Rap, A; Äijälä, M; Artaxo, P; Carslaw, K S; Chipperfield, M P; Ehn, M; Gilardoni, S; Heikkinen, L; Kulmala, M; Petäjä, T; Reddington, C L S; Rizzo, L V; Swietlicki, E; Vignati, E; Wilson, C

2018-01-11

The climate impact of deforestation depends on the relative strength of several biogeochemical and biogeophysical effects. In addition to affecting the exchange of carbon dioxide (CO 2 ) and moisture with the atmosphere and surface albedo, vegetation emits biogenic volatile organic compounds (BVOCs) that alter the formation of short-lived climate forcers (SLCFs), which include aerosol, ozone and methane. Here we show that a scenario of complete global deforestation results in a net positive radiative forcing (RF; 0.12 W m -2 ) from SLCFs, with the negative RF from decreases in ozone and methane concentrations partially offsetting the positive aerosol RF. Combining RFs due to CO 2 , surface albedo and SLCFs suggests that global deforestation could cause 0.8 K warming after 100 years, with SLCFs contributing 8% of the effect. However, deforestation as projected by the RCP8.5 scenario leads to zero net RF from SLCF, primarily due to nonlinearities in the aerosol indirect effect.

MODELING CRYPTOSPORIDIUM PARVUM OOCYST INACTIVATION AND BROMATE IN A FLOW-THROUGH OZONE CONTACTOR TREATING NATURAL WATER

EPA Science Inventory

A reactive transport model was developed to simultaneously predict Cryptosporidium parvum oocyst inactivation and bromate formation during ozonation of natural water. A mechanistic model previously established to predict bromate formation in organic-free synthetic waters w...

The Effects of Interactive Stratospheric Chemistry on Antarctic and Southern Ocean Climate Change in an AOGCM

NASA Technical Reports Server (NTRS)

Li, Feng; Newman, Paul; Pawson, Steven; Waugh, Darryn

2014-01-01

Stratospheric ozone depletion has played a dominant role in driving Antarctic climate change in the last decades. In order to capture the stratospheric ozone forcing, many coupled atmosphere-ocean general circulation models (AOGCMs) prescribe the Antarctic ozone hole using monthly and zonally averaged ozone field. However, the prescribed ozone hole has a high ozone bias and lacks zonal asymmetry. The impacts of these biases on model simulations, particularly on Southern Ocean and the Antarctic sea ice, are not well understood. The purpose of this study is to determine the effects of using interactive stratospheric chemistry instead of prescribed ozone on Antarctic and Southern Ocean climate change in an AOGCM. We compare two sets of ensemble simulations for the 1960-2010 period using different versions of the Goddard Earth Observing System 5 - AOGCM: one with interactive stratospheric chemistry, and the other with prescribed monthly and zonally averaged ozone and 6 other stratospheric radiative species calculated from the interactive chemistry simulations. Consistent with previous studies using prescribed sea surface temperatures and sea ice concentrations, the interactive chemistry runs simulate a deeper Antarctic ozone hole and consistently larger changes in surface pressure and winds than the prescribed ozone runs. The use of a coupled atmosphere-ocean model in this study enables us to determine the impact of these surface changes on Southern Ocean circulation and Antarctic sea ice. The larger surface wind trends in the interactive chemistry case lead to larger Southern Ocean circulation trends with stronger changes in northerly and westerly surface flow near the Antarctica continent and stronger upwelling near 60S. Using interactive chemistry also simulates a larger decrease of sea ice concentrations. Our results highlight the importance of using interactive chemistry in order to correctly capture the influences of stratospheric ozone depletion on climate change over Antarctic and the Southern Ocean.

Characterizing the seasonal cycle and vertical structure of ozone in Paris, France using four years of ground based LIDAR measurements in the lowermost troposphere

NASA Astrophysics Data System (ADS)

Klein, Amélie; Ancellet, Gérard; Ravetta, François; Thomas, Jennie L.; Pazmino, Andrea

2017-10-01

Systematic ozone LIDAR measurements were completed during a 4 year period (2011-2014) in Paris, France to study the seasonal variability of the vertical structure of ozone in the urban boundary layer. In addition, we use in-situ measurements from the surface air quality network that is located in Paris (AIRPARIF). Specifically, we use ozone and NO2 measurements made at two urban stations: Paris13 (60 m ASL) and the Eiffel Tower (310 m ASL) to validate and interpret the LIDAR profiles. Remote sensed tropospheric NO2 integrated columns from the SAOZ instrument located in Paris are also used to interpret ozone measurements. Comparison between ozone LIDAR measurements averaged from 250 m to 500 m and the Eiffel Tower in-situ measurements shows that the accuracy of the LIDAR (originally ±14 μg·m-3) is significantly improved (±7 μg·m-3) when a small telescope with a wide angular aperture is used. Results for the seasonal cycle of the ozone vertical gradient are found to be similar using two methods: (1) measured differences between AIRPARIF stations with measurements at 60 m ASL and 310 m ASL and (2) using LIDAR profiles from 300 m to the top of the Planetary Boundary Layer (PBL). Ozone concentrations measured by the LIDAR increase with altitude within the PBL, with a steeper gradient in winter (60 μg·m-3·km-1) and a less strong gradient in summer (20 μg·m-3·km-1). Results show that in winter, there is a sharp positive gradient of ozone at the surface, which is explained by ozone titration by NO combined with increased atmospheric stability in winter. In the afternoon during summer, photochemistry and vertical mixing are large enough to compensate for ozone titration near the surface, where NOx is emitted, and there is no gradient in ozone observed. In contrast, in the summer during the morning, ozone has a sharper positive vertical gradient similar to the winter values. Comparison of the vertically averaged ozone concentrations up to (0-3 km) and urban layer (0-310 m) ozone concentrations shows that the ratio between these two quantities is the largest in summer (86%) and the lowest in winter (49%). We conclude that satellite measurements that represent the 0-3 km integrated ozone column are not necessarily a good proxy for surface ozone and may lead to incorrect conclusions about the surface ozone seasonal variability. The ratio between the urban layer NO2 average concentration and the boundary layer NO2 average concentration obtained from SAOZ NO2 tropospheric columns is always less than 50%, meaning NO2 does not decrease linearly in the PBL, but with a sharper decrease close to the surface.

Lidar Observations of the Vertical Structure of Ozone and Aerosol during Wintertime High-Ozone Episodes Associated with Oil and Gas Exploration in the Uintah Basin

NASA Astrophysics Data System (ADS)

Senff, C. J.; Langford, A. O.; Banta, R. M.; Alvarez, R. J.; Weickmann, A.; Sandberg, S.; Marchbanks, R. D.; Brewer, A.; Hardesty, R. M.

2013-12-01

The Uintah Basin in northeast Utah has been experiencing extended periods of poor air quality in the winter months including very high levels of surface ozone. To investigate the causes of these wintertime ozone pollution episodes, two comprehensive studies were undertaken in January/February of 2012 and 2013. As part of these Uintah Basin Ozone Studies (UBOS), NOAA deployed its ground-based, scanning Tunable Optical Profiler for Aerosol and oZone (TOPAZ) lidar to document the vertical structure of ozone and aerosol backscatter from near the surface up to about 3 km above ground level (AGL). TOPAZ, along with a comprehensive set of chemistry and meteorological measurements, was situated in both years at the Horse Pool site at the northern edge of a large concentration of gas producing wells in the eastern part of the Uintah Basin. The 2012 study was characterized by unusually warm and snow-free condition and the TOPAZ lidar observed deep boundary layers (BL) and mostly well-mixed vertical ozone profiles at or slightly above tropospheric background levels. During UBOS 2013, winter weather conditions in the Uintah Basin were more typical with snow-covered ground and a persistent, shallow cold-pool layer. The TOPAZ lidar characterized with great temporal and spatial detail the evolution of multiple high-ozone episodes as well as cleanout events caused by the passage of synoptic-scale storm systems. Despite the snow cover, the TOPAZ observations show well-mixed afternoon ozone and aerosol profiles up to about 100 m AGL. After several days of pollutant buildup, BL ozone values reached 120-150 ppbv. Above the mixed layer, ozone values gradually decreased to tropospheric background values of around 50 ppbv throughout the several-hundred-meter-deep cold-pool layer and then stayed constant above that up to about 3 km AGL. During the ozone episodes, the lidar observations show no indication of either vertical or horizontal transport of high ozone levels to the surface, thus supporting the notion that ozone is locally produced in the Uintah Basin. In both winters, TOPAZ occasionally observed ozone titration as the NOx-rich plume from the nearby Bonanza power plant was advected over the Horse Pool site. In 2012, low ozone values due to titration were observed at the surface and throughout the well-mixed BL, while in 2013 low ozone values were confined to the upper part of the cold-pool layer above the BL. This suggests that power plant NOx was very likely not part of the precursor mix that led to the high surface ozone values observed in 2013.

Surface recombination of oxygen atoms in O2 plasma at increased pressure: II. Vibrational temperature and surface production of ozone

NASA Astrophysics Data System (ADS)

Lopaev, D. V.; Malykhin, E. M.; Zyryanov, S. M.

2011-01-01

Ozone production in an oxygen glow discharge in a quartz tube was studied in the pressure range of 10-50 Torr. The O3 density distribution along the tube diameter was measured by UV absorption spectroscopy, and ozone vibrational temperature TV was found comparing the calculated ab initio absorption spectra with the experimental ones. It has been shown that the O3 production mainly occurs on a tube surface whereas ozone is lost in the tube centre where in contrast the electron and oxygen atom densities are maximal. Two models were used to analyse the obtained results. The first one is a kinetic 1D model for the processes occurring near the tube walls with the participation of the main particles: O(3P), O2, O2(1Δg) and O3 molecules in different vibrational states. The agreement of O3 and O(3P) density profiles and TV calculated in the model with observed ones was reached by varying the single model parameter—ozone production probability (\\gamma_{O_{3}}) on the quartz tube surface on the assumption that O3 production occurs mainly in the surface recombination of physisorbed O(3P) and O2. The phenomenological model of the surface processes with the participation of oxygen atoms and molecules including singlet oxygen molecules was also considered to analyse \\gamma_{O_{3}} data obtained in the kinetic model. A good agreement between the experimental data and the data of both models—the kinetic 1D model and the phenomenological surface model—was obtained in the full range of the studied conditions that allowed consideration of the ozone surface production mechanism in more detail. The important role of singlet oxygen in ozone surface production was shown. The O3 surface production rate directly depends on the density of physisorbed oxygen atoms and molecules and can be high with increasing pressure and energy inputted into plasma while simultaneously keeping the surface temperature low enough. Using the special discharge cell design, such an approach opens up the possibility to develop compact ozonizers having high ozone yield at the low energy cost of O → O3 conversion.

Quantifying isentropic stratosphere-troposphere exchange of ozone

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Huang; Chen, Gang; Tang, Qi

There is increased evidence that stratosphere-troposphere exchange (STE) of ozone has a significant impact on tropospheric chemistry and radiation. Traditional diagnostics of STE consider the ozone budget in the lowermost stratosphere (LMS) as a whole. However, this can only render the hemispherically integrated ozone flux and therefore does not distinguish the exchange of ozone into low latitudes from that into high latitudes. The exchange of ozone at different latitudes may have different tropospheric impacts. This present study extends the traditional approach from the entire LMS to individual isentropic layers in the LMS and therefore gives the meridional distribution of STEmore » by the latitudes where each isentropic surface intersects the tropopause. The specified dynamics version of the Whole Atmosphere Community Climate Model is used to estimate the STE ozone flux on each isentropic surface. It is found that net troposphere-to-stratosphere ozone transport occurs in low latitudes along the 350–380 K isentropic surfaces and that net stratosphere-to-troposphere ozone transport takes place in the extratropics along the 280–350 K isentropes. Particularly, the seasonal cycle of extratropical STE ozone flux in the Northern Hemisphere displays a maximum in late spring and early summer, following the seasonal migration of the upper tropospheric jet and associated isentropic mixing. Moreover, differential diabatic heating and isentropic mixing tend to induce STE ozone fluxes in opposite directions, but the net effect results in a spatiotemporal pattern similar to the STE ozone flux associated with isentropic mixing.« less

Quantifying isentropic stratosphere-troposphere exchange of ozone

DOE PAGES

Yang, Huang; Chen, Gang; Tang, Qi; ...

2016-03-25

There is increased evidence that stratosphere-troposphere exchange (STE) of ozone has a significant impact on tropospheric chemistry and radiation. Traditional diagnostics of STE consider the ozone budget in the lowermost stratosphere (LMS) as a whole. However, this can only render the hemispherically integrated ozone flux and therefore does not distinguish the exchange of ozone into low latitudes from that into high latitudes. The exchange of ozone at different latitudes may have different tropospheric impacts. This present study extends the traditional approach from the entire LMS to individual isentropic layers in the LMS and therefore gives the meridional distribution of STEmore » by the latitudes where each isentropic surface intersects the tropopause. The specified dynamics version of the Whole Atmosphere Community Climate Model is used to estimate the STE ozone flux on each isentropic surface. It is found that net troposphere-to-stratosphere ozone transport occurs in low latitudes along the 350–380 K isentropic surfaces and that net stratosphere-to-troposphere ozone transport takes place in the extratropics along the 280–350 K isentropes. Particularly, the seasonal cycle of extratropical STE ozone flux in the Northern Hemisphere displays a maximum in late spring and early summer, following the seasonal migration of the upper tropospheric jet and associated isentropic mixing. Moreover, differential diabatic heating and isentropic mixing tend to induce STE ozone fluxes in opposite directions, but the net effect results in a spatiotemporal pattern similar to the STE ozone flux associated with isentropic mixing.« less

The effect of surface anisotropy on the accuracy of total ozone estimates from satellite observations

NASA Technical Reports Server (NTRS)

Fraser, R. S.; Ahmad, Z.

1978-01-01

The total amount of ozone in a vertical column of the earth's atmosphere is being derived from satellite measurements of the intensity of ultraviolet sunlight scattered by the earth-atmosphere system. The algorithm for deriving the ozone amount utilizes the assumption that the earth's surface reflects the incident light isotropically according to Lambert's law. Natural surface reflection deviates more or less from this law. Two extreme examples of anisotropic reflection from dark ocean and from bright snow are analyzed by means of models for their effects on the derived values of ozone.

Coincident Observations of Surface Ozone and NMVOCs over Abu Dhabi

NASA Astrophysics Data System (ADS)

Abbasi, Naveed; Majeed, Tariq; Iqbal, Mazhar; Tarasick, David; Davies, Jonathan; Riemer, Daniel; Apel, Eric

2016-07-01

The vertical profiles of ozone are measured coincidently with non-methane volatile organic compounds (NMVOCs) at the meteorological site located at the Abu Dhabi international airport (latitude 24.45N; longitude 54.22E) during the years 2012 - 2014. Some of the profiles show elevated surface ozone >95 ppbv during the winter months (December, January and February). The ground-level NMVOCs obtained from the gas chromatography-flame ionization detection/mass spectrometry system also show elevated values of acetylene, ethane, propane, butane, pentane, benzene, and toluene. NMVOCs and ozone abundances in other seasons are much lower than the values in winter season. NMVOCs are emitted from an extensive number of sources in urban environments including fuel production, distribution, and consumption, and serve as precursor of ozone. Transport sources contribute a substantial portion of the NMVOC burden to the urban atmosphere in developed regions. Abu Dhabi is located at the edge of the Arabian Gulf and is highly affected by emissions from petrochemical industries in the neighboring Gulf region. The preliminary results indicate that wintertime enhancement in ozone is associated with large values of NMVOCs at Abu Dhabi. The domestic production of surface ozone is estimated from the combination of oxygen recombination and NMVOCs and compared with the data. It is estimated that about 40-50% of ozone in Abu Dhabi is transported from the neighbouring petrochemical industries. We will present ozone sounding and NMVOCs data and our model estimates of surface ozone, including a discussion on the high levels of the tropospheric ozone responsible for contaminating the air quality in the UAE. This work is supported by National Research Foundation, UAE.

Cellulose and lignin biosynthesis is altered by ozone in wood of hybrid poplar (Populus tremula×alba)

PubMed Central

Richet, Nicolas; Afif, Dany; Huber, Françoise; Pollet, Brigitte; Banvoy, Jacques; El Zein, Rana; Lapierre, Catherine; Dizengremel, Pierre; Perré, Patrick; Cabané, Mireille

2011-01-01

Wood formation in trees is a dynamic process that is strongly affected by environmental factors. However, the impact of ozone on wood is poorly documented. The objective of this study was to assess the effects of ozone on wood formation by focusing on the two major wood components, cellulose and lignin, and analysing any anatomical modifications. Young hybrid poplars (Populus tremula×alba) were cultivated under different ozone concentrations (50, 100, 200, and 300 nl l−1). As upright poplars usually develop tension wood in a non-set pattern, the trees were bent in order to induce tension wood formation on the upper side of the stem and normal or opposite wood on the lower side. Biosynthesis of cellulose and lignin (enzymes and RNA levels), together with cambial growth, decreased in response to ozone exposure. The cellulose to lignin ratio was reduced, suggesting that cellulose biosynthesis was more affected than that of lignin. Tension wood was generally more altered than opposite wood, especially at the anatomical level. Tension wood may be more susceptible to reduced carbon allocation to the stems under ozone exposure. These results suggested a coordinated regulation of cellulose and lignin deposition to sustain mechanical strength under ozone. The modifications of the cellulose to lignin ratio and wood anatomy could allow the tree to maintain radial growth while minimizing carbon cost. PMID:21357770

Influence of mountains on Arctic tropospheric ozone

NASA Astrophysics Data System (ADS)

Seabrook, Jeffrey; Whiteway, James

2016-02-01

Tropospheric ozone was measured above Ellesmere Island in the Canadian Arctic during spring of 2008 using a differential absorption lidar. The observations were carried out at Eureka Weather Station, which is located between various mountain ranges. Analysis of the observations revealed that mountains had a significant effect on the vertical distribution of ozone. Ozone depletion events were observed when air that had spent significant time near to the frozen surface of the Arctic Ocean reached Eureka. This air arrived at Eureka by flowing over the surrounding mountains. Surface level ozone depletions were not observed during periods when mountains blocked the flow of air from over the sea ice. In the case of blocking there was an enhancement in the amount of ozone near the surface as air from the midtroposphere descended in the lee of the mountains. Three case studies from spring of 2008 are described.

Long-term trends of surface ozone and its influencing factors at the Mt Waliguan GAW station, China - Part 1: Overall trends and characteristics

NASA Astrophysics Data System (ADS)

Xu, Wanyun; Lin, Weili; Xu, Xiaobin; Tang, Jie; Huang, Jianqing; Wu, Hao; Zhang, Xiaochun

2016-05-01

Tropospheric ozone is an important atmospheric oxidant, greenhouse gas and atmospheric pollutant at the same time. The oxidation capacity of the atmosphere, climate, human and vegetation health can be impacted by the increase of the ozone level. Therefore, long-term determination of trends of baseline ozone is highly needed information for environmental and climate change assessment. So far, studies on the long-term trends of ozone at representative sites are mainly available for European and North American sites. Similar studies are lacking for China and many other developing countries. Measurements of surface ozone were carried out at a baseline Global Atmospheric Watch (GAW) station in the north-eastern Tibetan Plateau region (Mt Waliguan, 36°17' N, 100°54' E, 3816 m a.s.l.) for the period of 1994 to 2013. To uncover the variation characteristics, long-term trends and influencing factors of surface ozone at this remote site in western China, a two-part study has been carried out, with this part focusing on the overall characteristics of diurnal, seasonal and long-term variations and the trends of surface ozone. To obtain reliable ozone trends, we performed the Mann-Kendall trend test and the Hilbert-Huang transform (HHT) analysis on the ozone data. Our results confirm that the mountain-valley breeze plays an important role in the diurnal cycle of surface ozone at Waliguan, resulting in higher ozone values during the night and lower ones during the day, as was previously reported. Systematic diurnal and seasonal variations were found in mountain-valley breezes at the site, which were used in defining season-dependent daytime and nighttime periods for trend calculations. Significant positive trends in surface ozone were detected for both daytime (0.24 ± 0.16 ppbv year-1) and nighttime (0.28 ± 0.17 ppbv year-1). The largest nighttime increasing rate occurred in autumn (0.29 ± 0.11 ppbv year-1), followed by spring (0.24 ± 0.12 ppbv year-1), summer (0.22 ± 0.20 ppbv year-1) and winter (0.13 ± 0.10 ppbv year-1), respectively. The HHT spectral analysis identified four different stages with different positive trends, with the largest increase occurring around May 2000 and October 2010. The HHT results suggest that there were 2-4a, 7a and 11a periodicities in the time series of surface ozone at Waliguan. The results of this study can be used for assessments of climate and environment change and in the validation of chemistry-climate models.

Identifying and forecasting deep stratospheric ozone intrusions over the western United States from space

NASA Astrophysics Data System (ADS)

Lin, M.; Fiore, A. M.; Horowitz, L. W.; Cooper, O. R.; Langford, A. O.; Pan, L.; Liu, X.; Reddy, P. J.

2012-12-01

Recent studies have shown that deep stratospheric ozone intrusions can episodically enhance ground-level ozone above the health-based standard over the western U.S. in spring. Advanced warning of incoming intrusions could be used by state agencies to inform the public about poor air quality days. Here we explore the potential for using total ozone retrievals (version 5.2, level 3) at twice daily near global coverage from the AIRS instrument aboard the NASA Aqua satellite to identify stratospheric intrusions and forecast the eventual surface destination of transported stratospheric ozone. The method involves the correlation of AIRS daily total ozone columns at each 1ox1o grid box ~1-3 days prior to stratospheric enhancements to daily maximum 8-hour average ozone at a selected surface site using datasets from April to June in 2003-2011. The surface stratospheric enhancements are estimated by the GFDL AM3 chemistry-climate model which includes full stratospheric and tropospheric chemistry and is nudged to reanalysis winds. Our earlier work shows that the model presents deep stratospheric intrusions over the Western U.S. consistently with observations from AIRS, surface networks, daily ozone sondes, and aircraft lidar available in spring of 2010 during the NOAA CalNex field campaign. For the 15 surface sites in the U.S. Mountain West considered, a correlation coefficient of 0.4-0.7 emerges with AIRS ozone columns over 30o-50oN latitudes and 125o-105oW longitudes - variability in the AIRS column within this spatial domain indicates incoming intrusions. For each "surface receptor site", the spatial domain can narrow to an area ~5ox5o northwest of the individual site, with the strong correlation (0.5-0.7) occurring when the AIRS data is lagged by 1 day from the AM3 stratospheric enhancements in surface air. The spatial pattern of correlations is consistent with our process-oriented understanding developed from case studies of extreme intrusions. Surface observations during these events show that the sites experiencing elevated ozone levels are typically located over the southeastern side of the enhanced ozone columns captured by AIRS ~12 hours to 1 day prior. This first scoping study suggests there is potential to use near-daily global coverage of ozone in total column or in UT/LS levels from the space-based instruments (e.g. AIRS, OMI, MLS) to serve as a qualitative early-warning indicator of incoming stratospheric intrusions with a lead time of ~1-3 days. There is more skill in ~12 hours to 1 day as to where the intrusion will reach the surface, particularly during the ENSO years (i.e. 2003, 2008, 2010, 2011) when deep intrusions are more likely to occur as compared to other years. These space-based ozone products can also provide some indication of whether a historic exceedance was caused by an intrusion.

Formation of Ozonic Compound and Used as Therapeutic Agent in Medicine

NASA Astrophysics Data System (ADS)

Zhu, Lei; Ye, Chunyong; Min, Xinmin

2018-03-01

It has some encouraging results to use ozone in medicine. However, as ozone is usually in gas state, unstable and strong oxidability, it is difficult to be stored and used commonly. Ozone, ethylene, acrylic acid and the ozonic compounds were calculated to study the interaction between ozone and carrier material to form ozonide. The stability of the ozonide, or the bond strength between ozone and ions of carrier are controlled felicitously to release ozone from the ozonide with proper velocity. Ozone antimicrobial has been composed on the above principle. It can be used conveniently, especially for common families. There are some characteristics of ozone antimicrobial or ozone, such as universal applicability, efficiency and rapidity, security, strong penetrability, no drug resistance and sterilization and treatment simultaneity.

A climatology of visible surface reflectance spectra

NASA Astrophysics Data System (ADS)

Zoogman, Peter; Liu, Xiong; Chance, Kelly; Sun, Qingsong; Schaaf, Crystal; Mahr, Tobias; Wagner, Thomas

2016-09-01

We present a high spectral resolution climatology of visible surface reflectance as a function of wavelength for use in satellite measurements of ozone and other atmospheric species. The Tropospheric Emissions: Monitoring of Pollution (TEMPO) instrument is planned to measure backscattered solar radiation in the 290-740 nm range, including the ultraviolet and visible Chappuis ozone bands. Observation in the weak Chappuis band takes advantage of the relative transparency of the atmosphere in the visible to achieve sensitivity to near-surface ozone. However, due to the weakness of the ozone absorption features this measurement is more sensitive to errors in visible surface reflectance, which is highly variable. We utilize reflectance measurements of individual plant, man-made, and other surface types to calculate the primary modes of variability of visible surface reflectance at a high spectral resolution, comparable to that of TEMPO (0.6 nm). Using the Moderate-resolution Imaging Spectroradiometer (MODIS) Bidirection Reflectance Distribution Function (BRDF)/albedo product and our derived primary modes we construct a high spatial resolution climatology of wavelength-dependent surface reflectance over all viewing scenes and geometries. The Global Ozone Monitoring Experiment-2 (GOME-2) Lambertian Equivalent Reflectance (LER) product provides complementary information over water and snow scenes. Preliminary results using this approach in multispectral ultraviolet+visible ozone retrievals from the GOME-2 instrument show significant improvement to the fitting residuals over vegetated scenes.

Aromatic volatile organic compounds and their role in ground-level ozone formation in Russia

NASA Astrophysics Data System (ADS)

Berezina, E. V.; Moiseenko, K. B.; Skorokhod, A. I.; Elansky, N. F.; Belikov, I. B.

2017-05-01

This paper reports proton mass spectrometry data on aromatic volatile organic compounds (VOCs) (benzene, toluene, phenol, styrene, xylene, and propylbenzene) obtained in different Russian regions along the Trans-Siberian Railway from Moscow to Vladivostok, based on expedition data retrieved using the TRO-ICA-12 mobile laboratory in the summer of 2008. The contribution of aromatic VOCs to ozone formation in the cities and regions along the measurement route has been estimated quantitatively. The greatest contribution of aromatic VOCs to ozone formation is characteristic of large cities along the Trans-Siberian Railway (up to 7.5 ppbv O3) specified by the highest concentrations of aromatic VOCs (1-1.7 ppbv) and nitrogen oxides (>20 ppbv). The results obtained are indicative of a considerable contribution (30-50%) of anthropogenic emissions of VOCs to photochemical ozone generation in the large cities along the Trans-Siberian Railway in hot and dry weather against the background of a powerful natural factor such as isoprene emissions controlling the regional balance of ground-level ozone in warm seasons.

Global Ozone Distribution relevant to Human Health: Metrics and present day levels from the Tropospheric Ozone Assessment Report (TOAR)

NASA Astrophysics Data System (ADS)

Fleming, Z. L.; Doherty, R. M.; von Schneidemesser, E.; Cooper, O. R.; Malley, C.; Colette, A.; Xu, X.; Pinto, J. P.; Simpson, D.; Schultz, M. G.; Hamad, S.; Moola, R.; Solberg, S.; Feng, Z.

2017-12-01

Using stations from the TOAR surface ozone database, this study quantifies present-day global and regional distributions of five ozone metrics relevant for both short-term and long-term human exposure. These metrics were explored at ozone monitoring sites globally, and re-classified for this project as urban or non-urban using population densities and night-time lights. National surface ozone limit values are usually related to an annual number of exceedances of daily maximum 8-hour running mean (MDA8), with many countries not even having any ozone limit values. A discussion and comparison of exceedances in the different ozone metrics, their locations and the seasonality of exceedances provides clues as to the regions that potentially have more serious ozone health implications. Present day ozone levels (2010-2014) have been compared globally and show definite geographical differences (see Figure showing the annual 4th highest MDA8 for present day ozone for all non-urban stations). Higher ozone levels are seen in western compared to eastern US, and between southern and northern Europe, and generally higher levels in east Asia. The metrics reflective of peak concentrations show highest values in western North America, southern Europe and East Asia. A number of the metrics show similar distributions of North-South gradients, most prominent across Europe and Japan. The interquartile range of the regional ozone metrics was largest in East Asia, higher for urban stations in Asia but higher for non-urban stations in Europe and North America. With over 3000 monitoring stations included in this analysis and despite the higher densities of monitoring stations in Europe, north America and East Asia, this study provides the most comprehensive global picture to date of surface ozone levels in terms of health-relevant metrics.

Attribution of Trends and Variability in Surface Ozone over the United States

NASA Technical Reports Server (NTRS)

Strode, Sarah; Cooper, Owen; Damo, Megan; Logan, Jennifer; Rodriquez, Jose; Strahan, Susan; Witte, Jacquie

2013-01-01

Concentrations of tropospheric ozone, a greenhouse gas and air pollutant, are impacted by changes in precursor emissions as well meteorology and influx from the stratosphere. Observations show a decreasing trend in summertime surface ozone at rural stations in the eastern United States, while some western stations show increasing trends, particularly in springtime. We use the Global Modeling Initiative (GMI) global chemical transport model to investigate the roles of precursor emission changes, meteorological variability, and stratosphere-troposphere exchange (STE) in explaining observed trends in surface ozone from rural sites in the United States from 1991-2010. The model's interannual variability shows significant correlations with observations from many of the surface sites. We also compare the simulated ozone to ozonesonde data for several locations with sufficiently long records. We compare a simulation with time-dependent precursor emissions, including emission reductions over the United States and Europe and increases over Asia, to a simulation with fixed emissions to quantify the impact of changing emissions on the surface trends. The simulation with varying emissions reproduces much of the east-west difference in summertime ozone over the U.S., although it generally underestimates the negative trend in the East. In contrast, the fixed-emission simulation shows increasing ozone at both eastern and western sites. We will discuss possible causes of this behavior, including long-range transport and STE.

Comparison between assimilated and non-assimilated experiments of the MACCii global reanalysis near surface ozone

NASA Astrophysics Data System (ADS)

Tsikerdekis, Athanasios; Katragou, Eleni; Zanis, Prodromos; Melas, Dimitrios; Eskes, Henk; Flemming, Johannes; Huijnen, Vincent; Inness, Antje; Kapsomenakis, Ioannis; Schultz, Martin; Stein, Olaf; Zerefos, Christos

2014-05-01

In this work we evaluate near surface ozone concentrations of the MACCii global reanalysis using measurements from the EMEP and AIRBASE database. The eight-year long reanalysis of atmospheric composition data covering the period 2003-2010 was constructed as part of the FP7-funded Monitoring Atmospheric Composition and Climate project by assimilating satellite data into a global model and data assimilation system (Inness et al., 2013). The study mainly focuses in the differences between the assimilated and the non-assimilated experiments and aims to identify and quantify any improvements achieved by adding data assimilation to the system. Results are analyzed in eight European sub-regions and region-specific Taylor plots illustrate the evaluation and the overall predictive skill of each experiment. The diurnal and annual cycles of near surface ozone are evaluated for both experiments. Furthermore ozone exposure indices for crop growth (AOT40), human health (SOMO35) and the number of days that 8-hour ozone averages exceeded 60ppb and 90ppb have been calculated for each station based on both observed and simulated data. Results indicate mostly improvement of the assimilated experiment with respect to the high near surface ozone concentrations, the diurnal cycle and range and the bias in comparison to the non-assimilated experiment. The limitations of the comparison between assimilated and non-assimilated experiments for near surface ozone are also discussed.

A revised linear ozone photochemistry parameterization for use in transport and general circulation models: multi-annual simulations

NASA Astrophysics Data System (ADS)

Cariolle, D.; Teyssèdre, H.

2007-05-01

This article describes the validation of a linear parameterization of the ozone photochemistry for use in upper tropospheric and stratospheric studies. The present work extends a previously developed scheme by improving the 2-D model used to derive the coefficients of the parameterization. The chemical reaction rates are updated from a compilation that includes recent laboratory work. Furthermore, the polar ozone destruction due to heterogeneous reactions at the surface of the polar stratospheric clouds is taken into account as a function of the stratospheric temperature and the total chlorine content. Two versions of the parameterization are tested. The first one only requires the solution of a continuity equation for the time evolution of the ozone mixing ratio, the second one uses one additional equation for a cold tracer. The parameterization has been introduced into the chemical transport model MOCAGE. The model is integrated with wind and temperature fields from the ECMWF operational analyses over the period 2000-2004. Overall, the results from the two versions show a very good agreement between the modelled ozone distribution and the Total Ozone Mapping Spectrometer (TOMS) satellite data and the "in-situ" vertical soundings. During the course of the integration the model does not show any drift and the biases are generally small, of the order of 10%. The model also reproduces fairly well the polar ozone variability, notably the formation of "ozone holes" in the Southern Hemisphere with amplitudes and a seasonal evolution that follow the dynamics and time evolution of the polar vortex. The introduction of the cold tracer further improves the model simulation by allowing additional ozone destruction inside air masses exported from the high to the mid-latitudes, and by maintaining low ozone content inside the polar vortex of the Southern Hemisphere over longer periods in spring time. It is concluded that for the study of climate scenarios or the assimilation of ozone data, the present parameterization gives a valuable alternative to the introduction of detailed and computationally costly chemical schemes into general circulation models.

Links between extreme UV-radiation, total ozone, surface albedo and cloudiness: An analysis of 30 years of data from Switzerland and Austria

NASA Astrophysics Data System (ADS)

Rieder, H. E.; Staehelin, J.; Weihs, P.; Vuilleumier, L.; Blumthaler, M.; Holawe, F.; Lindfors, A.; Maeder, J. A.; Simic, S.; Wagner, J. E.; Walker, D.; Ribatet, M.

2009-04-01

Since the discovery of anthropogenic ozone depletion in the early 1970s (e.g. Molina and Rowland, 1974; Farman et al., 1985) the interest in stratospheric ozone trends and solar UV-B increased within the scientific community and the general public because of the link between reduced total column ozone and increased UV-radiation doses. Stratospheric ozone (e.g. Koch et al., 2005) and erythemal UV-radiation (e.g. Rieder et al., 2008) in the northern mid-latitudes are characterized by strong temporal variability. Long-term measurements of UV-B radiation are rare and datasets are only available for few locations and most of these measurements do not provide spectral information on the UV part of the spectra. During strong efforts in the reconstruction of erythemal UV, datasets of past UV-radiation doses became available for several measurement sites all over the globe. For Switzerland and Austria reconstructed UV datasets are available for 3 measurement sites (Davos, Sonnblick and Vienna) (Lindfors and Vuilleumier, 2005; Rieder et al., 2008). The world's longest ozone time series dating back to 1926 is available from Arosa, Switzerland, and is discussed in detail by Staehelin et al. (1998a,b). Recently new tools from extreme value theory have been applied to the Arosa time series to describe extreme events in low and high total ozone (Rieder et al., 2009). In our study we address the question of how much of the extremes in UV-radiation can be attributed to extremes in total ozone, high surface albedo and cloudiness. An analysis of the frequency distributions of such extreme events for the last decades is presented to gain a better understanding of the links between extreme erythemal UV-radiation, total ozone, surface albedo and clouds. References: Farman, J. C., Gardiner, B. G., and Shanklin, J. D.: Large losses of total ozone in Antarctica reveal seasonal ClOx/NOx interaction, Nature, 315, 207-210, 1985. Koch, G., Wernli, H., Schwierz, C., Staehelin, J., and Peter, T.: A composite study on the structure and formation of ozone miniholes and minihights over central Europe, J. Geophys. Res., 32, doi:10.1029/2004GL022062, 2005. Lindfors, A., and Vuilleumier, L.: Erythemal UV at Davos (Switzerland), 1926-2003, estimated using total ozone, sunshine duration, and snow depth, J. Geophys. Res., 110, D02104, doi:10.1029/2004JD005231, 2005. Molina, M. J., and Rowland, F. S.: Stratospheric sink for chlorofluoromethans: Chlorine atom-catalysed destruction of ozone, Nature, 249, 810-812, 1974. Rieder, H.E., Holawe, F., Simic, S., Blumthaler, M., Krzyscin, J.W., Wagner J.E., Schmalwieser A.W., and Weihs, P.: Reconstruction of erythemal UV-doses for two stations in Austria: A comparison between alpine and urban regions, Atmos. Chem. Phys., 8, 6309-6323, 2008. Rieder, H.E., Staehelin, J., Maeder, J.A., Ribatet, M., Stübi, R., Weihs, P., Holawe, F., Peter, T., and Davison, A.C.: From ozone mini holes and mini highs towards extreme value theory: New insights from extreme events and non stationarity, submitted to J. Geophys. Res., 2009. Staehelin, J., Kegel, R., and Harris, N. R.: Trend analysis of the homogenized total ozone series of Arosa (Switzerland), 1929-1996, J. Geophys. Res., 103(D7), 8389-8400, doi:10.1029/97JD03650, 1998a. Staehelin, J., Renaud, A., Bader, J., McPeters, R., Viatte, P., Hoegger, B., Bugnion, V., Giroud, M., and Schill, H.: Total ozone series at Arosa (Switzerland): Homogenization and data comparison, J. Geophys. Res., 103(D5), 5827-5842, doi:10.1029/97JD02402, 1998b.

DISINFECTION BY-PRODUCT FORMATION AND CONTROL BY OZONATION AND BIOTREATMENT

EPA Science Inventory

There is increasing interest in using ozone in water treatment because it is a strong disinfectant and is able to oxidize the precursors of some disinfection by-products (DBPs). However, ozonation itself produces DBPs, like aldehydes and ketones, and increases the concentration ...

Estimation of ozone dry deposition over Europe for the period 2071-2100

NASA Astrophysics Data System (ADS)

Komjáthy, Eszter; Gelybó, Györgyi; László Lagzi, István.; Mészáros, Róbert

2010-05-01

Ozone in the lower troposphere is a phytotoxic air pollutant which can cause injury to plant tissues, causing reduction in plant growth and productivity. In the last decades, several investigations have been carried out for the purpose to estimate ozone load over different surface types. At the same time, the changes of atmospheric variables as well as surface/vegetation parameters due to the global climate change could also strongly modify both temporal and spatial variations of ozone load over Europe. In this study, the possible effects of climate change on ozone deposition are analyzed. Using a sophisticated deposition model, ozone deposition was estimated on a regular grid over Europe for the period 2071-2100. Our aim is to determine the uncertainties and the possible degree of change in ozone deposition velocity as an important predictor of total ozone load using climate data from multiple climate models and runs. For these model calculations, results of the PRUDENCE (Predicting of Regional Scenarios and Uncertainties for Defining European Climate Change Risks and Effects) climate prediction project were used. As a first step, seasonal variations of ozone deposition over different vegetation types in case of different climate scenarios are presented in this study. Besides model calculations, in the frame of a sensitivity analyses, the effects of surface/vegetation parameters (e.g. leaf area index or stomatal resistance) on ozone deposition under a modified climate regime have also been analyzed.

Role of ozone and granular activated carbon in the removal of mutagenic compounds.

PubMed Central

Bourbigot, M M; Hascoet, M C; Levi, Y; Erb, F; Pommery, N

1986-01-01

The identification of certain organic compounds in drinking water has led water treatment specialists to be increasingly concerned about the eventual risks of such pollutants to the health of consumers. Our experiments focused on the role of ozone and granular activated carbon in removing mutagenic compounds and precursors that become toxic after chlorination. We found that if a sufficient dose of ozone is applied, its use does not lead to the creation of mutagenic compounds in drinking water and can even eliminate the initial mutagenicity of the water. The formation of new mutagenic compounds seems to be induced by ozonation that is too weak, although these mutagens can be removed by GAC filtration. Ozone used with activated carbon can be one of the best means for eliminating the compounds contributing to the mutagenicity of water. A combined treatment of ozone and activated carbon also decreases the chlorine consumption of the treated water and consequently reduces the formation of chlorinated organic compounds. PMID:3816720

Nitrosamines in pilot-scale and full-scale wastewater treatment plants with ozonation.

PubMed

Gerrity, Daniel; Pisarenko, Aleksey N; Marti, Erica; Trenholm, Rebecca A; Gerringer, Fred; Reungoat, Julien; Dickenson, Eric

2015-04-01

Ozone-based treatment trains offer a sustainable option for potable reuse applications, but nitrosamine formation during ozonation poses a challenge for municipalities seeking to avoid reverse osmosis and high-dose ultraviolet (UV) irradiation. Six nitrosamines were monitored in full-scale and pilot-scale wastewater treatment trains. The primary focus was on eight treatment trains employing ozonation of secondary or tertiary wastewater effluents, but two treatment trains with chlorination or UV disinfection of tertiary wastewater effluent and another with full advanced treatment (i.e., reverse osmosis and advanced oxidation) were also included for comparison. N-nitrosodimethylamine (NDMA) and N-nitrosomorpholine (NMOR) were the most prevalent nitrosamines in untreated (up to 89 ng/L and 67 ng/L, respectively) and treated wastewater. N-nitrosomethylethylamine (NMEA) and N-nitrosodiethylamine (NDEA) were detected at one facility each, while N-nitrosodipropylamine (NDPrA) and N-nitrosodibutylamine (NDBA) were less than their method reporting limits (MRLs) in all samples. Ozone-induced NDMA formation ranging from <10 to 143 ng/L was observed at all but one site, but the reasons for the variation in formation remain unclear. Activated sludge, biological activated carbon (BAC), and UV photolysis were effective for NDMA mitigation. NMOR was also removed with activated sludge but did not form during ozonation. Copyright © 2014 Elsevier Ltd. All rights reserved.

Ozone treatment of coal- and coffee grounds-based active carbons: Water vapor adsorption and surface fractal micropores

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tsunoda, Ryoichi; Ozawa, Takayoshi; Ando, Junichi

1998-09-15

Characteristics of the adsorption iostherms of water vapor on active carbons from coal and coffee grounds and those ozonized ones from the surface fractal dimension analysis are discussed. The upswing of the adsorption isotherms in the low relative pressure of coffee grounds-based active carbon, of which isotherms were not scarcely affected on ozonization, was attributed to the adsorption of water molecules on the metallic oxides playing the role of oxygen-surface complexes, which formed the corrugated surfaces on the basal planes of micropore walls with the surface fractal dimension D{sub s} > 2. On the other hand, coal-based active carbon withmore » D{sub s} < 2, which indicated the flat surfaces of micropore walls, showed little effect on the upswing even on ozonization, even though the adsorption amounts of water vapor were increased in the low relative pressure.« less

Secondary organic aerosol formation from ozone-initiated reactions with nicotine and secondhand tobacco smoke

NASA Astrophysics Data System (ADS)

Sleiman, Mohamad; Destaillats, Hugo; Smith, Jared D.; Liu, Chen-Lin; Ahmed, Musahid; Wilson, Kevin R.; Gundel, Lara A.

2010-11-01

We used controlled laboratory experiments to evaluate the aerosol-forming potential of ozone reactions with nicotine and secondhand smoke. Special attention was devoted to real-time monitoring of the particle size distribution and chemical composition of SOA as they are believed to be key factors determining the toxicity of SOA. The experimental approach was based on using a vacuum ultraviolet photon ionization time-of-flight aerosol mass spectrometer (VUV-AMS), a scanning mobility particle sizer (SMPS) and off-line thermal desorption coupled to mass spectrometry (TD-GC-MS) for gas-phase byproducts analysis. Results showed that exposure of SHS to ozone induced the formation of ultrafine particles (<100 nm) that contained high molecular weight nitrogenated species ( m/ z 400-500), which can be due to accretion/acid-base reactions and formation of oligomers. In addition, nicotine was found to contribute significantly (with yields 4-9%) to the formation of secondary organic aerosol through reaction with ozone. The main constituents of the resulting SOA were tentatively identified and a reaction mechanism was proposed to elucidate their formation. These findings identify a new component of thirdhand smoke that is associated with the formation of ultrafine particles (UFP) through oxidative aging of secondhand smoke. The significance of this chemistry for indoor exposure and health effects is highlighted.

The historic surface ozone record, 1896-1975, and its relation to modern measurements

NASA Astrophysics Data System (ADS)

Galbally, I. E.; Tarasick, D. W.; Stähelin, J.; Wallington, T. J.; Steinbacher, M.; Schultz, M.; Cooper, O. R.

2017-12-01

Tropospheric ozone is a greenhouse gas, a key component of atmospheric chemistry, and is detrimental to human health and plant productivity. The historic surface ozone record 1896-1975 has been constructed from measurements selected for (a) instrumentation whose ozone response can be traced to modern tropospheric ozone measurement standards, (b) samples taken when there is low probability of chemical interference and (c) sampling locations, heights and times when atmospheric mixing will minimise vertical gradients of ozone in the planetary boundary layer above and around the measurement location. Early measurements with the Schönbein filter paper technique cannot be related to modern methods with any degree of confidence. The potassium iodide-arsenite technique used at Montsouris for 1876-1910 is valid for measuring ozone; however, due to the presence of the interfering gases sulfur dioxide, ammonia and nitrogen oxides, the measured ozone concentrations are not representative of the regional atmosphere. The use of these data sets for trend analyses is not recommended. In total, 58 acceptable sets of measurements are currently identified, commencing in Europe in 1896, Greenland in 1932 and globally by the late 1950's. Between 1896 and 1944 there were 21 studies (median duration 5 days) with a median mole fraction of 23 nmol mol-1 (range of study averages 15-62 nmol mol-1). Between 1950 and 1975 there were 37 studies (median duration approx. 21 months) with a median mole fraction of 22 nmol mol-1 (range of study averages 13-49 nmol mol-1), all measured under conditions likely to give ozone mole fractions similar to those in the planetary boundary layer. These time series are matched with modern measurements from the Tropospheric Ozone Assessment Report (TOAR) Ozone Database and used to examine changes between the historic and modern observations. These historic ozone levels are higher than previously accepted for surface ozone in the late 19th early 20th Century. This historic surface ozone analysis provides a new test for historical reconstructions by Climate-Chemistry models.

Rate acceleration of the heterogeneous reaction of ozone with a model alkene at the air-ice interface at low temperatures.

PubMed

Ray, Debajyoti; Malongwe, Joseph K'Ekuboni; Klán, Petr

2013-07-02

The kinetics of the ozonation reaction of 1,1-diphenylethylene (DPE) on the surface of ice grains (also called "artificial snow"), produced by shock-freezing of DPE aqueous solutions or DPE vapor-deposition on pure ice grains, was studied in the temperature range of 268 to 188 K. A remarkable and unexpected increase in the apparent ozonation rates with decreasing temperature was evaluated using the Langmuir-Hinshelwood and Eley-Rideal kinetic models, and by estimating the apparent specific surface area of the ice grains. We suggest that an increase of the number of surface reactive sites, and possibly higher ozone uptake coefficients are responsible for the apparent rate acceleration of DPE ozonation at the air-ice interface at lower temperatures. The increasing number of reactive sites is probably related to the fact that organic molecules are displaced more to the top of a disordered interface (or quasi-liquid) layer on the ice surface, which makes them more accessible to the gas-phase reactants. The effect of NaCl as a cocontaminant on ozonation rates was also investigated. The environmental implications of this phenomenon for natural ice/snow are discussed. DPE was selected as an example of environmentally relevant species which can react with ozone. For typical atmospheric ozone concentrations in polar areas (20 ppbv), we estimated that its half-life on the ice surface would decrease from ∼5 days at 258 K to ∼13 h at 188 K at submonolayer DPE loadings.

THE OZONE REACTION WITH BUTADIENE: FORMATION OF TOXIC PRODUCTS. (R826236)

EPA Science Inventory

Abstract

The formation yields of acrolein, 1,2-epoxy-3-butene and OH radicals have been measured from reaction of ozone with 1,3-butadiene at room temperature and atmosphere pressure. 1,3,5-Trimethyl benzene was added to scavenge OH radicals in measurements of product ...

Surface modification of nitrogen-doped carbon nanotubes by ozone via atomic layer deposition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lushington, Andrew; Liu, Jian; Tang, Yongji

The use of ozone as an oxidizing agent for atomic layer deposition (ALD) processes is rapidly growing due to its strong oxidizing capabilities. However, the effect of ozone on nanostructured substrates such as nitrogen-doped multiwalled carbon nanotubes (NCNTs) and pristine multiwalled carbon nanotubes (PCNTs) are not very well understood and may provide an avenue toward functionalizing the carbon nanotube surface prior to deposition. The effects of ALD ozone treatment on NCNTs and PCNTs using 10 wt. % ozone at temperatures of 150, 250, and 300 °C are studied. The effect of ozone pulse time and ALD cycle number on NCNTs and PCNTsmore » was also investigated. Morphological changes to the substrate were observed by scanning electron microscopy and high resolution transmission electron microscopy. Brunauer-Emmett-Teller measurements were also conducted to determine surface area, pore size, and pore size distribution following ozone treatment. The graphitic nature of both NCNTs and PCNTs was determined using Raman analysis while x-ray photoelectron spectroscopy (XPS) was employed to probe the chemical nature of NCNTs. It was found that O{sub 3} attack occurs preferentially to the outermost geometric surface of NCNTs. Our research also revealed that the deleterious effects of ozone are found only on NCNTs while little or no damage occurs on PCNTs. Furthermore, XPS analysis indicated that ALD ozone treatment on NCNTs, at elevated temperatures, results in loss of nitrogen content. Our studies demonstrate that ALD ozone treatment is an effective avenue toward creating low nitrogen content, defect rich substrates for use in electrochemical applications and ALD of various metal/metal oxides.« less

Characterization of ozone decomposition in a soil slurry: kinetics and mechanism.

PubMed

Lim, Hyung-Nam; Choi, Hechul; Hwang, Tae-Moon; Kang, Joon-Wun

2002-01-01

A series of soil slurry experiments were performed in a carefully conceived reactor set-up to investigate the characteristics of the catalytic decomposition of ozone on a sand and iron surface. Real time on-line monitoring of ozone in the reaction module was possible using flow injection analysis coupled with a computer-controlled UV detector and data acquisition system. The effects of the soil media and size, ozone dosage, pH and p-CBA as a probe compound were examined at the given experimental conditions. Two apparent phases existed, and ozone instantaneously decomposed within one second in the first phase. These were defined as the instantaneous ozone demand (ID) phase, and the relatively slow decay stage. The interactions of ozone with the soil organic matter (SOM) and metal oxides were attributed mostly to the instantaneous decomposition of ozone. From the probe (p-CBA) experiments, 60-68% of total p-CBA removal occurred during the ID phase. The generation of hydroxyl radicals (OH.) was demonstrated and was closely related with metal oxides as well as SOM. Metal oxides in soil surface were considered to have relatively faster reaction rate with ozone and provide more favorable reactive sites to generate higher amount of OH. than SOM. Even at one-tenth concentration of the sands, a goethite-induced catalytic reaction outfitted the removal rate ofp-CBA among all the soils tested. More than 40% of total p-CBA removal occurred on the soil surface. It was inferred that the radical reaction with the probe compound seemed to take place not only on the soil surface but also in the solid-liquid interface. Ozone decomposition and the reaction between OH. and p-CBA appeared to be independent of any change in pH.

Stratospheric ozone changes under solar geoengineering: implications for UV exposure and air quality

NASA Astrophysics Data System (ADS)

Nowack, Peer Johannes; Abraham, Nathan Luke; Braesicke, Peter; Pyle, John Adrian

2016-03-01

Various forms of geoengineering have been proposed to counter anthropogenic climate change. Methods which aim to modify the Earth's energy balance by reducing insolation are often subsumed under the term solar radiation management (SRM). Here, we present results of a standard SRM modelling experiment in which the incoming solar irradiance is reduced to offset the global mean warming induced by a quadrupling of atmospheric carbon dioxide. For the first time in an atmosphere-ocean coupled climate model, we include atmospheric composition feedbacks for this experiment. While the SRM scheme considered here could offset greenhouse gas induced global mean surface warming, it leads to important changes in atmospheric composition. We find large stratospheric ozone increases that induce significant reductions in surface UV-B irradiance, which would have implications for vitamin D production. In addition, the higher stratospheric ozone levels lead to decreased ozone photolysis in the troposphere. In combination with lower atmospheric specific humidity under SRM, this results in overall surface ozone concentration increases in the idealized G1 experiment. Both UV-B and surface ozone changes are important for human health. We therefore highlight that both stratospheric and tropospheric ozone changes must be considered in the assessment of any SRM scheme, due to their important roles in regulating UV exposure and air quality.

Foreign and Domestic Contributions to Springtime Ozone Pollution over China

NASA Astrophysics Data System (ADS)

Ni, R.; Lin, J.; Yan, Y.; Lin, W.; Chen, H.

2017-12-01

Ozone is a critical air pollutant that damages human health and vegetation. Previous studies for the United States and Europe have shown large influences of foreign emissions on domestic ozone levels, whereas the relative contributions of foreign versus domestic emissions are much less clear for China. Here, we use a global-regional two-way coupled model system based on GEOS-Chem to quantify the contributions to springtime ozone over China from anthropogenic emissions in major source regions across the globe. Our results indicate considerable influences of foreign anthropogenic pollution on China's ozone pollution. Together, foreign anthropogenic emissions enhance springtime surface ozone over China by 3 12 ppb. Of all ozone over China produced by global anthropogenic emissions, foreign emissions contribute 40% near the surface, and the contribution increases with altitude until a value of 80% in the upper troposphere. Impact from Japan and Korea is 1 2 ppb over east coastal regions, and negligible in inland. Anthropogenic emissions of South and South-East Asia increase ozone over Tibet and the Yunnan-Guizhou Plateau by up to 5 ppb, and their contribution increases with height due to strong vertical transport. Pollution from North America and Europe mainly accompanies strong westerly winds and frequent cyclonic activities that are favorable to long-range transport. European anthropogenic pollution enhances surface ozone by 1 3 ppb over West and North China. Despite a much longer transport distance, the contribution from North America is greater than European contribution due to the nearly doubled amount of anthropogenic NMVOC emissions. The high percentage contribution of foreign anthropogenic emissions to China's ozone pollution can be partly explained by excessive domestic NOx emissions that suppress ozone production efficiency and even destroy ozone. Our study is relevant to Chinese ozone pollution control and global environmental protection collaboration.

Behavior, distribution and variability of surface ozone at an arid region in the south of Iberian Peninsula (Seville, Spain).

PubMed

Adame, José A; Lozano, Antonio; Bolívar, Juan P; De la Morena, Benito A; Contreras, Juan; Godoy, Francisca

2008-01-01

In order to improve our knowledge of the surface ozone in the south of the Iberian Peninsula, annual, monthly, weekly and daily ozone concentrations have been closely monitored in the Seville metropolitan area highlighting those episodes that exceed the European Ozone Directive. A three-year period (2003-2005) and eight ozone stations were used; five of them located in the city's busiest areas and the rest in adjacent zones ( approximately 25km). In addition, the wind regime was also studied in order to understand the main characteristics of the surface atmospheric dynamics. The lowest ozone concentrations 17-33microgm(-3) took place in January while the highest 57-95microgm(-3) occurred in June. The ozone concentration week-weekend differences from May to September indicate that this phenomenon does not affect the ozone stations analysed. Daily cycles show minimum values between 7:00 and 8:00 UTC and maximum at noon, exceeding 90microgm(-3) during summer months. From March to October the ozone concentrations were above the target value for the protection of human health, especially during the summer months, with values up to 30% over the limit. The information threshold has been exceeded at all ozone stations studied but with greater frequency in the stations far from the city centre. In addition, at these latter stations the alert threshold was also exceeded on six occasions. This study in the city of Seville indicates that the high ozone levels are due to local atmospheric effects, mainly since the ozone air masses may undergo recirculation processes. The ozone is transported to the city from the S-SW, having a major impact in the NE areas.

The Sources and Significance of Stratospheric Water Vapor: Mechanistic Studies from Equator to Pole

NASA Astrophysics Data System (ADS)

Smith, Jessica Birte

It is the future of the stratospheric ozone layer, which protects life at Earth's surface from harmful ultraviolet (UV) radiation, that is the focus of the present work. Fundamental changes in the composition and structure of the stratosphere in response to anthropogenic climate forcing may lead to catastrophic ozone loss under current, and even reduced, stratospheric halogen loading. In particular, the evolution toward a colder, wetter stratosphere, threatens to enhance the heterogeneous conversion of inorganic halogen from its reservoir species to its catalytically active forms, and thus promote in situ ozone loss. Water vapor concentrations control the availability of reactive surface area, which facilitates heterogeneous chemistry. Furthermore, the rates of the key heterogeneous processes are tightly controlled by the ambient humidity. Thus, credible predictions of UV dosage require a quantitative understanding of both the sensitivity of these chemical mechanisms to water vapor concentrations, and an elucidation of the processes controlling stratospheric water vapor concentrations. Toward this end, we present a set of four case studies utilizing high resolution in situ data acquired aboard NASA aircraft during upper atmospheric research missions over the past two decades. 1) We examine the broad scale humidity structure of the upper troposphere and lower stratosphere from the midlatitudes to the tropics, focusing on cirrus formation and dehydration at the cold-point tropical tropopause. The data show evidence for frequent supersaturation in clear air, and sustained supersaturation in the presence of cirrus. These results challenge the strict thermal control of the tropical tropopause. 2) We investigate the likelihood of cirrus-initiated activation of chlorine in the midlatitude lower stratosphere. At midlatitudes the transition from conditions near saturation below the local tropopause to undersaturated air above greatly reduces the probability of heterogeneous activation and in situ ozone loss in this region. 3) We probe the details of heterogeneous processing in the wintertime Arctic vortex, and find that in situ measurements of OH provide incontrovertible evidence for the heterogeneous reaction of HOCl with HCl. This reaction is critical to sustaining catalytically active chlorine and prolonging ozone loss in the springtime vortex. 4) We revisit the topic of midlatitude ozone loss with an emphasis upon the response of ozone in this region to changes in the chemical composition and thermal structure of the lower stratosphere induced by anthropogenic climate change. Specifically, we show evidence for episodic moisture plumes in the overworld stratosphere generated by the rapid evaporation of ice injected into this region by deep convection, and find that these high water vapor plumes have the potential to alter the humidity of the lower stratosphere, and drastically increase the rate of heterogeneous chemistry and in situ ozone loss, given sufficient reactive surface.

OZONE PRODUCTION FROM IRRADIATION OF ACETYLENE/CHLORINE MIXTURES IN AIR

EPA Science Inventory

The reaction of chlorine radicals with acetylene in air in the absence of oxides of nitrogen result In the formation of ozone. o ozone is observed when chlorine radicals react with methylacetylene or ethylacetylene under similar conditions. ormyl chloride is observed in all syste...

Summary of aircraft results for 1978 southeastern Virginia urban plume measurement study of ozone, nitrogen oxides, and methane

NASA Technical Reports Server (NTRS)

Gregory, G. L.; Wornom, D. E.; Mathis, J. J., Jr.; Sebacher, D. I.

1980-01-01

Ozone production was determined from aircraft and surface in situ measurements, as well as from an airborne laser absorption spectrometer. Three aircraft and approximately 10 surface stations provided air-quality data. Extensive meteorological, mixing-layer-height, and ozone-precursor data were also measured. Approximately 50 hrs (9 flight days) of data from the aircraft equipped to monitor ozone, nitrogen oxides, dewpoint temperature, and temperature are presented. In addition, each experiment conducted is discussed.

Study on an integrated process combining ozonation with ceramic ultra-filtration for decentralized supply of drinking water.

PubMed

Zhu, Jia; Fan, Xiao J; Tao, Yi; Wei, De Q; Zhang, Xi H

2014-09-19

An integrated process was specifically developed for the decentralized supply of drinking water from micro-polluted surface water in the rural areas of China. The treatment process combined ozonation with ceramic ultra-filtration (UF), coagulation for pre-treatment and granular activated carbon filtration. A flat-sheet ceramic membrane was used with a cut-off of 60 nm and the measurement of 254 mm (length) × 240 mm (width) × 6 mm (thickness). Ozonation and ceramic UF was set up whthin one reactor. The experimental results showed that the removal efficiencies of the dissolved organic carbon (DOC) and the formation potential of trihalomethanes (THMs), haloacetic acids (HAAs) and ammonia were 80%, 76%, 70% and 90%, respectively; that the turbidity of the product water was below 0.2 NTU and the particle count number (particles larger than 2 μm) was less than 50 counts per mL. The result also showed that all the pathogenic microorganisms were retained by the ceramic and that UF. Ozonation played a critical role in the control of membrane fouling and the removal of contaminants. Exactly, the membrane fouling can be controlled in situ with 3 mg L(-1) ozone at the permeate flux of 80 L m(-2) h(-1), yet the required dosage of ozone was dependent on the quality of the raw water. Therefore, this study is able to provide a highly compacted system for decentralized supply of high-quality drinking water in terms of both chemical and microbiological safety for the rural areas in China.

Wintertime ozone fluxes and profiles above a subalpine spruce-fir forest

Treesearch

Karl Zeller

2000-01-01

High rural concentrations of ozone (O3) are thought to be stratospheric in origin, advected from upwind urban sources, or photochemically generated locally by natural trace gas emissions. Ozone is known to be transported vertically downward from the above-canopy atmospheric surface layer and destroyed within stomata or on other biological and mineral surfaces. However...

Top-down NOX emissions over European cities from LOTOS-EUROS simulated and OMI observed tropospheric NO2 columns using the Exponentially Modified Gaussian approach

NASA Astrophysics Data System (ADS)

Verstraeten, Willem W.; Folkert Boersma, K.; Douros, John; Williams, Jason E.; Eskes, Henk H.; Delcloo, Andy

2017-04-01

High nitrogen oxides concentrations at the surface (NOX = NO + NO2) impact humans and ecosystem badly and play a key role in tropospheric chemistry. Surface NOX emissions drive major processes in regional and global chemistry transport models (CTM). NOX contributes to the formation of acid rain, act as aerosol precursors and is an important trace gas for the formation of tropospheric ozone (O3). Via tropospheric O3, NOX indirectly affects the production of the hydroxyl radical which controls the chemical lifetime of key atmospheric pollutants and reactive greenhouse gases. High NOX emissions are mainly observed in polluted regions produced by anthropogenic combustion from industrial, traffic and household activities typically observed in large and densely populated urban areas. Accurate NOX inventories are essential, but state-of the- art emission databases may vary substantially and uncertainties are high since reported emissions factors may differ in order of magnitude and more. To date, the modelled NO2 concentrations and lifetimes have large associated uncertainties due to the highly non-linear small-scale chemistry that occurs in urban areas and uncertainties in the reaction rate data, missing nitrogen (N) species and volatile organic compounds (VOC) emissions, and incomplete knowledge of nitrogen oxides chemistry. Any overestimation in the chemical lifetime may mask missing NOX chemistry in current CTM's. By simultaneously estimating both the NO2 lifetime and concentrations, for instance by using the Exponentially Modified Gaussian (EMG), a better surface NOX emission flux estimate can be obtained. Here we evaluate if the EMG methodology can reproduce the emissions input from the tropospheric NO2 columns simulated by the LOTOS-EUROS (Long Term Ozone Simulation-European Ozone Simulation) CTM model. We apply the EMG methodology on LOTOS-EUROS simulated tropospheric NO2 columns for the period April-September 2013 for 21 selected European urban areas under windy conditions (surface wind speeds > 3 m s-1). We then compare the top-down derived surface NOX emissions with the 2011 MACC-III emission inventory, used in the LOTOS-EUROS model as input to simulate the NO2 columns. We also apply the EMG methodology on OMI (Ozone Monitoring Instrument) tropospheric NO2 column data, providing us with real-time observation-based estimates of midday NO2 lifetime and NOX emissions over 21 European cities in 2013. Results indicate that the top-down derived NOX emissions from LOTOS-EUROS (respectively OMI) are comparable with the MACC-III inventory with a R2 of 0.99 (respectively R2 = 0.79). For St-Petersburg and Moscow the top-down NOX estimates from 2013 OMI data are biased low compared to the MACC-III inventory which uses a 2011 NOX emissions update.

Harvesting of Scenedesmus obliquus FSP-3 using dispersed ozone flotation.

PubMed

Cheng, Ya-Ling; Juang, Yu-Chuan; Liao, Guan-Yu; Tsai, Pei-Wen; Ho, Shih-Hsin; Yeh, Kuei-Ling; Chen, Chun-Yen; Chang, Jo-Shu; Liu, Jhy-Chern; Chen, Wen-Ming; Lee, Duu-Jong

2011-01-01

The Scenedesmus obliquus FSP-3, a species with excellent potential for CO(2) capture and lipid production, was harvested using dispersed ozone flotation. While air aeration does not, ozone produces effective solid-liquid separation through flotation. Ozone dose applied for sufficient algal flotation is similar to those used in practical drinking waterworks. The algae removal rate, surface charge, and hydrophobicity of algal cells, and fluorescence characteristics and proteins and polysaccharides contents of algogenic organic matter (AOM) were determined during ozonation. Proteins released from tightly bound AOM are essential to modifying the hydrophobicity of bubble surfaces for easy cell attachment and to forming a top froth layer for collecting floating cells. Humic substances in the suspension scavenge dosed ozone that adversely affects ozone flotation efficiency of algal cells. Copyright © 2010 Elsevier Ltd. All rights reserved.

Meteorological and chemical impacts on ozone formation: A case study in Hangzhou, China

NASA Astrophysics Data System (ADS)

Li, Kangwei; Chen, Linghong; Ying, Fang; White, Stephen J.; Jang, Carey; Wu, Xuecheng; Gao, Xiang; Hong, Shengmao; Shen, Jiandong; Azzi, Merched; Cen, Kefa

2017-11-01

Regional ozone pollution has become one of the most challenging problems in China, especially in the more economically developed and densely populated regions like Hangzhou. In this study, measurements of O3, CO, NOx and non-methane hydrocarbons (NMHCs), together with meteorological data, were obtained for the period July 1, 2013-August 15, 2013 at three sites in Hangzhou. These sites included an urban site (Zhaohui ;ZH;), a suburban site (Xiasha ;XS;) and a rural site (Qiandaohu ;QDH;). During the observation period, both ZH and XS had a higher ozone level than QDH, with exceeding rates of 41.3% and 47.8%, respectively. Elevated O3 levels in QDH were found at night, which could be explained by less prominent NO titration effect in rural area. Detailed statistical analysis of meteorological and chemical impacts on ozone formation was carried out for ZH, and higher ozone concentration was observed when the wind direction was from the east. This is possibly due to emissions of VOCs from XS, a typical chemical industrial park located in 30 km upwind area of ZH. A comprehensive comparison between three ozone episode periods and one non-episode period were made in ZH. It was concluded that elevated concentrations of precursors and temperatures, low relative humidity and wind speed and easterly-dominated wind direction contribute to urban ozone episodes in Hangzhou. VOCs reactivity analysis indicated that reactive alkenes like isoprene and isobutene contributed most to ozone formation. Three methods were applied to evaluate O3-VOCs-NOx sensitivity in ZH: VOCs/NOx ratio method, Smog Production Model (SPM) and Relative Incremental Reactivity (RIR). The results show that summer ozone in urban Hangzhou mostly presents VOCs-limited and transition region alternately. Our study implies that the increasing automobiles and VOCs emissions from upwind area could result in ozone pollution in urban Hangzhou, and synergistic reduction of VOCs and NOx will be more effective.

The ozonolysis of primary aliphatic amines in single and multicomponent fine particles

NASA Astrophysics Data System (ADS)

Zahardis, J.; Geddes, S.; Petrucci, G. A.

2007-10-01

The oxidative processing by ozone of the particulate amines octadecylamine (ODA) and hexadecylamine (HDA) is reported. Ozonolysis of these amines resulted in strong NO2- and NO3- ion signals that increased with ozone exposure as monitored by photoelectron resonance capture ionization aerosol mass spectrometry. These products suggest a mechanism of progressive oxidation of the particulate amines to nitro alkanes. Additionally, a strong ion signal at 125 m/z is assigned to the ion NO3-(HNO3). For ozonized mixed particles containing ODA or HDA + oleic acid (OL), with pO3≥3×10^{-7 atm, imine, secondary amide, and tertiary amide products were measured. These products most likely arise from reactions of amines with aldehydes (for imines) and stabilized Criegee intermediates (SCI) or secondary ozonides (for amides) from the fatty acid. The routes to amides via SCI and/or secondary ozonides was shown to be more important than comparable amide forming reactions between amines and organic acids, using azelaic acid as a test compound. Finally, direct evidence is provided for the formation of a surface barrier in the ODA + OL reaction system that resulted in the retention of OL at high ozone exposures (up to 10-3 atm for 17 s). This effect was not observed in HDA + OL or single component OL particles, suggesting that it may be a species-specific surfactant effect from an in situ generated amide or imine. Implications to tropospheric chemistry, including particle bound amines as sources of oxidized gas phase nitrogen species (e.g. NO2, NO3), formation of nitrogen enriched HULIS via ozonolysis of amines and source apportionment are discussed.}

The ozonolysis of primary aliphatic amines in fine particles

NASA Astrophysics Data System (ADS)

Zahardis, J.; Geddes, S.; Petrucci, G. A.

2008-02-01

The oxidative processing by ozone of the particulate amines octadecylamine (ODA) and hexadecylamine (HDA) is reported. Ozonolysis of these amines resulted in strong NO2- and NO3- ion signals that increased with ozone exposure as monitored by photoelectron resonance capture ionization aerosol mass spectrometry. These products suggest a mechanism of progressive oxidation of the particulate amines to nitroalkanes. Additionally, a strong ion signal at 125 m/z is assigned to the ion NO3- (HNO3). For ozonized mixed particles containing ODA or HDA + oleic acid (OL), with pO3≥3×10-7 atm, imine, secondary amide, and tertiary amide products were measured. These products most likely arise from reactions of amines with aldehydes (for imines) and stabilized Criegee intermediates (SCI) or secondary ozonides (for amides) from the fatty acid. The routes to amides via SCI and/or secondary ozonides were shown to be more important than comparable amide forming reactions between amines and organic acids, using azelaic acid as a test compound. Finally, direct evidence is provided for the formation of a surface barrier in the ODA + OL reaction system that resulted in the retention of OL at high ozone exposures (up to 10-3 atm for 17 s). This effect was not observed in HDA + OL or single component OL particles, suggesting that it may be a species-specific surfactant effect from an in situ generated amide or imine. Implications to tropospheric chemistry, including particle bound amines as sources of oxidized gas phase nitrogen species (e.g.~NO2, NO3), formation of nitrogen enriched HULIS via ozonolysis of amines and source apportionment are discussed.

Analysis of Ozone Levels from 2006 to 2016 in the Atlanta-Sandy Springs-Roswell Metropolitan Area

NASA Astrophysics Data System (ADS)

Dickinson, E.

2016-12-01

Ozone is a significant component of smog that persists in many large urban areas. Ozone is regulated by the U.S Environmental Protection Agency (EPA) as a criteria pollutant, and can lead to a variety of respiratory problems in sensitive groups. This study examines ozone concentrations in Atlanta-Sandy Springs- Roswell (Atlanta) metropolitan area, one of the largest urban areas in the Southeastern United States. Photochemical reactions involving oxides of nitrogen (NOx) and a variety of volatile organic compounds (VOCs) lead to ozone formation. The rate of ozone formation is exacerbated by Atlanta's hot and humid climate during the summers. Using data from EPA's Air Quality Systems database, this study analyzes ozone concentration data from regulatory monitoring sites in several counties that are in the metropolitan statistical area of Atlanta-Sandy Springs-Roswell, over a ten-year period (2006-2016). The study also looks at the meteorological conditions (such as temperature, wind speed, and humidity) over the same ten-year period (2006-2016) using data from the National Weather Service's Regional Airport Observations at Hartsfield-Jackson Airport in Atlanta. Based on a preliminary analysis of the ozone data, there is a downward trend in maximum daily 8-hour ozone concentration at all Atlanta-Sandy Springs-Roswell sites from 2006-2016. The decrease of ozone concentrations corresponds to three successively stricter National Ambient Air Quality Standards (NAAQS) for ozone (1997, 2008, and 2015) during the ten-year period of this study. The Atlanta area will be classified based on the 2015 ozone NAAQS, of 70 parts per billion, in the next few years. With EPA's upcoming attainment determination, this study looks at the recent trends in ozone concentrations and meteorology in the Atlanta area.

Effect of Ozone Treatment on Nano-Sized Silver Sulfide in Wastewater Effluent.

PubMed

Thalmann, Basilius; Voegelin, Andreas; von Gunten, Urs; Behra, Renata; Morgenroth, Eberhard; Kaegi, Ralf

2015-09-15

Silver nanoparticles used in consumer products are likely to be released into municipal wastewater. Transformation reactions, most importantly sulfidation, lead to the formation of nanoscale silver sulfide (nano-Ag2S) particles. In wastewater treatment plants (WWTP), ozonation can enhance the effluent quality by eliminating organic micropollutants. The effect of ozonation on the fate of nano-Ag2S, however, is currently unknown. In this study, we investigate the interaction of ozone with nano-Ag2S and evaluate the effect of ozonation on the short-term toxicity of WWTP effluent spiked with nano-Ag2S. The oxidation of nano-Ag2S by ozone resulted in a stoichiometric factor (number of moles of ozone required to oxidize one mole of sulfide to sulfate) of 2.91, which is comparable to the results obtained for the reaction of bisulfide (HS(-)) with ozone. The second-order rate constant for the reaction of nano-Ag2S with ozone (k = 3.1 × 10(4) M(-1) s(-1)) is comparable to the rate constant of fast-reacting micropollutants. Analysis of the ozonation products of nano-Ag2S by transmission electron microscopy (TEM) and X-ray absorption spectroscopy (XAS) revealed that ozonation dominantly led to the formation of silver chloride in WWTP effluent. After ozonation of the Ag2S-spiked effluent, the short-term toxicity for the green algae Chlamydomonas reinhardtii increased and reached EC50 values comparable to Ag(+). This study thus reveals that ozone treatment of WWTP effluent results in the oxidation of Ag2S and, hence, an increase of the Ag toxicity in the effluent, which may become relevant at elevated Ag concentrations.

Projections of Future Summertime Ozone over the U.S.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pfister, G. G.; Walters, Stacy; Lamarque, J. F.

This study uses a regional fully coupled chemistry-transport model to assess changes in surface ozone over the summertime U.S. between present and a 2050 future time period at high spatial resolution (12 km grid spacing) under the SRES A2 climate and RCP8.5 anthropogenic pre-cursor emission scenario. The impact of predicted changes in climate and global background ozone is estimated to increase surface ozone over most of the U.S; the 5th - 95th percentile range for daily 8-hour maximum surface ozone increases from 31-79 ppbV to 30-87 ppbV between the present and future time periods. The analysis of a set ofmore » meteorological drivers suggests that these mostly will add to increasing ozone, but the set of simulations conducted does not allow to separate this effect from that through enhanced global background ozone. Statistically the most robust positive feedbacks are through increased temperature, biogenic emissions and solar radiation. Stringent emission controls can counteract these feedbacks and if considered, we estimate large reductions in surface ozone with the 5th-95th percentile reduced to 27-55 ppbV. A comparison of the high-resolution projections to global model projections shows that even though the global model is biased high in surface ozone compared to the regional model and compared to observations, both the global and the regional model predict similar changes in ozone between the present and future time periods. However, on smaller spatial scales, the regional predictions show more pronounced changes between urban and rural regimes that cannot be resolved at the coarse resolution of global model. In addition, the sign of the changes in overall ozone mixing ratios can be different between the global and the regional predictions in certain regions, such as the Western U.S. This study confirms the key role of emission control strategies in future air quality predictions and demonstrates the need for considering degradation of air quality with future climate change in emission policy making. It also illustrates the need for high resolution modeling when the objective is to address regional and local air quality or establish links to human health and society.« less

Diagnostic Evaluation of Ozone Production and Horizontal Transport in a Regional Photochemical Air Quality Modeling System

EPA Science Inventory

A diagnostic model evaluation effort has been performed to focus on photochemical ozone formation and the horizontal transport process since they strongly impact the temporal evolution and spatial distribution of ozone (O₃) within the lower troposphere. Results from th...

The seasonality and geographic dependence of ENSO impacts on U.S. surface ozone variability

NASA Astrophysics Data System (ADS)

Xu, Li; Yu, Jin-Yi; Schnell, Jordan L.; Prather, Michael J.

2017-04-01

We examine the impact of El Niño-Southern Oscillation (ENSO) on surface ozone abundance observed over the continental United States (U.S.) during 1993-2013. The monthly ozone decreases (increases) during El Niño (La Niña) years with amplitude up to 1.8 ppb per standard deviation of Niño 3.4 index. The largest ENSO influences occur over two southern U.S. regions during fall when the ENSO develops and over two western U.S. regions during the winter to spring after the ENSO decays. ENSO affects surface ozone via chemical processes during warm seasons in southern regions, where favorable meteorological conditions occur, but via dynamic transport during cold seasons in western regions, where the ENSO-induced circulation variations are large. The geographic dependence and seasonality of the ENSO impacts imply that regulations regarding air quality and its exceedance need to be adjusted for different seasons and U.S. regions to account for the ENSO-driven patterns in surface ozone.

Kinetics of the heterogeneous photo oxidation of the pesticide bupirimate by OH-radicals and ozone under atmospheric conditions.

PubMed

Bouya, H; Errami, M; Chakir, A; Roth, E

2015-09-01

This article is concerned with the study of the photochemical degradation of bupirimate adsorbed on a quartz surface by atmospheric oxidants, namely ozone and OH radicals. OH oxidation experiments were conducted relative to two reference compounds, terbuthylazine and (4-chlorophenyl)(3,4-dimethoxyphenyl) methanone. Meanwhile, ozone oxidation experiments were performed in the absolute mode and were interpreted by both, the Surface Layer Reaction and the Gas Surface Reaction models of heterogeneous reactions. The obtained results show that the rate constants for the reactions between bupirimate and OH radicals and ozone are (cm(3)molecule(-1)s(-1)): (1.06 ± 0.87) × 10(-12) and (5.4 ± 0.3) × 10(-20), respectively. As a consequence, for the experimental conditions used in this study, the lifetime of bupirimate at quartz like surface/atmosphere interfaces is several months against ozone and a tenth of days against OH-radical. Copyright © 2015 Elsevier Ltd. All rights reserved.

Synoptic and meteorological drivers of extreme ozone concentrations over Europe

NASA Astrophysics Data System (ADS)

Otero, Noelia Felipe; Sillmann, Jana; Schnell, Jordan L.; Rust, Henning W.; Butler, Tim

2016-04-01

The present work assesses the relationship between local and synoptic meteorological conditions and surface ozone concentration over Europe in spring and summer months, during the period 1998-2012 using a new interpolated data set of observed surface ozone concentrations over the European domain. Along with local meteorological conditions, the influence of large-scale atmospheric circulation on surface ozone is addressed through a set of airflow indices computed with a novel implementation of a grid-by-grid weather type classification across Europe. Drivers of surface ozone over the full distribution of maximum daily 8-hour average values are investigated, along with drivers of the extreme high percentiles and exceedances or air quality guideline thresholds. Three different regression techniques are applied: multiple linear regression to assess the drivers of maximum daily ozone, logistic regression to assess the probability of threshold exceedances and quantile regression to estimate the meteorological influence on extreme values, as represented by the 95th percentile. The relative importance of the input parameters (predictors) is assessed by a backward stepwise regression procedure that allows the identification of the most important predictors in each model. Spatial patterns of model performance exhibit distinct variations between regions. The inclusion of the ozone persistence is particularly relevant over Southern Europe. In general, the best model performance is found over Central Europe, where the maximum temperature plays an important role as a driver of maximum daily ozone as well as its extreme values, especially during warmer months.

Quasi-Liquid Layer Formation on Ice under Stratospheric Conditions

NASA Technical Reports Server (NTRS)

McNeill, V. Faye; Loerting, Thomas; Trout, Bernhardt L.; Molina, Luisa T.; Molina, Mario J.

2004-01-01

Characterization of the interaction of hydrogen chloride (HCl) with ice is essential to understanding at a molecular level the processes responsible for ozone depletion involving polar stratospheric cloud (PSC) particles. To explain the catalytic role PSC particle surfaces play during chlorine activation, we proposed previously that HCl induces the formation of a disordered region on the ice surface, a quasi-liquid layer (QLL), at stratospheric conditions. The QLL is known to exist in pure ice crystals at temperatures near the melting point, but its existence at stratospheric temperatures (-85 C to -70 C) had not been reported yet. We studied the interaction of HCl with ice under stratospheric conditions using the complementary approach of a) ellipsometry to directly monitor the ice surface, using chemical ionization mass spectrometry (CIMS) to monitor the gas phase species present in the ellipsometry experiments, and b) flow-tube experiments with CIMS detection. Here we show that trace amounts of HCl induce QLL formation at stratospheric temperatures, and that the QLL enhances the chlorine-activation reaction of HCl with chlorine nitrate (ClONO2), and also enhances acetic acid (CH3COOH) adsorption.

High Wintertime Ozone in the Uinta Basin: Diurnal Mixing and Ozone Production Measured by Tethered Ozonesondes

NASA Astrophysics Data System (ADS)

Johnson, B.; Cullis, P.; Schnell, R. C.; Oltmans, S. J.; Sterling, C. W.; Jordan, A. F.; Hall, E.

2016-12-01

Extreme high ozone mixing ratios, far exceeding U.S. National Air Quality Standards, were observed in the Uinta Basin in January-February 2013 under conditions highly favorable for wintertime ozone production. Hourly average ozone mixing ratios increased from regional background levels of 40-50 ppbv to >160 ppbv during several multi-day episodes of prolonged temperature inversions over snow-covered ground within air confining topography. Extensive surface and tethered balloon profile measurements of ozone, meteorology, CH4, CO2, NO2 and a suite of non-methane hydrocarbons (NMHCs) link emissions from oil and natural gas extraction with the strong ozone production throughout the Basin. High levels of NMHCs that were well correlated with CH4 showed that abundant O3 precursors were available throughout the Basin where high ozone mixing ratios extended from the surface to the top of the inversion layer at 200 m above ground level. This layer was at a nearly uniform height across the Basin even though there are significant terrain variations. Tethered balloon measurements rising above the elevated levels of ozone within the cold pool layer beneath the inversion measured regional background O3 concentrations. Surface wind and direction data from tethered balloons showed a consistent diurnal pattern in the Basin that moved air with the highest levels of CH4 and ozone precursor NMHC's from the gas fields of the east-central portion of the Basin to the edges during the day, before draining back into the Basin at night.

Elimination of micropollutants and transformation products from a wastewater treatment plant effluent through pilot scale ozonation followed by various activated carbon and biological filters.

PubMed

Knopp, Gregor; Prasse, Carsten; Ternes, Thomas A; Cornel, Peter

2016-09-01

Conventional wastewater treatment plants are ineffective in removing a broad range of micropollutants, resulting in the release of these compounds into the aquatic environment, including natural drinking water resources. Ozonation is a suitable treatment process for micropollutant removal, although, currently, little is known about the formation, behavior, and removal of transformation products (TP) formed during ozonation. We investigated the elimination of 30 selected micropollutants (pharmaceuticals, X-ray contrast media, industrial chemicals, and TP) by biological treatment coupled with ozonation and, subsequently, in parallel with two biological filters (BF) or granular activated carbon (GAC) filters. The selected micropollutants were removed to very different extents during the conventional biological wastewater treatment process. Ozonation (specific ozone consumption: 0.87 ± 0.29 gO3 gDOC(-1), hydraulic retention time: 17 ± 3 min) eliminated a large number of the investigated micropollutants. Although 11 micropollutants could still be detected after ozonation, most of these were eliminated in subsequent GAC filtration at bed volumes (BV) of approximately 25,000 m(3) m(-3). In contrast, no additional removal of micropollutants was achieved in the BF. Ozonation of the analgesic tramadol led to the formation of tramadol-N-oxide that is effectively eliminated by GAC filters, but not by BF. For the antiviral drug acyclovir, the formation of carboxy-acyclovir was observed during activated sludge treatment, with an average concentration of 3.4 ± 1.4 μg L(-1) detected in effluent samples. Subsequent ozonation resulted in the complete elimination of carboxy-acyclovir and led to the formation of N-(4-carbamoyl-2-imino-5-oxo imidazolidin)-formamido-N-methoxyacetetic acid (COFA; average concentration: 2.6 ± 1.0 μg L(-1)). Neither the BF nor the GAC filters were able to remove COFA. These results highlight the importance of considering TP in the evaluation of advanced wastewater treatment processes. The results further indicate that post-treatment of ozonated wastewater with GAC filtration seems to be more suitable than BF, due to the sorption of formed TP to the activated carbon. Copyright © 2016 Elsevier Ltd. All rights reserved.

Deformation of the total ozone content field in the tropical zone

NASA Technical Reports Server (NTRS)

Vasilyev, Victor I.

1994-01-01

Presented are the ozone investigation results obtained in the tropical zone. Measurements of the total ozone content (TOC) were carried out by the ozonometer M-124. The ozonometer was automated to investigate the ozone intradiurnal variations and to increase precision of the TOC measurements. Obtained results allowed us to follow the effect of tropical cyclones (TC) on the TOC field. Several days before the TC formation the TOC increase is observed in daily mean course compared with the background one. Three types of trend can be singled out in the TOC intradiurnal course: zero, parabolic, quasi-linear. Maximum velocities of a trend are observed some days before the TC formation. Analogous harmonic constituents are mainly presented as spectrum of daily means of ozone, mean and absolute velocities of trend and dispersion as well as spectra of meteorological, hydrometeorological and actinometric values. Revealed is a number of day-to-day ozone variations concerned with large-scale circulations; moisture content in the atmosphere. Obtained are the data about short-period ozone waves (period less than a day). Thin-film silver sensors were used to measure the vertical ozone distribution (VOD). Atmospheric aerosol and VOD measurements were carried out simultaneously, they gave data of the VOD layered structure, where the VOD local minima coincided with the position of aerosol layers' maxima.

Characteristics of 1 year of observational data of VOCs, NOx and O3 at a suburban site in Guangzhou, China

NASA Astrophysics Data System (ADS)

Zou, Y.; Deng, X. J.; Zhu, D.; Gong, D. C.; Wang, H.; Li, F.; Tan, H. B.; Deng, T.; Mai, B. R.; Liu, X. T.; Wang, B. G.

2015-06-01

Guangzhou, one of China's megacities, is beset with frequent occurrence of high-concentration ozone events. In this study, online instruments were used to simultaneously monitor ozone, nitrogen oxides (NOx) and volatile organic compounds (VOCs) at GPACS (the Guangzhou Panyu Atmospheric Composition Station) of the China Meteorological Administration, from June 2011 to May 2012, in order to determine their characteristics, the effect of VOCs on ozone photochemical production and the relationship between VOC / NOx ratio and ozone formation. The results showed that during the observation period, the seasonal variation of ozone concentration was lower in spring and winter compared to summer and autumn, which is opposite that for VOCs and NOx. In terms of VOCs, aromatics had the largest ozone formation potential, among which toluene, xylenes, ethylbenzene, 1,2,4-trimethylbenzene and 1,3,5-trimethylbenzene were the most important species, with a total contribution of about 44%. As the VOC / NOx ratios were very high during high-concentration ozone events that occur all year round, we speculate ozone production was likely to be NOx-limited regime (12:00-16:00 LT) in Guangzhou. Further investigation based on numerical models is needed in the future to obtain more detailed and robust conclusions.

Analysis of TES Satellite Ozone Observations from 2005 to 2013 to Understand Global Air Pollution Transport

NASA Astrophysics Data System (ADS)

Kladar, R. M.; Cooper, O. R.

2015-12-01

To better understand the causes of ozone formation and transport, we create and analyze global satellite ozone retrieval products for ground level to upper tropospheric ozone concentrations over the years 2005 to 2013 using the Tropospheric Emission Spectrometer (TES) that rides aboard the NASA Aura satellite. Many global and regional tropospheric ozone trends are not fully understood. Observing many different pressure levels between 1000 hPa to 215 hPa, we focus on the areas where model and other observation strategies disagree, namely the Arabian Peninsula, the Australian outback, and the southern Sahara. We observe (and these areas may be experiencing) unusually high ozone concentrations. We also comment on the historically high ozone areas such as China, Northern India, western Europe, and the western and southern United States and how known phenomena compare to our observations. Many observations confirm known mechanisms of ozone formation and transport, such as the effect of the yearly monsoon cycle in South, Southeast, and East Asia. Others, such as the surprisingly high monthly average concentrations on the Arabian Peninsula and Southern Sahara, deserve more thorough investigation. Several hypotheses for these disagreement areas are put forward here. Lastly, we comment on the usefulness of the TES instrument for trends analysis and future global observations.

Is the ozone climate penalty robust in Europe?

NASA Astrophysics Data System (ADS)

Colette, Augustin; Andersson, Camilla; Baklanov, Alexander; Bessagnet, Bertrand; Brandt, Jørgen; Christensen, Jesper H.; Doherty, Ruth; Engardt, Magnuz; Geels, Camilla; Giannakopoulos, Christos; Hedegaard, Gitte B.; Katragkou, Eleni; Langner, Joakim; Lei, Hang; Manders, Astrid; Melas, Dimitris; Meleux, Frédérik; Rouïl, Laurence; Sofiev, Mikhail; Soares, Joana; Stevenson, David S.; Tombrou-Tzella, Maria; Varotsos, Konstantinos V.; Young, Paul

2015-08-01

Ozone air pollution is identified as one of the main threats bearing upon human health and ecosystems, with 25 000 deaths in 2005 attributed to surface ozone in Europe (IIASA 2013 TSAP Report #10). In addition, there is a concern that climate change could negate ozone pollution mitigation strategies, making them insufficient over the long run and jeopardising chances to meet the long term objective set by the European Union Directive of 2008 (Directive 2008/50/EC of the European Parliament and of the Council of 21 May 2008) (60 ppbv, daily maximum). This effect has been termed the ozone climate penalty. One way of assessing this climate penalty is by driving chemistry-transport models with future climate projections while holding the ozone precursor emissions constant (although the climate penalty may also be influenced by changes in emission of precursors). Here we present an analysis of the robustness of the climate penalty in Europe across time periods and scenarios by analysing the databases underlying 11 articles published on the topic since 2007, i.e. a total of 25 model projections. This substantial body of literature has never been explored to assess the uncertainty and robustness of the climate ozone penalty because of the use of different scenarios, time periods and ozone metrics. Despite the variability of model design and setup in this database of 25 model projection, the present meta-analysis demonstrates the significance and robustness of the impact of climate change on European surface ozone with a latitudinal gradient from a penalty bearing upon large parts of continental Europe and a benefit over the North Atlantic region of the domain. Future climate scenarios present a penalty for summertime (JJA) surface ozone by the end of the century (2071-2100) of at most 5 ppbv. Over European land surfaces, the 95% confidence interval of JJA ozone change is [0.44; 0.64] and [0.99; 1.50] ppbv for the 2041-2070 and 2071-2100 time windows, respectively.

The Interplay of Climate Change and Air Pollution on Health.

PubMed

Orru, H; Ebi, K L; Forsberg, B

2017-12-01

Air pollution significantly affects health, causing up to 7 million premature deaths annually with an even larger number of hospitalizations and days of sick leave. Climate change could alter the dispersion of primary pollutants, particularly particulate matter, and intensify the formation of secondary pollutants, such as near-surface ozone. The purpose of the review is to evaluate the recent evidence on the impacts of climate change on air pollution and air pollution-related health impacts and identify knowledge gaps for future research. Several studies modelled future ozone and particulate matter concentrations and calculated the resulting health impacts under different climate scenarios. Due to climate change, ozone- and fine particle-related mortalities are expected to increase in most studies; however, results differ by region, assumed climate change scenario and other factors such as population and background emissions. This review explores the relationships between climate change, air pollution and air pollution-related health impacts. The results highly depend on the climate change scenario used and on projections of future air pollution emissions, with relatively high uncertainty. Studies primarily focused on mortality; projections on the effects on morbidity are needed.

Fate of Chloromethanes in the Atmospheric Environment: Implications for Human Health, Ozone Formation and Depletion, and Global Warming Impacts.

PubMed

Tsai, Wen-Tien

2017-09-21

Among the halogenated hydrocarbons, chloromethanes (i.e., methyl chloride, CH₃Cl; methylene chloride, CH₂Cl₂; chloroform, CHCl₃; and carbon tetrachloride, CCl₄) play a vital role due to their extensive uses as solvents and chemical intermediates. This article aims to review their main chemical/physical properties and commercial/industrial uses, as well as the environment and health hazards posed by them and their toxic decomposition products. The environmental properties (including atmospheric lifetime, radiative efficiency, ozone depletion potential, global warming potential, photochemical ozone creation potential, and surface mixing ratio) of these chlorinated methanes are also reviewed. In addition, this paper further discusses their atmospheric fates and human health implications because they are apt to reside in the lower atmosphere when released into the environment. According to the atmospheric degradation mechanism, their toxic degradation products in the troposphere include hydrogen chloride (HCl), carbon monoxide (CO), chlorine (Cl₂), formyl chloride (HCOCl), carbonyl chloride (COCl₂), and hydrogen peroxide (H₂O₂). Among them, COCl₂ (also called phosgene) is a powerful irritating gas, which is easily hydrolyzed or thermally decomposed to form hydrogen chloride.

Nicotiana tabacum as model for ozone - plant surface reactions

NASA Astrophysics Data System (ADS)

Jud, Werner; Fischer, Lukas; Wohlfahrt, Georg; Tissier, Alain; Canaval, Eva; Hansel, Armin

2015-04-01

Elevated tropospheric ozone concentrations are considered a toxic threat to plants, responsible for global crop losses with associated economic costs of several billion dollars per year. The ensuing injuries have been related to the uptake of ozone through the stomatal pores and oxidative effects damaging the internal leaf tissue. A striking question of current research is the environment and plant specific partitioning of ozone loss between gas phase, stomatal or plant surface sink terms. Here we show results from ozone fumigation experiments using various Nicotiana Tabacum varieties, whose surfaces are covered with different amounts of unsaturated diterpenoids exuded by their glandular trichomes. Exposure to elevated ozone levels (50 to 150 ppbv) for 5 to 15 hours in an exceptionally clean cuvette system did neither result in a reduction of photosynthesis nor caused any visible leaf damage. Both these ozone induced stress effects have been observed previously in ozone fumigation experiments with the ozone sensitive tobacco line Bel-W3. In our case ozone fumigation was accompanied by a continuous release of oxygenated volatile organic compounds, which could be clearly associated to their condensed phase precursors for the first time. Gas phase reactions of ozone were avoided by choosing a high enough gas exchange rate of the plant cuvette system. In the case of the Ambalema variety, that is known to exude only the diterpenoid cis-abienol, ozone fumigation experiments yield the volatiles formaldehyde and methyl vinyl ketone (MVK). The latter could be unequivocally separated from isomeric methacrolein (MACR) by the aid of a Selective Reagent Ion Time-of-Flight Mass Spectrometer (SRI-ToF-MS), which was switched every six minutes from H3O+ to NO+ primary ion mode and vice versa. Consistent with the picture of an ozone protection mechanism caused by reactive diterpenoids at the leaf surface are the results from dark-light experiments. The ozone loss obtained from the difference of ozone measured before and after the plant cuvette was investigated as a function of stomatal opening. Switching from dark to light conditions and thus opening the stomata only a small increase in ozone loss was observed for the Ambalema variety (25%). In the case of the 3H02 variety, a line known to emit almost no diterpenoids, the ozone loss increased by more than 100% when changing from dark to light conditions. It is anticipated that the described effect is of importance also for other plant species emitting low-volatility unsaturated organic compounds (e.g. in form of exudates or resins).

Surface ozone in the White Mountains of California

Treesearch

Joel Burley; Andrzej Bytnerowicz

2011-01-01

Surface ozone concentrations are presented for four high-elevation sites along a northesouth transect along the spine of the White Mountains and a fifth site located at lower elevation approximately 15 km to the west on the floor of the Owens Valley. The ozone data, which were collected from mid-June through mid-October of 2009, include results from two sites, White...

THE GAS PHASE REACTION OF OZONE WITH 1,3-BUTADIENE: FORMATION YIELDS OF SOME TOXIC PRODUCTS. (R826236)

EPA Science Inventory

The formation yields of acrolein, 1,2-epoxy-3-butene and OH radicals have been measured from reaction of ozone with 1,3-butadiene at room temperature and atmosphere pressure. 1,3,5-Trimethyl benzene was added to scavenge OH radicals in measurements of product yields. In separa...

Interannual variability of the Antarctic ozone hole in a GCM. Part 2: A comparison of unforced and QBO-induced variability

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shindell, D.T.; Rind, D.; Balachandran, N.

1999-06-15

Simulations were performed with the Goddard Institute for Space Studies GCM including a prescribed quasi-biennial oscillation (QBO), applied at a constant maximum value, and a physically realistic parameterization of the heterogeneous chemistry responsible for severe polar ozone loss. While the QBO is primarily a stratospheric phenomenon, in this model the QBO modulates the amount and propagation of planetary wave energy in the troposphere as well as in the stratosphere. Dynamical activity is greater in the easterly than in the unforced case, while westerly years are dynamically more quiescent. By altering zonal winds and potential vorticity, the QBO forcing changes themore » refraction of planetary waves beginning in midwinter, causing the lower-stratospheric zonal average temperatures at Southern Hemisphere high latitudes to be [approximately]3--5 K warmer in the easterly phase than in the westerly during the late winter and early spring. Ozone loss varies nonlinearly with temperature, due to the sharp threshold for formation of heterogeneous chemistry surfaces, so that the mean daily total mass of ozone depleted in this region during September was 8.7 [times] 10[sup 10] kg in the QBO easterly maximum, as compared with 12.0 [times] 10[sup 10] kg in the westerly maximum and 10.3 [times] 10[sup 10] kg in the unforced case. Through this mechanism, the midwinter divergence of the Eliassen-Palm flux is well correlated with the subsequent springtime total ozone loss (R[sup 2] = 0.6). The chemical ozone loss differences are much larger than QBO-induced transport differences in the authors' model. Inclusion of the QBO forcing also increased the maximum variability in total ozone loss from the [approximately]20% value found in the unforced runs to [approximately]50%. These large variations in ozone depletion are very similar in size to the largest observed variations in the severity of the ozone hole. The results suggest that both random variability and periodic QBO forcing are important components, perhaps explaining some of the difficulties encountered in previous attempts to correlate the severity of the ozone hole with the QBO phase.« less

Water Reclamation Using a Ceramic Nanofiltration Membrane and Surface Flushing with Ozonated Water

PubMed Central

Hoang, Anh T.; Okuda, Tetsuji; Takeuchi, Haruka; Tanaka, Hiroaki; Nghiem, Long D.

2018-01-01

A new membrane fouling control technique using ozonated water flushing was evaluated for direct nanofiltration (NF) of secondary wastewater effluent using a ceramic NF membrane. Experiments were conducted at a permeate flux of 44 L/m2h to evaluate the ozonated water flushing technique for fouling mitigation. Surface flushing with clean water did not effectively remove foulants from the NF membrane. In contrast, surface flushing with ozonated water (4 mg/L dissolved ozone) could effectively remove most foulants to restore the membrane permeability. This surface flushing technique using ozonated water was able to limit the progression of fouling to 35% in transmembrane pressure increase over five filtration cycles. Results from this study also heighten the need for further development of ceramic NF membrane to ensure adequate removal of pharmaceuticals and personal care products (PPCPs) for water recycling applications. The ceramic NF membrane used in this study showed approximately 40% TOC rejection, and the rejection of PPCPs was generally low and highly variable. It is expected that the fouling mitigation technique developed here is even more important for ceramic NF membranes with smaller pore size and thus better PPCP rejection. PMID:29671797

Broad features of surface ozone variations over Indian region

NASA Technical Reports Server (NTRS)

Shende, R. R.; Jayaraman, K.; Sreedharan, C. R.; Tiwari, V. S.

1994-01-01

Surface ozone concentration at three Indian stations - New Delhi (28.6 deg N), Pune (18.5 deg N) and Thiruvananthapuram (formerly Trivandrum (8.3 deg N) - has been measured since 1973 with the help of an electrochemical continuous ozone recorder. These stations show diurnal, seasonal and annual cycles in surface ozone. Daily changes show that the minimum value occurs at sunrise and maximum in the afternoon. As regards seasonal variations, Thiruvananthapuram and Pune have a minimum value during monsoon season (June to August) while at New Delhi the minimum value occurs in January. However, New Delhi also records low ozone amount during monsoon season identical to the amounts show at Thiruvananthapuram and Pune. The annual cycles at these stations have been compared with similar measurements in the northern and southern hemispheres. The Indian measurements agree well with the annual cycles at these stations. Further, the analysis of the Indian data indicates that the major contribution in surface ozone comes from the natural sources like stratospheric-tropospheric exchange, turbulence, and mixing in the boundary layer; however, a small contribution from anthropogenic sources cannot be ruled out at Pune and probably at New Delhi, especially in winter and summer seasons.

Water Reclamation Using a Ceramic Nanofiltration Membrane and Surface Flushing with Ozonated Water.

PubMed

Fujioka, Takahiro; Hoang, Anh T; Okuda, Tetsuji; Takeuchi, Haruka; Tanaka, Hiroaki; Nghiem, Long D

2018-04-19

A new membrane fouling control technique using ozonated water flushing was evaluated for direct nanofiltration (NF) of secondary wastewater effluent using a ceramic NF membrane. Experiments were conducted at a permeate flux of 44 L/m²h to evaluate the ozonated water flushing technique for fouling mitigation. Surface flushing with clean water did not effectively remove foulants from the NF membrane. In contrast, surface flushing with ozonated water (4 mg/L dissolved ozone) could effectively remove most foulants to restore the membrane permeability. This surface flushing technique using ozonated water was able to limit the progression of fouling to 35% in transmembrane pressure increase over five filtration cycles. Results from this study also heighten the need for further development of ceramic NF membrane to ensure adequate removal of pharmaceuticals and personal care products (PPCPs) for water recycling applications. The ceramic NF membrane used in this study showed approximately 40% TOC rejection, and the rejection of PPCPs was generally low and highly variable. It is expected that the fouling mitigation technique developed here is even more important for ceramic NF membranes with smaller pore size and thus better PPCP rejection.

Ozone production process in pulsed positive dielectric barrier discharge

NASA Astrophysics Data System (ADS)

Ono, Ryo; Oda, Tetsuji

2007-01-01

The ozone production process in a pulsed positive dielectric barrier discharge (DBD) is studied by measuring the spatial distribution of ozone density using a two-dimensional laser absorption method. DBD occurs in a 6 mm point-to-plane gap with a 1 mm-thick glass plate placed on the plane electrode. First, the propagation of DBD is observed using a short-gated ICCD camera. It is shown that DBD develops in three phases: primary streamer, secondary streamer and surface discharge phases. Next, the spatial distribution of ozone density is measured. It is shown that ozone is mostly produced in the secondary streamer and surface discharge, while only a small amount of ozone is produced in the primary streamer. The rate coefficient of the ozone production reaction, O + O2 + M → O3 + M, is estimated to be 2.5 × 10-34 cm6 s-1.

Formation of N-nitrosodimethylamine (NDMA) by ozonation of dyes and related compounds.

PubMed

Oya, Masami; Kosaka, Koji; Asami, Mari; Kunikane, Shoichi

2008-12-01

Formation of N-nitrosodimethylamine (NDMA) by ozonation of commercially available dyes and related compounds was investigated. Ozonation was conducted using a semi-batch type reactor, and ozone concentration in gas phase and the ozone gas flow were 10 mg L(-1) and 1.0 L min(-1), respectively. NDMA was formed by 15 min of ozonation of seven out of eight selected target compounds (0.05 mM) at pH 7. All the target compounds with N,N-dimethylamino functions were NDMA precursors in ozonation. The lowest and highest NDMA concentrations after ozonation of the target compounds were 13 ng L(-1) for N,N-dimethylformamide (DMF) and 1600 ng L(-1) for N,N-dimethyl-p-phenylenediamine (DMPD), respectively. NDMA concentrations after 15 min of ozonation of 0.05 mM methylene blue (MB) and DMPD increased with an increase in pH in its range of 6-8. The effects of coexisting compounds on NDMA concentrations after 15 min of ozonation of 0.05 mM MB and DMPD were examined at pH 7. NDMA concentrations after ozonation of MB and DMPD increased by the presence of 0.05 mM (0.7 mg L(-1) as N) nitrite (NO(2)(-)); 5000 ng L(-1) for MB and 4000 ng L(-1) for DMPD. NDMA concentration after MB ozonation decreased by the presence of 5mM tertiary butyl alcohol (TBA), a hydroxyl radical (HO.) scavenger, but that after DMPD ozonation was increased by the presence of TBA. NDMA concentrations after ozonation of MB and DMPD were not affected by the presence of 0.16 mM (5.3 mg L(-1)) hydrogen peroxide (H(2)O(2)). When 0.05 mM MB and DMPD were added to the Yodo and Tone river water samples, NDMA concentrations after 15 min of their ozonation at pH 7 increased compared with those in the case of addition to ultrapure water samples.

Fungicide residue remediation on table grapes using ozone fumigation

USDA-ARS?s Scientific Manuscript database

Ozone fumigation was explored as a means for degrading contemporary organic fungicides related to table grape production. Separate fumigations were conducted in a flow-through chamber on fungicides sorbed to model abiotic glass surfaces or to table grapes. Gaseous ozone at constant ozone concentrati...

Ozone decomposition

PubMed Central

Batakliev, Todor; Georgiev, Vladimir; Anachkov, Metody; Rakovsky, Slavcho

2014-01-01

Catalytic ozone decomposition is of great significance because ozone is a toxic substance commonly found or generated in human environments (aircraft cabins, offices with photocopiers, laser printers, sterilizers). Considerable work has been done on ozone decomposition reported in the literature. This review provides a comprehensive summary of the literature, concentrating on analysis of the physico-chemical properties, synthesis and catalytic decomposition of ozone. This is supplemented by a review on kinetics and catalyst characterization which ties together the previously reported results. Noble metals and oxides of transition metals have been found to be the most active substances for ozone decomposition. The high price of precious metals stimulated the use of metal oxide catalysts and particularly the catalysts based on manganese oxide. It has been determined that the kinetics of ozone decomposition is of first order importance. A mechanism of the reaction of catalytic ozone decomposition is discussed, based on detailed spectroscopic investigations of the catalytic surface, showing the existence of peroxide and superoxide surface intermediates. PMID:26109880

Diverse policy implications for future ozone and surface UV in a changing climate

NASA Astrophysics Data System (ADS)

Butler, A. H.; Daniel, J. S.; Portmann, R. W.; Ravishankara, A. R.; Young, P. J.; Fahey, D. W.; Rosenlof, K. H.

2016-06-01

Due to the success of the Montreal Protocol in limiting emissions of ozone-depleting substances, concentrations of atmospheric carbon dioxide, nitrous oxide, and methane will control the evolution of total column and stratospheric ozone by the latter half of the 21st century. As the world proceeds down the path of reducing climate forcing set forth by the 2015 Conference of the Parties to the United Nations Framework Convention on Climate Change (COP 21), a broad range of ozone changes are possible depending on future policies enacted. While decreases in tropical stratospheric ozone will likely persist regardless of the future emissions scenario, extratropical ozone could either remain weakly depleted or even increase well above historical levels, with diverse implication for ultraviolet (UV) radiation. The ozone layer’s dependence on future emissions of these gases creates a complex policy decision space for protecting humans and ecosystems, which includes unexpected options such as accepting nitrous oxide emissions in order to maintain historical column ozone and surface UV levels.

Damages of surface ozone: evidence from agricultural sector in China

NASA Astrophysics Data System (ADS)

Yi, Fujin; McCarl, Bruce A.; Zhou, Xun; Jiang, Fei

2018-03-01

This study measures the damages that surface ozone pollution causes within the Chinese agricultural sector under 2014 conditions. It also analyzes the agricultural benefits of ozone reductions. The analysis is done using a partial equilibrium model of China’s agricultural sector. Results indicate that there are substantial, spatially differentiated damages that are greatest in ozone-sensitive crop growing areas with higher ozone concentrations. The estimated damage to China’s agricultural sector range is between CNY 1.6 trillion and 2.2 trillion, which for comparison is about one fifth of 2014 agricultural revenue. When considering concentration reduction we find a 30% ozone reduction yields CNY 678 billion in sectoral benefits. These benefits largely fall to consumers with producers losing as the production gains lead to lower prices.

Expected ozone benefits of reducing nitrogen oxide (NOx) emissions from coal-fired electricity generating units in the eastern United States.

PubMed

Vinciguerra, Timothy; Bull, Emily; Canty, Timothy; He, Hao; Zalewsky, Eric; Woodman, Michael; Aburn, George; Ehrman, Sheryl; Dickerson, Russell R

2017-03-01

On hot summer days in the eastern United States, electricity demand rises, mainly because of increased use of air conditioning. Power plants must provide this additional energy, emitting additional pollutants when meteorological conditions are primed for poor air quality. To evaluate the impact of summertime NO x emissions from coal-fired electricity generating units (EGUs) on surface ozone formation, we performed a series of sensitivity modeling forecast scenarios utilizing EPA 2018 version 6.0 emissions (2011 base year) and CMAQ v5.0.2. Coal-fired EGU NO x emissions were adjusted to match the lowest NO x rates observed during the ozone seasons (April 1-October 31) of 2005-2012 (Scenario A), where ozone decreased by 3-4 ppb in affected areas. When compared to the highest emissions rates during the same time period (Scenario B), ozone increased ∼4-7 ppb. NO x emission rates adjusted to match the observed rates from 2011 (Scenario C) increased ozone by ∼4-5 ppb. Finally in Scenario D, the impact of additional NO x reductions was determined by assuming installation of selective catalytic reduction (SCR) controls on all units lacking postcombustion controls; this decreased ozone by an additional 2-4 ppb relative to Scenario A. Following the announcement of a stricter 8-hour ozone standard, this analysis outlines a strategy that would help bring coastal areas in the mid-Atlantic region closer to attainment, and would also provide profound benefits for upwind states where most of the regional EGU NO x originates, even if additional capital investments are not made (Scenario A). With the 8-hr maximum ozone National Ambient Air Quality Standard (NAAQS) decreasing from 75 to 70 ppb, modeling results indicate that use of postcombustion controls on coal-fired power plants in 2018 could help keep regions in attainment. By operating already existing nitrogen oxide (NO x ) removal devices to their full potential, ozone could be significantly curtailed, achieving ozone reductions by up to 5 ppb in areas around the source of emission and immediately downwind. Ozone improvements are also significant (1-2 ppb) for areas affected by cross-state transport, especially Mid-Atlantic coast regions that had struggled to meet the 75 ppb standard.

The potential near-source ozone impacts of upstream oil and gas industry emissions.

PubMed

Olaguer, Eduardo P

2012-08-01

Increased drilling in urban areas overlying shale formations and its potential impact on human health through decreased air quality make it important to estimate the contribution of oil and gas activities to photochemical smog. Flares and compressor engines used in natural gas operations, for example, are large sources not only of NOx but also offormaldehyde, a hazardous air pollutant and powerful ozone precursor We used a neighborhood scale (200 m horizontal resolution) three-dimensional (3D) air dispersion model with an appropriate chemical mechanism to simulate ozone formation in the vicinity ofa hypothetical natural gas processing facility, based on accepted estimates of both regular and nonroutine emissions. The model predicts that, under average midday conditions in June, regular emissions mostly associated with compressor engines may increase ambient ozone in the Barnett Shale by more than 3 ppb beginning at about 2 km downwind of the facility, assuming there are no other major sources of ozone precursors. Flare volumes of 100,000 cubic meters per hour ofnatural gas over a period of 2 hr can also add over 3 ppb to peak 1-hr ozone somewhatfurther (>8 km) downwind, once dilution overcomes ozone titration and inhibition by large flare emissions of NOx. The additional peak ozone from the hypothetical flare can briefly exceed 10 ppb about 16 km downwind. The enhancements of ambient ozone predicted by the model are significant, given that ozone control strategy widths are of the order of a few parts per billion. Degrading the horizontal resolution of the model to 1 km spuriously enhances the simulated ozone increases by reducing the effectiveness of ozone inhibition and titration due to artificial plume dilution.

Climate change impacts on projections of excess mortality at ...

EPA Pesticide Factsheets

We project the change in ozone-related mortality burden attributable to changes in climate between a historical (1995-2005) and near-future (2025-2035) time period while incorporating a non-linear and synergistic effect of ozone and temperature on mortality. We simulate air quality from climate projections varying only biogenic emissions and holding anthropogenic emissions constant, thus attributing changes in ozone only to changes in climate and independent of changes in air pollutant emissions. We estimate non-linear, spatially varying, ozone-temperature risk surfaces for 94 US urban areas using observeddata. Using the risk surfaces and climate projections we estimate daily mortality attributable to ozone exceeding 40 p.p.b. (moderate level) and 75 p.p.b. (US ozone NAAQS) for each time period. The average increases in city-specific median April-October ozone and temperature between time periods are 1.02 p.p.b. and 1.94 °F; however, the results variedby region . Increases in ozone because of climate change result in an increase in ozone mortality burden. Mortality attributed to ozone exceeding 40 p.p.b. increases by 7.7% (1 .6-14.2%). Mortality attributed to ozone exceeding 75 p.p.b. increases by 14.2% (1.628.9%). The absolute increase in excess ozone mortality is larger for changes in moderate ozone levels, reflecting the larger number of days with moderate ozone levels. In this study we evaluate changes in ozone related mortality due to changes in biogenic f

Impacts of Interactive Stratospheric Chemistry on Antarctic and Southern Ocean Climate Change in the Goddard Earth Observing System Version 5 (GEOS-5)

NASA Technical Reports Server (NTRS)

Li, Feng; Vikhliaev, Yury V.; Newman, Paul A.; Pawson, Steven; Perlwitz, Judith; Waugh, Darryn W.; Douglass, Anne R.

2016-01-01

Stratospheric ozone depletion plays a major role in driving climate change in the Southern Hemisphere. To date, many climate models prescribe the stratospheric ozone layer's evolution using monthly and zonally averaged ozone fields. However, the prescribed ozone underestimates Antarctic ozone depletion and lacks zonal asymmetries. In this study we investigate the impact of using interactive stratospheric chemistry instead of prescribed ozone on climate change simulations of the Antarctic and Southern Ocean. Two sets of 1960-2010 ensemble transient simulations are conducted with the coupled ocean version of the Goddard Earth Observing System Model, version 5: one with interactive stratospheric chemistry and the other with prescribed ozone derived from the same interactive simulations. The model's climatology is evaluated using observations and reanalysis. Comparison of the 1979-2010 climate trends between these two simulations reveals that interactive chemistry has important effects on climate change not only in the Antarctic stratosphere, troposphere, and surface, but also in the Southern Ocean and Antarctic sea ice. Interactive chemistry causes stronger Antarctic lower stratosphere cooling and circumpolar westerly acceleration during November-December-January. It enhances stratosphere-troposphere coupling and leads to significantly larger tropospheric and surface westerly changes. The significantly stronger surface wind stress trends cause larger increases of the Southern Ocean Meridional Overturning Circulation, leading to year-round stronger ocean warming near the surface and enhanced Antarctic sea ice decrease.

Effects and mechanism on Kapton film under ozone exposure in a ground near space simulator

NASA Astrophysics Data System (ADS)

Wei, Qiang; Yang, Guimin; Liu, Gang; Jiang, Haifu; Zhang, Tingting

2018-05-01

The effect on aircraft materials in the near space environment is a key part of air-and-space integration research. Ozone and aerodynamic fluids are important organizational factors in the near space environment and both have significant influences on the performance of aircraft materials. In the present paper a simulated ozone environment was used to test polyimide material that was rotated at the approximate velocity of 150-250 m/s to form an aerodynamic fluid field. The goal was to evaluate the performance evolution of materials under a comprehensive environment of ozone molecular corrosion and aerodynamic fluids. The research results show that corrosion and sputtering by ozone molecules results in Kapton films exhibiting a rugged "carpet-like" morphology exhibits an increase in surface roughness. The morphology after ozone exposure led to higher surface roughness and an increase in surface optical diffuse reflection, which is expressed by the lower optical transmittance and the gradual transition from light orange to brown. The mass loss test, XPS, and FTIR analysis show that the molecular chains on the surface of the Kapton film are destroyed resulting in Csbnd C bond breaking to form small volatile molecules such as CO2 or CO, which are responsible for a linear increase in mass loss per unit area. The Csbnd N and Csbnd O structures exhibit weakening tendency under ozone exposure. The present paper explores the evaluation method for Kapton's adaptability under the ozone exposure test in the near space environment, and elucidates the corrosion mechanism and damage mode of the polyimide material under the combined action of ozone corrosion and the aerodynamic fluid. This work provides a methodology for studying materials in the near-space environment.

Tobacco smoke aging in the presence of ozone: A room-sized chamber study

NASA Astrophysics Data System (ADS)

Petrick, Lauren M.; Sleiman, Mohamad; Dubowski, Yael; Gundel, Lara A.; Destaillats, Hugo

2011-09-01

Exposure to tobacco pollutants that linger indoors after smoking has taken place ( thirdhand smoke, THS) can occur over extended periods and is modulated by chemical processes involving atmospheric reactive species. This study investigates the role of ozone and indoor surfaces in chemical transformations of tobacco smoke residues. Gas and particle constituents of secondhand smoke (SHS) as well as sorbed SHS on chamber internal walls and model materials (cotton, paper, and gypsum wallboard) were characterized during aging. After smoldering 10 cigarettes in a 24-m 3 room size chamber, gas-phase nicotine was rapidly removed by sorption to chamber surfaces, and subsequently re-emitted during ventilation with clean air to a level of ˜10% that during the smoking phase. During chamber ventilation in the presence of ozone (180 ppb), ozone decayed at a rate of 5.6 h -1 and coincided with a factor of 5 less nicotine sorbed to wallboard. In the presence of ozone, no gas phase nicotine was detected as a result of re-emission, and higher concentrations of nicotine oxidation products were observed than when ventilation was performed with ozone-free air. Analysis of the model surfaces showed that heterogeneous nicotine-ozone reaction was faster on paper than cotton, and both were faster than on wallboard. However, wallboard played a dominant role in ozone-initiated reaction in the chamber due to its large total geometric surface area and sink potential compared to the other substrates. This study is the first to show in a room-sized environmental chamber that the heterogeneous ozone chemistry of sorbed nicotine generates THS constituents of concern, as observed previously in bench-top studies. In addition to the main oxidation products (cotinine, myosmine and N-methyl formamide), nicotine-1-oxide was detected for the first time.

Evaluation of the Community Multiscale Air Quality Model for Simulating Winter Ozone Formation in the Uinta Basin.

EPA Science Inventory

The Weather Research and Forecasting (WRF) and Community Multiscale Air Quality (CMAQ) models were used to simulate a 10 day high‐ozone episode observed during the 2013 Uinta Basin Winter Ozone Study (UBWOS). The baseline model had a large negative bias when compared to ozo...

The lasting effect of limonene-induced particle formation on air quality in a genuine indoor environment.

PubMed

Rösch, Carolin; Wissenbach, Dirk K; von Bergen, Martin; Franck, Ulrich; Wendisch, Manfred; Schlink, Uwe

2015-09-01

Atmospheric ozone-terpene reactions, which form secondary organic aerosol (SOA) particles, can affect indoor air quality when outdoor air mixes with indoor air during ventilation. This study, conducted in Leipzig, Germany, focused on limonene-induced particle formation in a genuine indoor environment (24 m(3)). Particle number, limonene and ozone concentrations were monitored during the whole experimental period. After manual ventilation for 30 min, during which indoor ozone levels reached up to 22.7 ppb, limonene was introduced into the room at concentrations of approximately 180 to 250 μg m(-3). We observed strong particle formation and growth within a diameter range of 9 to 50 nm under real-room conditions. Larger particles with diameters above 100 nm were less affected by limonene introduction. The total particle number concentrations (TPNCs) after limonene introduction clearly exceed outdoor values by a factor of 4.5 to 41 reaching maximum concentrations of up to 267,000 particles cm(-3). The formation strength was influenced by background particles, which attenuated the formation of new SOA with increasing concentration, and by ozone levels, an increase of which by 10 ppb will result in a six times higher TPNC. This study emphasizes indoor environments to be preferred locations for particle formation and growth after ventilation events. As a consequence, SOA formation can produce significantly higher amounts of particles than transported by ventilation into the indoor air.

Chemistry of Volatile Organic Compounds in the Los Angeles Basin: Formation of Oxygenated Compounds and Determination of Emission Ratios

NASA Astrophysics Data System (ADS)

de Gouw, J. A.; Gilman, J. B.; Kim, S.-W.; Alvarez, S. L.; Dusanter, S.; Graus, M.; Griffith, S. M.; Isaacman-VanWertz, G.; Kuster, W. C.; Lefer, B. L.; Lerner, B. M.; McDonald, B. C.; Rappenglück, B.; Roberts, J. M.; Stevens, P. S.; Stutz, J.; Thalman, R.; Veres, P. R.; Volkamer, R.; Warneke, C.; Washenfelder, R. A.; Young, C. J.

2018-02-01

We analyze an expanded data set of oxygenated volatile organic compounds (OVOCs) in air measured by several instruments at a surface site in Pasadena near Los Angeles during the National Oceanic and Atmospheric Administration California Nexus study in 2010. The contributions of emissions, chemical formation, and removal are quantified for each OVOC using CO as a tracer of emissions and the OH exposure of the sampled air masses calculated from hydrocarbon ratios. The method for separating emissions from chemical formation is evaluated using output for Pasadena from the Weather Research and Forecasting-Chemistry model. The model is analyzed by the same method as the measurement data, and the emission ratios versus CO calculated from the model output agree for ketones with the inventory used in the model but overestimate aldehydes by 70%. In contrast with the measurements, nighttime formation of OVOCs is significant in the model and is attributed to overestimated precursor emissions and overestimated rate coefficients for the reactions of the precursors with ozone and NO3. Most measured aldehydes correlated strongly with CO at night, suggesting a contribution from motor vehicle emissions. However, the emission ratios of most aldehydes versus CO are higher than those reported in motor vehicle emissions and the aldehyde sources remain unclear. Formation of several OVOCs is investigated in terms of the removal of specific precursors. Direct emissions of alcohols and aldehydes contribute significantly to OH reactivity throughout the day, and these emissions should be accurately represented in models describing ozone formation.

Effect of Pre-ozonation on Haloacetic Acids Formation in Ganga River Water at Kanpur, India

NASA Astrophysics Data System (ADS)

Naladala, Nagasrinivasa Rao; Singh, Rambabu; Katiyar, Kumud Lata Devi; Bose, Purnendu; Dutta, Venkatesh

2017-11-01

Almost all natural water bodies which are considered to be sustainable sources of drinking water contain organic matter in dissolved form and pathogens. This dissolved organic matter and pathogens cannot be removed effectively through traditional filtering processes in drinking water treatment plants. Chlorination of such water for disinfection results in large amounts of disinfection by-products (DBPs), mainly trihalomethanes and haloacetic acids (HAAs), which showed many health effects like cancer and reproductive problems in lab animals and in human beings as well. Complete removal of dissolved organic carbon (DOC), which is a precursor compound for HAAs formation, is impossible from a practical point of view; hence, it will be better if DOC activity towards DBPs formation can be reduced via some process. The present article describes the process of pre-ozonating post-coagulated Ganga River water at Kanpur in a continuous flow mode and its effect on HAAs formation. Nearly 58% reduction in HAAs formation was observed during this study at higher doses of ozone.

Ozone and limonene in indoor air: a source of submicron particle exposure.

PubMed Central

Wainman, T; Zhang, J; Weschler, C J; Lioy, P J

2000-01-01

Little information currently exists regarding the occurrence of secondary organic aerosol formation in indoor air. Smog chamber studies have demonstrated that high aerosol yields result from the reaction of ozone with terpenes, both of which commonly occur in indoor air. However, smog chambers are typically static systems, whereas indoor environments are dynamic. We conducted a series of experiments to investigate the potential for secondary aerosol in indoor air as a result of the reaction of ozone with d-limonene, a compound commonly used in air fresheners. A dynamic chamber design was used in which a smaller chamber was nested inside a larger one, with air exchange occurring between the two. The inner chamber was used to represent a model indoor environment and was operated at an air exchange rate below 1 exchange/hr, while the outer chamber was operated at a high air exchange rate of approximately 45 exchanges/hr. Limonene was introduced into the inner chamber either by the evaporation of reagent-grade d-limonene or by inserting a lemon-scented, solid air freshener. A series of ozone injections were made into the inner chamber during the course of each experiment, and an optical particle counter was used to measure the particle concentration. Measurable particle formation and growth occurred almost exclusively in the 0.1-0.2 microm and 0.2-0.3 microm size fractions in all of the experiments. Particle formation in the 0.1-0.2 microm size range occurred as soon as ozone was introduced, but the formation of particles in the 0.2-0.3 microm size range did not occur until at least the second ozone injection occurred. The results of this study show a clear potential for significant particle concentrations to be produced in indoor environments as a result of secondary particle formation via the ozone-limonene reaction. Because people spend the majority of their time indoors, secondary particles formed in indoor environments may make a significant contribution to overall particle exposure. This study provides data for assessing the impact of outdoor ozone on indoor particles. This is important to determine the efficacy of the mass-based particulate matter standards in protecting public health because the indoor secondary particles can vary coincidently with the variations of outdoor fine particles in summer. PMID:11133393

Ozone and limonene in indoor air: a source of submicron particle exposure.

PubMed

Wainman, T; Zhang, J; Weschler, C J; Lioy, P J

2000-12-01

Little information currently exists regarding the occurrence of secondary organic aerosol formation in indoor air. Smog chamber studies have demonstrated that high aerosol yields result from the reaction of ozone with terpenes, both of which commonly occur in indoor air. However, smog chambers are typically static systems, whereas indoor environments are dynamic. We conducted a series of experiments to investigate the potential for secondary aerosol in indoor air as a result of the reaction of ozone with d-limonene, a compound commonly used in air fresheners. A dynamic chamber design was used in which a smaller chamber was nested inside a larger one, with air exchange occurring between the two. The inner chamber was used to represent a model indoor environment and was operated at an air exchange rate below 1 exchange/hr, while the outer chamber was operated at a high air exchange rate of approximately 45 exchanges/hr. Limonene was introduced into the inner chamber either by the evaporation of reagent-grade d-limonene or by inserting a lemon-scented, solid air freshener. A series of ozone injections were made into the inner chamber during the course of each experiment, and an optical particle counter was used to measure the particle concentration. Measurable particle formation and growth occurred almost exclusively in the 0.1-0.2 microm and 0.2-0.3 microm size fractions in all of the experiments. Particle formation in the 0.1-0.2 microm size range occurred as soon as ozone was introduced, but the formation of particles in the 0.2-0.3 microm size range did not occur until at least the second ozone injection occurred. The results of this study show a clear potential for significant particle concentrations to be produced in indoor environments as a result of secondary particle formation via the ozone-limonene reaction. Because people spend the majority of their time indoors, secondary particles formed in indoor environments may make a significant contribution to overall particle exposure. This study provides data for assessing the impact of outdoor ozone on indoor particles. This is important to determine the efficacy of the mass-based particulate matter standards in protecting public health because the indoor secondary particles can vary coincidently with the variations of outdoor fine particles in summer.

Top-Down Constraints on Air Quality Model Emissions of NH3, NOx, and SO2 using Surface, Aircraft, and Satellite Data

NASA Astrophysics Data System (ADS)

Alvarado, M. J.; Lonsdale, C. R.; Winijkul, E.; Brodowski, C. M.; Cady-Pereira, K.; Henze, D. K.; Capps, S.

2016-12-01

Accurate modeling of the formation of ozone (O3) and fine particulate matter (PM2.5) requires accurate estimates of the emissions of precursor species such as ammonia (NH3), nitrogen oxides (NOx = NO+NO2) and sulfur dioxide (SO2). Here we present an evaluation of the 2011 EPA National Emission Inventory for NH3, NOx, and SO2 using CMAQv5.0.2 and data from the 2013 NOAA Southeast Nexus (SENEX) field campaign. Model results are compared to surface and aircraft measurements during each campaign, as well as satellite NH3 observations from the NOAA Cross-track Infrared Sounder (CrIS) and satellite observations of NO2 and SO2 from the NASA Ozone Monitoring Instrument (OMI). We also present an evaluation of the California Air Resources Board (CARB) NH3 emissions for 2012 using CMAQ and the CrIS NH3 observations. We discuss the lessons learned in using CrIS NH3 observations in the southeast US, where CMAQ predicts most of the gas-phase NH3 is very close to the surface, and contrast this with the use of CrIS NH3 observations over California. We discuss the use of two methods - a mass balance approach and an approach using the CMAQ adjoint - to optimize these emissions and evaluate the improvement in model performance for gas-phase NH3, NOx, and SO2, as well as for the formation of O3 and PM2.5.

Simultaneous removal of 2,4,6-tribromophenol from water and bromate ion minimization by ozonation.

PubMed

Gounden, Asogan N; Singh, Sooboo; Jonnalagadda, Sreekantha B

2018-06-02

The study investigates the degradation of 2,4,6-tribromophenol (2,4,6-TBP) and the influence of solution pH, alkalinity, H 2 O 2 and O 3 dosage. Debromination efficiency of 2,4,6-TBP was the highest in basic water (pH = 10.61). The extent of TOC removal compared favourably with the amount of substrate converted, suggesting favourable mineralization of oxygenated by-products (OBPs). Ozonation in basic water favoured the formation of toxicBrO 3 - , while in acidic water (pH = 2.27) BrO 3 - yield was lowest. In acidic water the presence of CO 3 2- showed negligible effect on conversion, TOC and  BrO 3 - yield compared to ozonation alone. In basic water both 2,4,6-TBP conversion and TOC removal decreased with an increase in CO 3 2- , hence minimizing BrO 3 - formation. The O 3 /H 2 O 2 process showed an improvement in the debromination efficiency and TOC data revealed that total mineralization of OBP's was achieved. However, only 10% H 2 O 2 was able to effectively decrease BrO 3 - formation. Increasing the ozone concentration from 20 to 100 ppm enhanced the conversion of 2,4,6-TBP and TOC removal. At low ozone concentrations poor mineralization of OBP's occurred, while complete mineralization was achieved at higher ozone dose. The reaction pathways for ozone degradation of 2,4,6-TBP in acidic and basic waters is proposed. Copyright © 2018 Elsevier B.V. All rights reserved.

Use of North American and European air quality networks to evaluate global chemistry-climate modeling of surface ozone

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schnell, J. L.; Prather, M. J.; Josse, B.

Here we test the current generation of global chemistry–climate models in their ability to simulate observed, present-day surface ozone. Models are evaluated against hourly surface ozone from 4217 stations in North America and Europe that are averaged over 1° × 1° grid cells, allowing commensurate model–measurement comparison. Models are generally biased high during all hours of the day and in all regions. Most models simulate the shape of regional summertime diurnal and annual cycles well, correctly matching the timing of hourly (~ 15:00 local time (LT)) and monthly (mid-June) peak surface ozone abundance. The amplitude of these cycles is lessmore » successfully matched. The observed summertime diurnal range (~ 25 ppb) is underestimated in all regions by about 7 ppb, and the observed seasonal range (~ 21 ppb) is underestimated by about 5 ppb except in the most polluted regions, where it is overestimated by about 5 ppb. The models generally match the pattern of the observed summertime ozone enhancement, but they overestimate its magnitude in most regions. Most models capture the observed distribution of extreme episode sizes, correctly showing that about 80 % of individual extreme events occur in large-scale, multi-day episodes of more than 100 grid cells. The models also match the observed linear relationship between episode size and a measure of episode intensity, which shows increases in ozone abundance by up to 6 ppb for larger-sized episodes. Lastly, we conclude that the skill of the models evaluated here provides confidence in their projections of future surface ozone.« less

Use of North American and European air quality networks to evaluate global chemistry-climate modeling of surface ozone

DOE PAGES

Schnell, J. L.; Prather, M. J.; Josse, B.; ...

2015-09-25

Here we test the current generation of global chemistry–climate models in their ability to simulate observed, present-day surface ozone. Models are evaluated against hourly surface ozone from 4217 stations in North America and Europe that are averaged over 1° × 1° grid cells, allowing commensurate model–measurement comparison. Models are generally biased high during all hours of the day and in all regions. Most models simulate the shape of regional summertime diurnal and annual cycles well, correctly matching the timing of hourly (~ 15:00 local time (LT)) and monthly (mid-June) peak surface ozone abundance. The amplitude of these cycles is lessmore » successfully matched. The observed summertime diurnal range (~ 25 ppb) is underestimated in all regions by about 7 ppb, and the observed seasonal range (~ 21 ppb) is underestimated by about 5 ppb except in the most polluted regions, where it is overestimated by about 5 ppb. The models generally match the pattern of the observed summertime ozone enhancement, but they overestimate its magnitude in most regions. Most models capture the observed distribution of extreme episode sizes, correctly showing that about 80 % of individual extreme events occur in large-scale, multi-day episodes of more than 100 grid cells. The models also match the observed linear relationship between episode size and a measure of episode intensity, which shows increases in ozone abundance by up to 6 ppb for larger-sized episodes. Lastly, we conclude that the skill of the models evaluated here provides confidence in their projections of future surface ozone.« less

The QBO and interannual variation in total ozone

NASA Technical Reports Server (NTRS)

Lait, Leslie R.; Schoeberl, Mark R.; Newman, Paul A.; Stolarski, Richard S.

1988-01-01

Garcia and Soloman (1987) have noted that the October monthly mean minimum total ozone amounts south of 30 S were modulated by a quasibiennial oscillation (QBO) signal. The precise mechanism behind this effect, however, is unclear. Is the modulation brought about by the circulation-produced QBO signal in the ozone concentration itself, or does the temperature QBO modulate the formation of polar stratospheric clouds (PSCs), leading to changes in the chemically induced Antarctic spring ozone decline rate. Or is some other phenomenon involved. To investigate the means through which the QBO effect occurs, a series of correlation studies has been made between polar ozone and QBO signal in ozone and temperature.

Combination of UV absorbance and electron donating capacity to assess degradation of micropollutants and formation of bromate during ozonation of wastewater effluents.

PubMed

Chon, Kangmin; Salhi, Elisabeth; von Gunten, Urs

2015-09-15

In this study, the changes in UV absorbance at 254 nm (UVA254) and electron donating capacity (EDC) were investigated as surrogate indicators for assessing removal of micropollutants and bromate formation during ozonation of wastewater effluents. To measure the EDC, a novel method based on size exclusion chromatography followed by a post-column reaction was developed and calibrated against an existing electrochemical method. Low specific ozone doses led to a more efficient abatement of EDC than of UVA254. This was attributed to the abatement of phenolic moieties in the dissolved organic matter (DOM), which lose their EDC upon oxidation, but are partially transformed into quinones, which still absorb in the measured UV range. For higher specific ozone doses, the relative EDC abatement was lower than the relative UVA abatement, which can be explained by the oxidation of UV absorbing moieties (e.g. non-activated aromatic compounds), which contribute less to EDC. The abatement of the selected micropollutants (i.e., 17α-ethinylestradiol (EE2), carbamazepine (CBZ), atenolol (ATE), bezafibrate (BZF), ibuprofen (IBU), and p-chlorobenzoic acid (pCBA)) varied significantly depending on their reactivity with ozone in the examined specific ozone dose range of 0-1.45 mgO3/mgDOC. The decrease of EE2 and CBZ with high ozone reactivity was linearly proportional to the reduction of the relative residuals of UVA254 and EDC. The abatement of ATE, BZF, IBU, and pCBA with intermediate to low ozone reactivities was not significant in a first phase (UVA254/UVA254,0 = 1.00-0.70; EDC/EDC0 = 1.00-0.56) while their abatement was more efficient than the degradation of the relative residual UVA254 and much more noticeable than the degradation of the relative residual EDC in a second phase (UVA254/UVA254,0 = 0.70-0.25; EDC/EDC0 = 0.56-0.25) because the partially destroyed UV absorbing and electron donating DOM moieties become recalcitrant to ozone attack. Bromate formation was pronounced for specific ozone doses >0.25 mgO3/mgDOC. At these ozone doses, the residual DOM competes less with bromide for ozone as the electron-rich DOM moieties are almost completely degraded. Overall, these results imply that a combination of the relative residual UVA254 and EDC more truly reflects the intrinsic reactivity of DOM associated with the removal of micropollutants and bromate formation than the single use of the UV absorbance-based surrogate indicators. Copyright © 2015 Elsevier Ltd. All rights reserved.

Soybean Cultivar Variation in Response to Elevated Ozone Concentration

USDA-ARS?s Scientific Manuscript database

Crop losses to ozone damage are conservatively estimated to cost $1 to $3 billion in the U.S. These costs will rise as surface-level ozone increases over this century. A critical step in maximizing soybean yield in a future of rising tropospheric ozone is identifying variation in cultivar responses,...

Multi-Model Comparison of Lateral Boundary Contributions to Surface Ozone Over the United States

EPA Science Inventory

As the National Ambient Air Quality Standards (NAAQS) for ozone become more stringent, there has been growing attention on characterizing the contributions and the uncertainties in ozone from outside the US to the ozone concentrations within the US. The third phase of the Air Qua...

Impact of Enhanced Ozone Deposition and Halogen Chemistry on Tropospheric Ozone over the Northern Hemisphere.

PubMed

Sarwar, Golam; Gantt, Brett; Schwede, Donna; Foley, Kristen; Mathur, Rohit; Saiz-Lopez, Alfonso

2015-08-04

Fate of ozone in marine environments has been receiving increased attention due to the tightening of ambient air quality standards. The role of deposition and halogen chemistry is examined through incorporation of an enhanced ozone deposition algorithm and inclusion of halogen chemistry in a comprehensive atmospheric modeling system. The enhanced ozone deposition treatment accounts for the interaction of iodide in seawater with ozone and increases deposition velocities by 1 order of magnitude. Halogen chemistry includes detailed chemical reactions of organic and inorganic bromine and iodine species. Two different simulations are completed with the halogen chemistry: without and with photochemical reactions of higher iodine oxides. Enhanced deposition reduces mean summer-time surface ozone by ∼3% over marine regions in the Northern Hemisphere. Halogen chemistry without the photochemical reactions of higher iodine oxides reduces surface ozone by ∼15% whereas simulations with the photochemical reactions of higher iodine oxides indicate ozone reductions of ∼48%. The model without these processes overpredicts ozone compared to observations whereas the inclusion of these processes improves predictions. The inclusion of photochemical reactions for higher iodine oxides leads to ozone predictions that are lower than observations, underscoring the need for further refinement of the halogen emissions and chemistry scheme in the model.

Ozone Variability and Anomalies Observed During SENEX and SEAC4RS Campaigns in 2013

NASA Astrophysics Data System (ADS)

Kuang, Shi; Newchurch, Michael J.; Thompson, Anne M.; Stauffer, Ryan M.; Johnson, Bryan J.; Wang, Lihua

2017-10-01

Tropospheric ozone variability occurs because of multiple forcing factors including surface emission of ozone precursors, stratosphere-to-troposphere transport (STT), and meteorological conditions. Analyses of ozonesonde observations made in Huntsville, AL, during the peak ozone season (May to September) in 2013 indicate that ozone in the planetary boundary layer was significantly lower than the climatological average, especially in July and August when the Southeastern United States (SEUS) experienced unusually cool and wet weather. Because of a large influence of the lower stratosphere, however, upper tropospheric ozone was mostly higher than climatology, especially from May to July. Tropospheric ozone anomalies were strongly anticorrelated (or correlated) with water vapor (or temperature) anomalies with a correlation coefficient mostly about 0.6 throughout the entire troposphere. The regression slopes between ozone and temperature anomalies for surface up to midtroposphere are within 3.0-4.1 ppbv K-1. The occurrence rates of tropospheric ozone laminae due to STT are ≥50% in May and June and about 30% in July, August, and September suggesting that the stratospheric influence on free-tropospheric ozone could be significant during early summer. These STT laminae have a mean maximum ozone enhancement over the climatology of 52 ± 33% (35 ± 24 ppbv) with a mean minimum relative humidity of 2.3 ± 1.7%.

Sensitivity analysis of surface ozone to emission controls in Beijing and its neighboring area during the 2008 Olympic Games.

PubMed

Gao, Yi; Zhang, Meigen

2012-01-01

The regional air quality modeling system RAMS (regional atmospheric modeling system)-CMAQ (community multi-scale air quality modeling system) is applied to analyze temporal and spatial variations in surface ozone concentration over Beijing and its surrounding region from July to October 2008. Comparison of simulated and observed meteorological elements and concentration of nitrogen oxides (NOx) and ozone at one urban site and three rural sites during Olympic Games show that model can generally reproduce the main observed feature of wind, temperature and ozone, but NOx concentration is overestimated. Although ozone concentration decreased during Olympics, high ozone episodes occurred on 24 July and 24 August with concentration of 360 and 245 microg/m3 at Aoyuncun site, respectively. The analysis of sensitive test, with and without emission controls, shows that emission controls could reduce ozone concentration in the afternoon when ozone concentration was highest but increase it at night and in the morning. The evolution of the weather system during the ozone episodes (24 July and 24 August) indicates that hot and dry air and a stable weak pressure field intensified the production of ozone and allowed it to accumulate. Process analysis at the urban site and rural site shows that under favorable weather condition on 24 August, horizontal transport was the main contributor of the rural place and the pollution from the higher layer would be transported to the surface layer. On 24 July, as the wind velocity was smaller, the impact of transport on the rural place was not obvious.

Tropospheric Ozone Lidar Network (TOLNet) - Long-term Tropospheric Ozone and Aerosol Profiling for Satellite Continuity and Process Studies

NASA Astrophysics Data System (ADS)

Newchurch, M.; Al-Saadi, J. A.; Alvarez, R. J.; Burris, J.; Cantrell, W.; Chen, G.; De Young, R.; Hardesty, R.; Hoff, R. M.; Kaye, J. A.; kuang, S.; Langford, A. O.; LeBlanc, T.; McDermid, I. S.; McGee, T. J.; Pierce, R.; Senff, C. J.; Sullivan, J. T.; Szykman, J.; Tonnesen, G.; Wang, L.

2012-12-01

An interagency research initiative for ground-based ozone and aerosol lidar profiling recently funded by NASA has important applications to air-quality studies in addition to the goal of serving the GEO-CAPE and other air-quality missions. Ozone is a key trace-gas species, a greenhouse gas, and an important pollutant in the troposphere. High spatial and temporal variability of ozone affected by various physical and photochemical processes motivates the high spatio-temporal lidar profiling of tropospheric ozone for improving the simulation and forecasting capability of the photochemical/air-quality models, especially in the boundary layer where the resolution and precision of satellite retrievals are fundamentally limited. It is well known that there are large discrepancies between the surface and upper-air ozone due to titration, surface deposition, diurnal processes, free-tropospheric transport, and other processes. Near-ground ozone profiling has been technically challenging for lidars due to some engineering difficulties, such as near-range saturation, field-of-view overlap, and signal processing issues. This initiative provides an opportunity for us to solve those engineering issues and redesign the lidars aimed at long-term, routine ozone/aerosol observations from the near surface to the top of the troposphere at multiple stations (i.e., NASA/GSFC, NASA/LaRC, NASA/JPL, NOAA/ESRL, UAHuntsville) for addressing the needs of NASA, NOAA, EPA and State/local AQ agencies. We will present the details of the science investigations, current status of the instrumentation development, data access/protocol, and the future goals of this lidar network. Ozone lidar/RAQMS comparison of laminar structures.

Crystal-face-selective adsorption of Au nanoparticles onto polycrystalline diamond surfaces.

PubMed

Kondo, Takeshi; Aoshima, Shinsuke; Hirata, Kousuke; Honda, Kensuke; Einaga, Yasuaki; Fujishima, Akira; Kawai, Takeshi

2008-07-15

Crystal-face-selective adsorption of Au nanoparticles (AuNPs) was achieved on polycrystalline boron-doped diamond (BDD) surface via the self-assembly method combined with a UV/ozone treatment. To the best of our knowledge, this is the first report of crystal-face-selective adsorption on an inorganic solid surface. Hydrogen-plasma-treated BDD samples and those followed by UV/ozone treatment for 2 min or longer showed almost no adsorption of AuNP after immersion in the AuNP solution prepared by the citrate reduction method. However, the samples treated by UV/ozone for 10 s showed AuNP adsorption on their (111) facets selectively after the immersion. Moreover, the sample treated with UV/ozone for 40-60 s showed AuNP adsorption on the whole surface. These results indicate that the AuNP adsorption behavior can be controlled by UV/ozone treatment time. This phenomenon was highly reproducible and was applied to a two-step adsorption method, where AuNPs from different batches were adsorbed on the (111) and (100) surface in this order. Our findings may be of great value for the fabrication of advanced nanoparticle-based functional materials via bottom-up approaches with simple macroscale procedures.

Seasonal Changes in Tropospheric Ozone Concentrations over South Korea and Its Link to Ozone Precursors

NASA Astrophysics Data System (ADS)

Jung, H. C.; Moon, B. K.; Wie, J.

2017-12-01

Concentration of tropospheric ozone over South Korea has steadily been on the rise in the last decades, mainly due to rapid industrializing and urbanizing in the Eastern Asia. To identify the characteristics of tropospheric ozone in South Korea, we fitted a sine function to the surface ozone concentration data from 2005 to 2014. Based on fitted sine curves, we analyzed the shifts in the dates on which ozone concentration reached its peak in the calendar year. Ozone monitoring sites can be classified into type types: where the highest annual ozone concentration kept occurring sooner (Esites) and those that kept occurring later (Lsites). The seasonal analysis shows that the surface ozone had increased more rapidly in Esites than in Lsites in the past decade during springtime and vice-versa during summertime. We tried to find the reason for the different seasonal trends with the relationship between ozone and ozone precursors. As a result, it was found that the changes in the ground-level ozone concentration in the spring and summer times are considerably influenced by changes in nitrogen dioxide concentration, and this is closely linked to the destruction (production) process of ozone by nitrogen dioxide in spring (summer). The link between tropospheric ozone and nitrogen dioxide discussed in this study will have to be thoroughly examined through climate-chemistry modeling in the future. Acknowledgements This research was supported by the Korea Ministry of Environment (MOE) as "Climate Change Correspondence Program."

Ozone depletion - Ultraviolet radiation and phytoplankton biology in Antarctic waters

NASA Technical Reports Server (NTRS)

Smith, R. C.; Prezelin, B. B.; Baker, K. S.; Bidigare, R. R.; Boucher, N. P.; Coley, T.; Karentz, D.; Macintyre, S.; Matlick, H. A.; Menzies, D.

1992-01-01

The near-50-percent thinning of the stratospheric ozone layer over the Antarctic, with increased passage of mid-UV radiation to the surface of the Southern Ocean, has prompted concern over possible radiation damage to the near-surface phytoplankton communities that are the bases of Antarctic marine ecosystems. As the ozone layer thinned, a 6-week study of the marginal ice zone of the Bellingshousen Sea in the austral spring of 1990 noted sea-surface and depth-dependent ratios of mid-UV irradiance to total irradiance increased, and mid-UV inhibition of photosynthesis increased. A 6-12 percent reduction in primary production associated with ozone depletion was estimated to have occurred over the course of the present study.

Regional trend analysis of surface ozone observations from monitoring networks in eastern North America, Europe and East Asia

NASA Astrophysics Data System (ADS)

Chang, K. L.; Petropavlovskikh, I. V.; Cooper, O. R.; Schultz, M.; Wang, T.

2017-12-01

Surface ozone is a greenhouse gas and pollutant detrimental to human health and crop and ecosystem productivity. The Tropospheric Ozone Assessment Report (TOAR) is designed to provide the research community with an up-to-date observation-based overview of tropospheric ozone's global distribution and trends. The TOAR Surface Ozone Database contains ozone metrics at thousands of monitoring sites around the world, densely clustered across mid-latitude North America, western Europe and East Asia. Calculating regional ozone trends across these locations is challenging due to the uneven spacing of the monitoring sites across urban and rural areas. To meet this challenge we conducted a spatial and temporal trend analysis of several TOAR ozone metrics across these three regions for summertime (April-September) 2000-2014, using the generalized additive mixed model (GAMM). Our analysis indicates that East Asia has the greatest human and plant exposure to ozone pollution among investigating regions, with increasing ozone levels through 2014. The results also show that ozone mixing ratios continue to decline significantly over eastern North America and Europe, however, there is less evidence for decreases of daytime average ozone at urban sites. The present-day spatial coverage of ozone monitors in East Asia (South Korea and Japan) and eastern North America is adequate for estimating regional trends by simply taking the average of the individual trends at each site. However the European network is more sparsely populated across its northern and eastern regions and therefore a simple average of the individual trends at each site does not yield an accurate regional trend. This analysis demonstrates that the GAMM technique can be used to assess the regional representativeness of existing monitoring networks, indicating those networks for which a regional trend can be obtained by simply averaging the trends of all individual sites and those networks that require a more sophisticated statistical approach.

Rate and reaction probability of the surface reaction between ozone and dihydromyrcenol measured in a bench scale reactor and a room-sized chamber

NASA Astrophysics Data System (ADS)

Shu, Shi; Morrison, Glenn C.

2012-02-01

Low volatility terpenoids emitted from consumer products can react with ozone on surfaces and may significantly alter concentrations of ozone, terpenoids and reaction products in indoor air. We measured the reaction probability and a second-order surface-specific reaction rate for the ozonation of dihydromyrcenol, a representative indoor terpenoid, adsorbed onto polyvinylchloride (PVC), glass, and latex paint coated spheres. The reaction probability ranged from (0.06-8.97) × 10 -5 and was very sensitive to humidity, substrate and mass adsorbed. The average surface reaction probability is about 10 times greater than that for the gas-phase reaction. The second-order surface-specific rate coefficient ranged from (0.32-7.05) × 10 -15 cm 4 s -1 molecule -1and was much less sensitive to humidity, substrate, or mass adsorbed. We also measured the ozone deposition velocity due to adsorbed dihydromyrcenol on painted drywall in a room-sized chamber, Based on that, we calculated the rate coefficient ((0.42-1.6) × 10 -15 cm 4 molecule -1 s -1), which was consistent with that derived from bench-scale experiments for the latex paint under similar conditions. We predict that more than 95% of dihydromyrcenol oxidation takes place on indoor surfaces, rather than in building air.

A measurement/model comparison of ozone photochemical loss in the Antarctic ozone hole using Polar Ozone and Aerosol Measurement observations and the Match technique

NASA Astrophysics Data System (ADS)

Hoppel, Karl; Bevilacqua, Richard; Canty, Timothy; Salawitch, Ross; Santee, Michelle

2005-10-01

The Polar Ozone and Aerosol Measurement (POAM III) instrument has provided 6 years (1998 to present) of Antarctic ozone profile measurements, which detail the annual formation of the ozone hole. During the period of ozone hole formation the measurement latitude follows the edge of the polar night and presents a unique challenge for comparing with model simulations. The formation of the ozone hole has been simulated by using a photochemical box model with an ensemble of trajectories, and the results were sampled at the measurement latitude for comparison with the measured ozone. The agreement is generally good but very sensitive to the model dynamics and less sensitive to changes in the model chemistry. In order to better isolate the chemical ozone loss the Match technique was applied to 5 years of data to directly calculate ozone photochemical loss rates. The measured loss rates are specific to the high solar zenith angle conditions of the POAM-Match trajectories and are found to increase slowly from July to early August and then increase rapidly until mid-September. The Match results are sensitive to the choice of meteorological analysis used for the trajectory calculations. The ECMWF trajectories yield the smallest, and perhaps most accurate, peak loss rates that can be reproduced by a photochemical model using standard JPL 2002 kinetics, assuming reactive bromine (BrOx) of 14 pptv based solely on contributions from CH3Br and halons, and without requiring ClOx to exceed the upper limit for available inorganic chlorine of 3.7 ppbv. Larger Match ozone loss rates are found for the late August and early September period if trajectories based on UKMO and NCEP analyses are employed. Such loss rates require higher values for ClO and/or BrO than can be simulated using JPL 2002 chemical kinetics and complete activation of chlorine. In these cases, the agreement between modeled and measured loss rates is significantly improved if the model employs larger ClOOCl cross sections (e.g., Burkholder et al., 1990) and BrOx of 24 ppt which reflects significant contributions from very short-lived bromocarbons to the inorganic bromine budget.

Sensitivity of U.S. surface ozone to future emissions and climate changes

NASA Astrophysics Data System (ADS)

Tao, Zhining; Williams, Allen; Huang, Ho-Chun; Caughey, Michael; Liang, Xin-Zhong

2007-04-01

The relative contributions of projected future emissions and climate changes to U.S. surface ozone concentrations are investigated focusing on California, the Midwest, the Northeast, and Texas. By 2050 regional average ozone concentrations increase by 2-15% under the IPCC SRES A1Fi (``dirty'') scenario, and decrease by 4-12% under the B1 (relatively ``clean'') scenario. However, the magnitudes of ozone changes differ significantly between major metropolitan and rural areas. These ozone changes are dominated by the emissions changes in 61% area of the contiguous U.S. under the B1 scenario, but are largely determined by the projected climate changes in 46% area under the A1Fi scenario. In the ozone responses to climate changes, the biogenic emissions changes contribute strongly over the Northeast, moderately in the Midwest, and negligibly in other regions.

Role of carbonyls and aromatics in the formation of tropospheric ozone in Rio de Janeiro, Brazil.

PubMed

da Silva, Débora Bonfim Neves; Martins, Eduardo Monteiro; Corrêa, Sergio Machado

2016-05-01

The ozone in Rio de Janeiro has been in violation of national air quality standards. Among all of the monitoring stations, the Bangu neighbourhood has the most violations of the national standard of 160 μg m(-3) for the years 2012 and 2013. This study evaluated the reactivity of the carbonyls and aromatics in the tropospheric ozone formation processes. The samples were collected between July and October of 2013. Carbonyls were sampled using SiO2 cartridges coated with C18 and impregnated with 2,4-dinitrophenylhydrazine and were analysed by HPLC. Activated carbon cartridges and GC/MS were used to measure the concentration of monoaromatic hydrocarbons. An air quality monitoring station provided the concentrations of the criteria pollutants and the meteorological parameters. Cluster analysis and a Pearson correlation matrix were used to determine the formation of groups and the correlation of the variables. The evaluation of the volatile organic compounds (VOC) reaction with OH radicals and the MIR scale was used to extrapolate the reactivity of VOCs to the ozone formation. The average concentrations obtained were 19.7 and 51.9 μg m(-3) for formaldehyde and acetaldehyde, respectively. The mean concentrations obtained for aromatics were 1.5, 6.7, 1.5, 2.6 and 1.6 μg m(-3) for benzene, toluene, ethyl benzene, m+p-xylene and o-xylene, respectively. The cluster analysis indicated the presence of three similar groups, with one formed by gaseous criteria pollutants, another formed by the meteorological parameters, ozone and fine particles, and the last group formed by the aromatics. For the two reactivity scales evaluated, acetaldehyde and toluene were the main ozone precursors.

Effects of storage in ozonised slurry ice on the sensory and microbial quality of sardine (Sardina pilchardus).

PubMed

Campos, Carmen A; Rodríguez, Oscar; Losada, Vanesa; Aubourg, Santiago P; Barros-Velázquez, Jorge

2005-08-25

The use of slurry ice, both alone and in combination with ozone, as compared with traditional flake ice was investigated as a new refrigeration system for the storage of sardine (Sardina pilchardus). Microbiological, chemical and sensory analyses were carried out throughout a storage period of 22 days. According to sensory analyses, sardine specimens stored in ozonised slurry ice had a shelf life of 19 days, while counterpart batches stored in slurry ice or flake ice had shelf lives of 15 and 8 days, respectively. Storage in ozonised slurry ice led to significantly lower counts of aerobic mesophiles, psychrotrophic bacteria, anaerobes, coliforms, and both lipolytic and proteolytic microorganisms in sardine muscle, and of surface counts of mesophiles and psychrotrophic bacteria in sardine skin as compared with the slurry ice and the flake ice batches. In all cases, the slurry ice batch also exhibited significantly lower microbial counts, both in muscle and skin, than the flake ice batch. Chemical parameters revealed that the use of slurry ice slowed down the formation of TVB-N and TMA-N to a significant extent in comparison with storage in flake ice. A combination of slurry ice with ozone also allowed a better control of pH and TMA-N formation as compared with slurry ice alone. This work demonstrates that the combined use of slurry ice and ozone for the storage of sardine can be recommended to improve the quality and extend the shelf life of this fish species.

VOCs emission characteristics and priority control analysis based on VOCs emission inventories and ozone formation potentials in Zhoushan

NASA Astrophysics Data System (ADS)

Wang, Qiaoli; Li, Sujing; Dong, Minli; Li, Wei; Gao, Xiang; Ye, Rongmin; Zhang, Dongxiao

2018-06-01

Zhoushan is an island city with booming tourism and service industry, but also has many developed VOCs and/or NOX emission industries. It is necessary to carry out regional VOCs and O3 pollution control in Zhoushan as the only new area owns the provincial economic and social administration rights. Anthropogenic VOCs emission inventories were built based on emission factor method and main emission sources were identified according to the emission inventories. Then, localized VOCs source profiles were built based on in-site sampling and referring to other studies. Furthermore, ozone formation potentials (OFPs) profiles were built through VOCs source profiles and maximum incremental reactivity (MIR) theory. At last, the priority control analysis results showed that industrial processes, especially surface coating, are the key of VOCs and O3 control. Alkanes were the most emitted group, accounting for 58.67%, while aromatics contributed the most to ozone production accounting for 69.97% in total OFPs. n-butane, m/p-xylene, i-pentane, n-decane, toluene, propane, n-undecane, o-xylene, methyl cyclohexane and ethyl benzene were the top 10 VOC species that should be preferentially controlled for VOCs emission control. However, m/p-xylene, o-xylene, ethylene, n-butane, toluene, propene, 1,2,4-trimethyl benzene, 1,3,5-trimethyl benzene, ethyl benzene and 1,2,3-trimethyl benzene were the top 10 VOC species that required preferential control for O3 pollution control.

Novel test procedure to evaluate the treatability of wastewater with ozone.

PubMed

Schindler Wildhaber, Yael; Mestankova, Hana; Schärer, Michael; Schirmer, Kristin; Salhi, Elisabeth; von Gunten, Urs

2015-05-15

Organic micropollutants such as pharmaceuticals, estrogens or pesticides enter the environment continuously through the effluent of municipal wastewater treatment plants (WWTPs). Enhanced treatment of wastewater (WW) by ozone (O3) is probably one of the simplest measures for abatement of organic micropollutants to avoid their discharge to the aquatic environment. During ozonation most organic micropollutants present in treated WW are oxidized either by a direct reaction with O3 or by secondarily formed hydroxyl radicals (OH). However, undesired oxidation by-products from the oxidative transformation of matrix components can also be formed. A modular laboratory decision tool based on the findings of previous investigations is presented to test the feasibility of ozonation as an option to upgrade specific WWTPs. These modules consist of investigations to assess (i) the matrix effects on ozone stability, (ii) the efficiency of micropollutant removal, (iii) the oxidation by-product formation, as well as (iv) bioassays to measure specific and unspecific toxicity of the treated WWs. Matrix effects on ozone stability (quantified as O3 and OH exposures) can give first indications on the suitability of an ozonation step. Ozonation of WWs yielding O3 and OH exposures and micropollutant abatement similar to reference values evoked a significant improvement of the water quality as indicated by a broad range of bioassays. Irregular behavior of the ozonation points towards unknown compounds, possibly leading to the formation of undesired degradation products. It has been observed that in such WWs ozonation partly enhanced toxicity. In summary, the presented tiered laboratory test procedure represents a relatively cheap and straight-forward methodology to evaluate the feasibility of ozonation to upgrade specific WWTPs for micropollutant removal based on chemical and biological measurements. Copyright © 2015 Elsevier Ltd. All rights reserved.

Levofloxacin oxidation by ozone and hydroxyl radicals: kinetic study, transformation products and toxicity.

PubMed

Hamdi El Najjar, Nasma; Touffet, Arnaud; Deborde, Marie; Journel, Romain; Leitner, Nathalie Karpel Vel

2013-10-01

This work was carried out to investigate the fate of the antibiotic levofloxacin upon oxidation with ozone and hydroxyl radicals. A kinetic study was conducted at 20 °C for each oxidant. Ozonation experiments were performed using a competitive kinetic method with carbamazepin as competitor. Significant levofloxacin removal was observed during ozonation and a rate constant value of 6.0×10(4) M(-1) s(-1) was obtained at pH 7.2. An H2O2/UV system was used for the formation of hydroxyl radicals HO. The rate constant of HO was determined in the presence of a high H2O2 concentration. The kinetic expressions yielded a [Formula: see text] value of 4.5×10(9) M(-1) s(-1) at pH 6.0 and 5.2×10(9) M(-1) s(-1) at pH 7.2. These results were used to develop a model to predict the efficacy of the ozonation process and pharmaceutical removal was estimated under different ozonation conditions (i.e. oxidant concentrations and contact times). The results showed that levofloxacin was completely degraded by molecular ozone during ozonation of water and that hydroxyl radicals had no effect in real waters conditions. Moreover, LC/MS/MS and toxicity assays using Lumistox test were performed to identify ozonation transformation products. Under these conditions, four transformation products were observed and their chemical structures were proposed. The results showed an increase in toxicity during ozonation, even after degradation of all of the observed transformation products. The formation of other transformation products not identified under our experimental conditions could be responsible for the observed toxicity. These products might be ozone-resistant and more toxic to Vibrio fisheri than levofloxacin. Copyright © 2013 Elsevier Ltd. All rights reserved.

The effects of welding parameters on ultra-violet light emissions, ozone and CrVI formation in MIG welding.

PubMed

Dennis, J H; Mortazavi, S B; French, M J; Hewitt, P J; Redding, C R

1997-01-01

This paper describes the relationships between ultra-violet emission, ozone generation and CrVI production in MIG welding which were measured as a function of shield gas flow rate, welding voltage, electrode stick-out and shield gas composition using an automatic welding rig that permitted MIG welding under reproducible conditions. The experimental results are interpreted in terms of the physico-chemical processes occurring in the micro- and macro-environments of the arc as part of research into process modification to reduce occupational exposure to ozone and CrVI production rates in MIG welding. We believe the techniques described here, and in particular the use of what we have termed u.v.-ozone measurements, will prove useful in further study of ozone generation and CrVI formation and may be applied in the investigation of engineering control of occupational exposure in MIG and other welding process such as Manual Metal Arc (MMA) and Tungsten Inert Gas (TIG).

78 FR 29032 - Approval and Promulgation of Implementation Plans Tennessee: Revisions to Volatile Organic...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-05-17

... tropospheric ozone formation. The compounds were added by EPA through a rulemaking action which provided for... consistent with federal law. Tropospheric ozone, commonly known as smog, occurs when VOC and nitrogen oxide (NO X ) react in the atmosphere. Because of the harmful health effects of ozone, EPA limits the amount...

Synoptic meteorological conditions associated with high spring and summer ozone levels at a rural site in the Eastern Mediterranean

NASA Astrophysics Data System (ADS)

Kalabokas, Pavlos; Repapis, Christos; Mihalopoulos, Nikos; Zerefos, Christos

2017-04-01

For the identification of the nature of spring and summertime ozone episodes, rural ozone measurements from the Eastern Mediterranean station of Finokalia-Crete, Greece during the first 4-year period of its record (1998-2001) have been analyzed with emphasis on periods of high ozone concentrations, according to the daily variation of the afternoon (12:00 - 18:00) ozone values. For the 7% highest spring and summertime ozone episodes composite NOAA/ESRL reanalysis maps of various meteorological parameters and/or their anomalies (geopotential height, specific humidity, vertical wind velocity omega, vector wind speed and temperature) have been examined together with their corresponding HYSPLIT back trajectories. This work is a continuation of a previous first approach regarding summer highest and lowest surface ozone episodes in Finokalia and other Central and Eastern Mediterranean stations (Kalabokas et al., 2008), which is now extended to more meteorological parameters and higher pressure levels. The results show that the examined synoptic meteorological condition during springtime ozone episodes over the Eastern Mediterranean station of Finokalia are quite similar with those conditions during high ozone springtime episodes observed at rural stations over the Western Mediterranean (Kalabokas et al., 2016). On the other hand the summer time synoptic conditions corresponding to highest surface ozone episodes at Finokalia are comparable with the conditions encountered during highest ozone episodes in the lower troposphere following analysis of MOZAIC vertical profiles over the Aegean Sea and the Eastern Mediterranean (Kalabokas et al., 2015 and references therein). During the highest ozone episodes, for both examined seasons, the transport of tropospheric ozone-rich air masses through atmospheric subsidence influences significantly the boundary layer and surface ozone concentrations. In particular, the geographic areas with observed tropospheric subsidence seem to be the transition regions between high and low pressure synoptic meteorological systems. References Kalabokas, P. D., Mihalopoulos, N., Ellul, R., Kleanthous, S., and Repapis, C. C., 2008. An investigation of the meteorological and photochemical factors influencing the background rural and marine surface ozone levels in the Central and Eastern Mediterranean, Atmos. Environ., 42, 7894-7906. Kalabokas P. D., Thouret V., Cammas J.-P., Volz-Τhomas A., Boulanger D., Repapis C.C., 2015. The geographical distribution of meteorological parameters associated with high and low summer ozone levels in the lower troposphere and the boundary layer over the eastern Mediterranean (Cairo case), Tellus B, 67, 27853, http://dx.doi.org/10.3402/tellusb.v67.27853. Kalabokas P., J. Hjorth, G. Foret, G. Dufour, M. Eremenko, G. Siour, J. Cuesta, M. Beekmann, 2016. An investigation on the origin of regional spring time ozone episodes in the Western Mediterranean and Central Europe. Atmos. Chem. Phys. Discuss., doi:10.5194/acp-2016-615.

Modeling the uncertainty of several VOC and its impact on simulated VOC and ozone in Houston, Texas

NASA Astrophysics Data System (ADS)

Pan, Shuai; Choi, Yunsoo; Roy, Anirban; Li, Xiangshang; Jeon, Wonbae; Souri, Amir Hossein

2015-11-01

A WRF-SMOKE-CMAQ modeling system was used to study Volatile Organic Compound (VOC) emissions and their impact on surface VOC and ozone concentrations in southeast Texas during September 2013. The model was evaluated against the ground-level Automated Gas Chromatograph (Auto-GC) measurement data from the Texas Commission on Environmental Quality (TCEQ). The comparisons indicated that the model over-predicted benzene, ethylene, toluene and xylene, while under-predicting isoprene and ethane. The mean biases between simulated and observed values of each VOC species showed clear daytime, nighttime, weekday and weekend variations. Adjusting the VOC emissions using simulated/observed ratios improved model performance of each VOC species, especially mitigating the mean bias substantially. Simulated monthly mean ozone showed a minor change: a 0.4 ppb or 1.2% increase; while a change of more than 5 ppb was seen in hourly ozone data on high ozone days, this change moved model predictions closer to observations. The CMAQ model run with the adjusted emissions better reproduced the variability in the National Aeronautics and Space Administration (NASA)'s Ozone Monitoring Instrument (OMI) formaldehyde (HCHO) columns. The adjusted model scenario also slightly better reproduced the aircraft HCHO concentrations from NASA's DISCOVER-AQ campaign conducted during the simulation episode period; Correlation, Mean Bias and RMSE improved from 0.34, 1.38 ppb and 2.15 ppb to 0.38, 1.33 ppb and 2.08 ppb respectively. A process analysis conducted for both industrial/urban and rural areas suggested that chemistry was the main process contributing to ozone production in both areas, while the impact of chemistry was smaller in rural areas than in industrial and urban areas. For both areas, the positive chemistry contribution increased in the sensitivity simulation largely due to the increase in emissions. Nudging VOC emissions to match the observed concentrations shifted the ozone hotspots outside the industrial/urban region and enhanced the peaked ozone in the outflow region with consistent southerly/southeasterly winds during the afternoon time (1-5 pm). This study helps in the understanding of these processes which are critical to constrain high peak ozone values in the outflow regions. The results indicate that formation of ozone in the outflow could complicate attainment status in neighboring counties.

Air quality during the 2008 Beijing Olympics: secondary pollutants and regional impact

NASA Astrophysics Data System (ADS)

Wang, T.; Nie, W.; Gao, J.; Xue, L. K.; Gao, X. M.; Wang, X. F.; Qiu, J.; Poon, C. N.; Meinardi, S.; Blake, D.; Ding, A. J.; Chai, F. H.; Zhang, Q. Z.; Wang, W. X.

2010-05-01

This paper presents the first results of the atmospheric measurements of trace gases and aerosols at three surface sites in and around Beijing before and during the 2008 Olympics. We focus on secondary pollutants including ozone, fine sulfate and nitrate, and the contribution of regional sources in summer 2008. The results reveal different responses of secondary pollutants to the control measures from primary pollutants. Ambient concentrations of vehicle-related nitrogen oxides (NOx) and volatile organic compounds (VOCs) at an urban site dropped by 25% and 20-45% in the first two weeks after full control was put in place, but the levels of ozone, sulfate and nitrate in PM2.5 increased by 16%, 64%, 37%, respectively, compared to the period prior to the full control; wind data and back trajectories indicated the contribution of regional pollution from the North China Plain. Air quality (for both primary and secondary pollutants) improved significantly during the Games, which were also associated with the changes in weather conditions (prolonged rainfall, decreased temperature, and more frequent air masses from clean regions). A comparison of the ozone data at three sites on eight ozone-pollution days, when the air masses were from the southeast-south-southwest sector, showed that regional pollution sources contributed 34%-88% to the peak ozone concentrations in urban Beijing. Ozone production efficiencies at two sites were low (~3 ppbv/ppbv), indicating that ozone formation was being controlled by VOCs. Compared with data collected in 2005 at a downwind site, the concentrations of ozone, sulfur dioxide (SO2), total sulfur (SO2+PM2.5 sulfate), carbon monoxide (CO), reactive aromatics (toluene and xylenes) sharply decreased (by 8-64%) in 2008, but no significant changes were observed for the concentrations of PM2.5, fine sulfate, total odd reactive nitrogen (NOy), and longer lived alkanes and benzene. We suggest that these results indicate the success of the government's efforts in reducing emissions of SO2, CO, and VOCs in Beijing. However, further control of regional emissions is needed for significant reductions of ozone and fine particulate pollution in Beijing.

Lightning NOx and Impacts on Air Quality

NASA Technical Reports Server (NTRS)

Murray, Lee T.

2016-01-01

Lightning generates relatively large but uncertain quantities of nitrogen oxides, critical precursors for ozone and hydroxyl radical (OH), the primary tropospheric oxidants. Lightning nitrogen oxide strongly influences background ozone and OH due to high ozone production efficiencies in the free troposphere, effecting small but non-negligible contributions to surface pollutant concentrations. Lightning globally contributes 3-4 ppbv of simulated annual-mean policy-relevant background (PRB) surface ozone, comprised of local, regional, and hemispheric components, and up to 18 ppbv during individual events. Feedbacks via methane may counter some of these effects on decadal time scales. Lightning contributes approximately 1 percent to annual-mean surface particulate matter, as a direct precursor and by promoting faster oxidation of other precursors. Lightning also ignites wildfires and contributes to nitrogen deposition. Urban pollution influences lightning itself, with implications for regional lightning-nitrogen oxide production and feedbacks on downwind surface pollution. How lightning emissions will change in a warming world remains uncertain.

Ozone maxima over Southern Africa: A mid-latitude link

NASA Technical Reports Server (NTRS)

Barsby, Jane; Diab, Roseanne D.

1994-01-01

The relationship between patterns of total ozone and day-to-day weather was explored over South Africa for the period 1987 to 1988. Generally, there was a fairly poor relationship (variance less than 20 percent) between total ozone and the heights of the 100, 300 and 500 hPa geopotential heights at 5 South African stations. However, over a shorter period, October to December 1988, fluctuations in the height of the 300 hPa surface accounted for 53 percent of the variance in total ozone at Cape Town. High ozone amounts are associated with the lowering of the 300 hPa surface in the presence of an upper-air trough. The role of the mid-latitude westerly waves in this respect is discussed.

New Insights in Tropospheric Ozone and its Variability

NASA Technical Reports Server (NTRS)

Oman, Luke D.; Douglass, Anne R.; Ziemke, Jerry R.; Rodriquez, Jose M.

2011-01-01

We have produced time-slice simulations using the Goddard Earth Observing System Version 5 (GEOS-5) coupled to a comprehensive stratospheric and tropospheric chemical mechanism. These simulations are forced with observed sea surface temperatures over the past 25 years and use constant specified surface emissions, thereby providing a measure of the dynamically controlled ozone response. We examine the model performance in simulating tropospheric ozone and its variability. Here we show targeted comparisons results from our simulations with a multi-decadal tropical tropospheric column ozone dataset obtained from satellite observations of total column ozone. We use SHADOZ ozonesondes to gain insight into the observed vertical response and compare with the simulated vertical structure. This work includes but is not limited to ENSO related variability.

Sensitivity analysis of ozone formation and transport for a central California air pollution episode.

PubMed

Jin, Ling; Tonse, Shaheen; Cohan, Daniel S; Mao, Xiaoling; Harley, Robert A; Brown, Nancy J

2008-05-15

We developed a first- and second-order sensitivity analysis approach with the decoupled direct method to examine spatial and temporal variations of ozone-limiting reagents and the importance of local vs upwind emission sources in the San Joaquin Valley of central California for a 5 day ozone episode (Jul 29th to Aug 3rd, 2000). Despite considerable spatial variations, nitrogen oxides (NO(x)) emission reductions are overall more effective than volatile organic compound (VOC) control for attaining the 8 h ozone standard in this region for this episode, in contrast to the VOC control that works better for attaining the prior 1 h ozone standard. Interbasin source contributions of NO(x) emissions are limited to the northern part of the SJV, while anthropogenic VOC (AVOC) emissions, especially those emitted at night, influence ozone formation in the SJV further downwind. Among model input parameters studied here, uncertainties in emissions of NO(x) and AVOC, and the rate coefficient of the OH + NO2 termination reaction, have the greatest effect on first-order ozone responses to changes in NO(x) emissions. Uncertainties in biogenic VOC emissions only have a modest effect because they are generally not collocated with anthropogenic sources in this region.

Removal of sulfa drugs by sewage treatment in aqueous solution systems: activated carbon treatment and ozone oxidation.

PubMed

Ogata, Fumihiko; Tominaga, Hisato; Kangawa, Moe; Inoue, Kenji; Kawasaki, Naohito

2012-01-01

This study investigates the activated carbon (AC) treatment and ozone oxidation of the sulfa drugs--sulfamethoxazole (SMX), sulfamonomethoxine (SMM), sulfadimidine (SDD), and sulfadimethoxine (SDM)--in aqueous solution systems. Three AC samples were prepared from Shirasagi (AC1 and AC2) and coal (AC3), and the surface functional groups, solution pH, specific surface areas, pore volumes, and morphologies of the three samples were evaluated. The specific surface areas were in the following order: AC1 (1391 m²/g) > AC2 (1053 m²/g) > AC3 (807 m²/g). The pore volume and mean pore diameter of AC3 were greater than those of AC1 and AC2. The concentration of sulfa drugs adsorbed onto the AC samples reached equilibrium within 150 h. Experimental data of the adsorption rate were fitted to a pseudo-second-order model. The amount of sulfa drugs adsorbed onto the AC samples was in the order of SDM < SMM < SDD < SMX; the mechanism of adsorption of the sulfa drugs onto the AC samples depended on the hydrophobicity of the AC surface. The adsorption isotherm data were fitted to Freundlich and Langmuir models. Ozone was generated from oxygen gas using an A-27 ozone generator, and the complete degradation of the sulfa drugs by ozone treatment at 60 mL/min was achieved within 50 min. Ozone treatment caused the structure of the sulfa drugs to decompose via ozone oxidation.

Comparison of Wintertime Ozone Production Associated With Oil and Gas Extraction Activity in Wyoming and Utah

NASA Astrophysics Data System (ADS)

Oltmans, S. J.; Schnell, R. C.; Mefford, T. K.; Neely, R. R., III

2012-12-01

The wintertime cold, reduced sunlight conditions of the mid-latitudes of continental interior locations are normally not considered to be conducive to significant ozone production. Recent observations have shattered this expectation with hourly ozone mixing ratios regularly exceeding 100 ppb measured in January, February and March in the states of Wyoming and Utah in the United States. Maximum daily eight hour average ozone mixing ratios have exceeded 100 ppb, far exceeding the U.S. threshold of 75 ppb. Conditions under which this dramatic ozone production takes place include a mix of high levels of ozone precursors (NOx and VOCs), a very stable and shallow boundary layer, snow cover providing enhanced UV radiation, and air confining terrain features. The high levels of precursors have been tied to oil and gas extraction activities in the affected regions. Under the requisite meteorological conditions where high pressure, low winds, and snow-covered ground are present extremely stable and shallow (~50-200 m) boundary layers persist. The highly reflective snow cover provides enhanced photolysis rates that in February can exceed those in June. For several winters in Utah and Wyoming with large ozone enhancements, the time series of various meteorological (wind, temperature, solar radiation, snow cover) and chemical parameters (ozone and NOx) show a somewhat different progression of high ozone events between the two locations. In the Unitah Basin of Utah high ozone formation conditions are more persistent throughout the winter than in the Pinedale Anticline region of Wyoming. This is likely a function of the differing topography of the two areas. However, for individual events the two sites show a similar progression of rapid ozone formation each day. Sites in both Utah and Wyoming just outside the oil and gas extraction activity areas show little or no enhanced ozone. Winters without the requisite meteorological conditions also do not experience high ozone events.

Radiative effects due to North American anthropogenic and lightning emissions: Global and regional modeling

NASA Astrophysics Data System (ADS)

Martini, Matus Novak

We analyze the contribution of North American (NA) lightning and anthropogenic emissions to summertime ozone concentrations, radiative forcing, and exports from North America using the global University of Maryland chemistry transport model (UMD-CTM) and the regional scale Weather Research and Forecasting model with chemistry (WRF-Chem). Lightning NO contributes by 15--20 ppbv to upper tropospheric ozone concentrations over the United States with the effects of NA lightning on ozone seen as far east as North Africa and Europe. Using the UMD-CTM, we compare changes in surface and column ozone amounts due to the NOx State Implementation Plan (SIP) Call with the natural variability in ozone due to changes in meteorology and lightning. Comparing early summer 2004 with 2002, surface ozone decreased by up to 5 ppbv due to the NO x SIP Call while changes in meteorology and lightning resulted in a 0.3--1.4 ppbv increase in surface ozone. Ozone column variability was driven primarily by changes in lightning NO emissions, especially over the North Atlantic. As part of our WRF-Chem analysis, we modify the radiation schemes to use model-calculated ozone (interactive ozone) instead of climatological ozone profiles and conduct multiple 4-day simulations of July 2007. We found that interactive ozone increased the outgoing longwave radiation (OLR) by 3 W m-2 decreasing the bias with respect to remotely sensed OLR. The improvement is due to a high bias in the climatological ozone profiles. The interactive ozone had a small impact on mean upper troposphere temperature (-0.15°C). The UMD-CTM simulations indicate that NA anthropogenic emissions are responsible for more ozone export but less ozone radiative forcing than lightning NO emissions. Over the North Atlantic, NA anthropogenic emissions contributed 0.15--0.30 W m-2 to the net downward radiative flux at the tropopause while NA lightning contributed 0.30--0.50 W m-2. The ozone export from anthropogenic emissions was almost twice as large as that from lightning emissions. The WRF-Chem simulations show that the export of reactive nitrogen was 23%--28% of the boundary layer emissions and 26%--38% of the total emissions including lightning NO.

The Impact of TexAQS 2000 on Air Quality Planning in Houston

NASA Astrophysics Data System (ADS)

Thomas, J. W.; Price, J. H.

2002-12-01

Before the Texas 2000 Air Quality Study (TexAQS 2000) the State used the Urban Airshed Model to model nine different episodes in Houston with very poor results: only one episode met EPA model performance criteria. Questions existed regarding emissions uncertainties, meteorological modeling, and model chemistry. NOAA, DOE, and SOS led more than 35 organizations and 250 investigators who participated in TexAQS 2000. Major findings from TexAQS 2000 are: 1. There are two types of meteorological patterns that lead to ozone episodes in the Houston area: (i) stagnation associated with the sea breeze flow reversal causes a pool of industrial emissions and ozone to accumulate, then to move across the city as the wind flow picks up and (ii) plumes of ozone form when relatively persistent winds carry the emissions away from the city and industrial areas. 2. The chemistry that produces high ozone concentrations and rapid rises in ozone in the Houston area has been explained: multiple investigators in TexAQS 2000 have documented more rapid and more efficient formation of ozone in the plume from the Houston industrial area than any of them has observed in any previous field study. Houston's exceptionally rapid ozone formation arises from large amounts of anthropogenic VOCs in the atmosphere, often from the same plants that provide sufficient NOx. 3. This rapid and efficient ozone formation results most often from the presence of a specific subclass of hydrocarbons called light olefins, primarily ethylene and propylene. 4. Sometimes it is other specific hydrocarbons that cause the rapid formation of high concentrations of ozone, and sometimes it is just the total mass of a lot of relatively unreactive hydrocarbons. 5. The current emissions inventory for ethylene and propylene, as well as other VOCs, underestimates their routine emissions by a factor of roughly five to ten or perhaps even more. 6. It is not clear whether the emissions causing Houston's rapid ozone formation are the results of upsets or of routine operations or both. Each of the research groups in TexAQS 2000 has found that the data are consistent with routine emissions; however, their analyses do not exclude the possibility of multiple releases per day that would not be readily distinguishable from continuous emissions. 7. Further analysis of the data collected in 2000 and 2001 will be necessary to refine the estimates of the discrepancy between reported and actual VOC emissions and assign top-down VOC emissions inventory corrections for the current round of regulatory modeling. 8. Additional work will need to continue for the next few years with the cooperation of industry to develop an adequate bottom-up emissions inventory for VOCs. 9. The opportunity to compare regulatory modeling results to state-of-the-science aircraft measurements is a major advance in determining whether photochemical models are getting the right answers for the right reasons. Doing so is critical to development of effective and cost-effective control strategies. Without TexAQS 2000 and subsequent findings, the one-hour ozone control strategies for Houston would not address the problem correctly. What's next? The challenges of the impending 8-hour ozone standard will demand even more precision in our technical work to develop efficient and cost-effective strategies to demonstrate attainment. There is a proposal to conduct another major field study in 2005 to build on our current understanding of the science for ozone, fine particulate matter, and regional haze in Texas.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Meadows, J.; Smith, R.C.

Uric acid effectively reduced hemolysis and methemoglobin formation in bovine and swine erythrocytes bubbled with ozone in vitro. In bovine erythrocytes, formation of thiobarbituric acid-reactive material was inhibited by uric acid, but there was little immediate protection for the swine cells. Antioxidant protection was due to preferential degradation of the uric acid by ozone. These results provide evidence to support the hypothesis that in plasma, uric acid can provide antioxidant protection for erythrocytes.

Impact of Stratospheric Ozone Zonal Asymmetries on the Tropospheric Circulation

NASA Technical Reports Server (NTRS)

Tweedy, Olga; Waugh, Darryn; Li, Feng; Oman, Luke

2015-01-01

The depletion and recovery of Antarctic ozone plays a major role in changes of Southern Hemisphere (SH) tropospheric climate. Recent studies indicate that the lack of polar ozone asymmetries in chemistry climate models (CCM) leads to a weaker and warmer Antarctic vortex, and smaller trends in the tropospheric mid-latitude jet and the surface pressure. However, the tropospheric response to ozone asymmetries is not well understood. In this study we report on a series of integrations of the Goddard Earth Observing System Chemistry Climate Model (GEOS CCM) to further examine the effect of zonal asymmetries on the state of the stratosphere and troposphere. Integrations with the full, interactive stratospheric chemistry are compared against identical simulations using the same CCM except that (1) the monthly mean zonal mean stratospheric ozone from first simulation is prescribed and (2) ozone is relaxed to the monthly mean zonal mean ozone on a three day time scale. To analyze the tropospheric response to ozone asymmetries, we examine trends and quantify the differences in temperatures, zonal wind and surface pressure among the integrations.

TOLNet ozone lidar intercomparison during the discover-aq and frappé campaigns

NASA Astrophysics Data System (ADS)

Newchurch, Michael J.; Alvarez, Raul J.; Berkoff, Timothy A.; Carrion, William; DeYoung, Russell J.; Ganoe, Rene; Gronoff, Guillaume; Kirgis, Guillaume; Kuang, Shi; Langford, Andy O.; Leblanc, Thierry; McGee, Thomas J.; Pliutau, Denis; Senff, Christoph; Sullivan, John T.; Sumnicht, Grant; Twigg, Laurence W.; Wang, Lihua

2018-04-01

The Tropospheric Ozone Lidar Network (TOLNet) is a unique network of lidar systems that measure atmospheric profiles of ozone and aerosols, to contribute to air-quality studies, atmospheric modeling, and satellite validation efforts. The accurate characterization of these lidars is of critical interest, and is necessary to determine cross-instrument calibration uniformity. From July to August 2014, three lidars, the TROPospheric OZone (TROPOZ) lidar, the Tunable Optical Profiler for Aerosol and oZone (TOPAZ) lidar, and the Langley Mobile Ozone Lidar (LMOL), of TOLNet participated in the "Deriving Information on Surface conditions from Column and Vertically Resolved Observations Relevant to Air Quality" (DISCOVER-AQ) mission and the "Front Range Air Pollution and Photochemistry Éxperiment" (FRAPPÉ) to measure sub-hourly ozone variations from near the surface to the top of the troposphere. Although large differences occur at few individual altitudes in the near field and far field range, the TOLNet lidars agree with each other within ±4%. These results indicate excellent measurement accuracy for the TOLNet lidars that is suitable for use in air-quality and ozone modeling efforts.

[Observation of ozone dry deposition in the field of winter wheat.

PubMed

Li, Shuo; Zheng, You Fei; Wu, Rong Jun; Yin, Ji Fu; Xu, Jing Xin; Zhao, Hui; Sun, Jian

2016-06-01

Ozone is one of the main atmospheric pollutants over surface layer, and its increasing surface ozone concentration and its impact on main crops have become the focus of the public. In order to explore ozone deposition law and environmental factors influencing ozone deposition process, this study used the micrometeorological methods and carried out the experiment under natural conditions. The results showed that during the observational period (the vigorously growing season of wheat), the mean value of ozone flux was -0.35 μg·m -2 ·s -1 (the negative sign indicated that the deposition direction was toward the ground). The mean rate of ozone deposition was 0.55 cm·s -1 . The mean value of aerodynamic resistance was 30 s·m -1 , the mean value of sub-layer resistance was 257 s·m -1 , and that of the canopy layer stomatic resistance was 163 s·m -1 . All the test parameters presented distinct diurnal fluctuation. The ozone deposition resistance was influenced by friction velocity, solar radiation velocity, temperature, relative humidity and other factors.

Feasibility of Sensing Tropospheric Ozone with MODIS 9.6 Micron Observations

NASA Technical Reports Server (NTRS)

Prabhakara, C.; Iacovazzi, R., Jr.; Moon-Yoo, Jung

2004-01-01

With the infrared observations made by the Moderate Resolution Imaging Spectrometer (MODIS) on board the EOS-Aqua satellite, which include the 9.73 micron channel, a method is developed to deduce horizontal patterns of tropospheric ozone in cloud free conditions on a scale of about 100 km. It is assumed that on such small scale, at a given instant, horizontal changes in stratospheric ozone are small compared to that in the troposphere. From theoretical simulations it is found that uncertainties in the land surface emissivity and the vertical thermal stratification in the troposphere can lead to significant errors in the inferred tropospheric ozone. Because of this reason in order to derive horizontal patterns of tropospheric ozone in a given geographic area a tuning of this method is necessary with the help of a few dependent cases. After tuning, this method is applied to independent cases of MODIS data taken over Los Angeles basin in cloud free conditions to derive horizontal distribution of ozone in the troposphere. Preliminary results indicate that the derived patterns of ozone resemble crudely the patterns of surface ozone reported by EPA.

Using Source Apportionment to Evaluate the Cross State Transport of Ozone in the Eastern United States

NASA Astrophysics Data System (ADS)

Goldberg, D. L.; Canty, T. P.; Hembeck, L.; Vinciguerra, T.; Carpenter, S. F.; Anderson, D. C.; Salawitch, R. J.; Dickerson, R. R.

2014-12-01

The amount of air pollution crossing state lines has great policy implications. Using the ozone source apportionment tool (OSAT) in the Comprehensive Air-Quality Model with Extensions (CAMx) version 6.10, we can quantify how much ozone is generated locally versus transported from upwind locations. Initial results show that up to 70% of the surface ozone in Maryland during poor air quality days in the summer of July 2011 can be attributed to pollution from outside of the state's borders. Modifications to the CB05 gas-phase chemistry mechanism, supported by literature recommendations and improve agreement with NASA's DISCOVER-AQ Maryland aircraft campaign, can further increase this percentage. Additionally, we show the role of upwind sources and background ozone has become increasingly important as local emissions of ozone precursors continue to drop, starting with the steep reductions imposed in 2002 in response to Maryland's State Implementation Plan submitted to EPA. This study suggests future efforts to control surface ozone must include a meaningful strategy for dealing with cross-state transport of ozone precursors.

Polar stratospheric clouds and ozone depletion

NASA Technical Reports Server (NTRS)

Toon, Owen B.; Turco, Richard P.

1991-01-01

A review is presented of investigations into the correlation between the depletion of ozone and the formation of polar stratospheric clouds (PSCs). Satellite measurements from Nimbus 7 showed that over the years the depletion from austral spring to austral spring has generally worsened. Approximately 70 percent of the ozone above Antarctica, which equals about 3 percent of the earth's ozone, is lost during September and October. Various hypotheses for ozone depletion are discussed including the theory suggesting that chlorine compounds might be responsible for the ozone hole, whereby chlorine enters the atmosphere as a component of chlorofluorocarbons produced by humans. The three types of PSCs, nitric acid trihydrate, slowly cooling water-ice, and rapidly cooling water-ice clouds act as important components of the Antarctic ozone depletion. It is indicated that destruction of the ozone will be more severe each year for the next few decades, leading to a doubling in area of the Antarctic ozone hole.

Approach for detecting mutagenicity of biodegraded and ozonated pharmaceuticals, metabolites and transformation products from a drinking water perspective.

PubMed

Gartiser, Stefan; Hafner, Christoph; Kronenberger-Schäfer, Kerstin; Happel, Oliver; Trautwein, Christoph; Kümmerer, Klaus

2012-09-01

Many pharmaceuticals and related metabolites are not efficiently removed in sewage treatment plants and enter into surface water. There, they might be subject of drinking water abstraction and treatment by ozonation. In this study, a systematic approach for producing and effect-based testing of transformation products (TPs) during the drinking water ozonation process is proposed. For this, two pharmaceutical parent substances, three metabolites and one environmental degradation product were investigated with respect to their biodegradability and fate during drinking water ozonation. The Ames test (TA98, TA100) was used for the identification of mutagenic activity present in the solutions after testing inherent biodegradability and/or after ozonation of the samples. Suspicious results were complemented with the umu test. Due to the low substrate concentration required for ozonation, all ozonated samples were concentrated via solid phase extraction (SPE) before performing the Ames test. With the exception of piracetam, all substances were only incompletely biodegradable, suggesting the formation of stable TPs. Metformin, piracetam and guanylurea could not be removed completely by the ozonation process. We received some evidence that technical TPs are formed by ozonation of metformin and piracetam, whereas all tested metabolites were not detectable by analytical means after ozonation. In the case of guanylurea, one ozonation TP was identified by LC/MS. None of the experiments showed an increase of mutagenic effects in the Ames test. However, the SPE concentration procedure might lead to false-positive results due to the generation of mutagenic artefacts or might lead to false-negative results by missing adequate recovery efficiency. Thus, these investigations should always be accompanied by process blank controls that are carried out along the whole ozonation and SPE procedure. The study presented here is a first attempt to investigate the significance of transformation products by a systematic approach. However, the adequacy and sensitivity of the methodology need to be further investigated. The approach of combining biodegradation and ozonation with effect-based assays is a promising tool for the early detection of potential hazards from TPs as drinking water contaminants. It can support the strategy for the evaluation of substances and metabolites in drinking water. A multitude of possible factors which influence the results have to be carefully considered, among them the selectivity and sensibility of the mutagenicity test applied, the extraction method for concentrating the relevant compounds and the biocompatibility of the solvent. Therefore, the results have to be carefully interpreted, and possible false-negative and false-positive results should be considered.

Tropospheric Ozone Source Attribution in Southern California during Summer 2014 Based on Lidar Measurements and Model Simulations

NASA Technical Reports Server (NTRS)

Granados Munoz, Maria Jose; Johnson, Matthew S.; Leblanc, Thierry

2016-01-01

In the past decades, significant efforts have been made to increase tropospheric ozone long-term monitoring. A large number of ground-based, airborne and space-borne instruments are currently providing valuable data to contribute to better understand tropospheric ozone budget and variability. Nonetheless, most of these instruments provide in-situ surface and column-integrated data, whereas vertically resolved measurements are still scarce. Besides ozonesondes and aircraft, lidar measurements have proven to be valuable tropospheric ozone profilers. Using the measurements from the tropospheric ozone differential absorption lidar (DIAL) located at the JPL Table Mountain Facility, California, and the GEOS-Chem and GEOS-5 model outputs, the impact of the North American monsoon on tropospheric ozone during summer 2014 is investigated. The influence of the Monsoon lightning-induced NOx will be evaluated against other sources (e.g. local anthropogenic emissions and the stratosphere) using also complementary data such as backward-trajectories analysis, coincident water vapor lidar measurements, and surface ozone in-situ measurements.

Ozonation of cooling tower waters

NASA Technical Reports Server (NTRS)

Humphrey, M. F.; French, K. R.; Howe, R. D. (Inventor)

1979-01-01

Continuous ozone injection into water circulating between a cooling tower and heat exchanger with heavy scale deposits inhibits formation of further deposits, promotes flaking of existing deposits, inhibits chemical corrosion and controls algae and bacteria.

Derived Emission Rates and Photochemical Production Rates of Volatile Organic Compounds (VOCs) Associated with Oil and Natural Gas Operations in the Uintah Basin, UT During a Wintertime Ozone Formation Event

NASA Astrophysics Data System (ADS)

Koss, A.; De Gouw, J. A.; Warneke, C.; Gilman, J.; Lerner, B. M.; Graus, M.; Yuan, B.; Edwards, P. M.; Brown, S. S.; Wild, R. J.; Roberts, J. M.; Bates, T. S.; Quinn, P.

2014-12-01

The Uintah Basin, an oil and natural gas extraction field in Utah, experienced extremely high levels of volatile organic compounds (VOCs) and ozone during the winter of 2013 - up to 100 ppmv carbon and 150 ppbv O3. Here we interpret VOCs measured during an ozone formation event from 31 Jan 2013 to 8 Feb 2013. Ratios of VOCs show strong diurnal cycles and week-long trends. A simple analysis was applied to ratios of aromatic VOCs measured by proton transfer reaction mass spectrometer (PTR-MS) to explain these trends and to estimate emission rates of aromatic VOCs from oil and natural gas extraction, VOC emission ratios relative to benzene, and ambient [OH]. The analysis incorporates the following assumptions: (1) the source composition of emitted VOCs and their emission rates were temporally and spatially constant, and (2) the removal of VOCs was governed by reaction with OH, diurnal profile of which is constrained by measured photolysis rates. The main findings are (1) the emission rate of methane, extrapolated from the emission rate of benzene, is on the same order as an independent estimate from aircraft measurements of methane in 2012, (2) the derived aromatic emission ratios are consistent with source contributions from both oil and gas producing wells, and (3) calculated daily OH concentrations are low, peaking at 1x106 molecules cm-3. The analysis was extended to investigate secondary production of oxygenated VOCs measured by PTR-MS. The analysis is able to explain daytime production, but it does not adequately explain nighttime behavior, which may be affected by complex deposition to snow and ice surfaces. The relative carbon mass of primary and secondary compounds was calculated and compared to observations. At the end of the ozone formation event (day 6), our analysis predicts that secondary (oxidized) VOCs should comprise about 40% of total carbon mass. However, only 12% of these compounds are accounted for by measured oxygenated VOCs and organic aerosol. Additionally, formation rates of measured oxygenated VOCs did not sum to the total primary compound oxidation rate. The disparity is likely due to both incomplete measurements of oxygenated products and VOC loss to deposition.

How to most effectively expand the global surface ozone observing network

NASA Astrophysics Data System (ADS)

Sofen, E. D.; Bowdalo, D.; Evans, M. J.

2016-02-01

Surface ozone observations with modern instrumentation have been made around the world for more than 40 years. Some of these observations have been made as one-off activities with short-term, specific science objectives and some have been made as part of wider networks which have provided a foundational infrastructure of data collection, calibration, quality control, and dissemination. These observations provide a fundamental underpinning to our understanding of tropospheric chemistry, air quality policy, atmosphere-biosphere interactions, etc. brought together eight of these networks to provide a single data set of surface ozone observations. We investigate how representative this combined data set is of global surface ozone using the output from a global atmospheric chemistry model. We estimate that on an area basis, 25 % of the globe is observed (34 % land, 21 % ocean). Whereas Europe and North America have almost complete coverage, other continents, Africa, South America, Australia, and Asia (12-17 %) show significant gaps. Antarctica is surprisingly well observed (78 %). Little monitoring occurs over the oceans, with the tropical and southern oceans particularly poorly represented. The surface ozone over key biomes such as tropical forests and savanna is almost completely unmonitored. A chemical cluster analysis suggests that a significant number of observations are made of polluted air masses, but cleaner air masses whether over the land or ocean (especially again in the tropics) are significantly under-observed. The current network is unlikely to see the impact of the El Niño-Southern Oscillation (ENSO) but may be capable of detecting other planetary-scale signals. Model assessment and validation activities are hampered by a lack of observations in regions where the models differ substantially, as is the ability to monitor likely changes in surface ozone over the next century. Using our methodology we are able to suggest new sites which would help to close the gap in our ability to measure global surface ozone. An additional 20 surface ozone monitoring sites (a 20 % increase in the World Meteorological Organization Global Atmosphere Watch (WMO GAW) ozone sites or a 1 % increase in the total background network) located on 10 islands and in 10 continental regions would almost double the area observed. The cost of this addition to the network is small compared to other expenditure on atmospheric composition research infrastructure and would provide a significant long-term benefit to our understanding of the composition of the atmosphere, information which will also be available for consideration by air quality control managers and policy makers.

Organic aerosol formation in citronella candle plumes.

PubMed

Bothe, Melanie; Donahue, Neil McPherson

2010-09-01

Citronella candles are widely used as insect repellants, especially outdoors in the evening. Because these essential oils are unsaturated, they have a unique potential to form secondary organic aerosol (SOA) via reaction with ozone, which is also commonly elevated on summer evenings when the candles are often in use. We investigated this process, along with primary aerosol emissions, by briefly placing a citronella tealight candle in a smog chamber and then adding ozone to the chamber. In repeated experiments, we observed rapid and substantial SOA formation after ozone addition; this process must therefore be considered when assessing the risks and benefits of using citronella candle to repel insects.

The characteristics of tropospheric ozone seasonality observed from ozone soundings at Pohang, Korea.

PubMed

Kim, Jae H; Lee, H J; Lee, S H

2006-07-01

This paper presents the first analysis of vertical ozone sounding measurements over Pohang, Korea. The main focus is to analyze the seasonal variation of vertical ozone profiles and determine the mechanisms controlling ozone seasonality. The maxima ozone at the surface and in the free troposphere are observed in May and June, respectively. In comparison with the ozone seasonality at Oki (near sea level) and Happo (altitude of 1840 m) in Japan, which are located at the same latitude as of Pohang, we have found that the time of the ozone maximum at the Japanese sites is always a month earlier than at Pohang. Analysis of the wind flow at the surface shows that the wind shifts from westerly to southerly in May over Japan, but in June over Pohang. However, this wind shift above boundary layer occurs a month later. This wind shift results in significantly smaller amounts of ozone because the southerly wind brings clean wet tropical air. It has been suggested that the spring ozone maximum in the lower troposphere is due to polluted air transported from China. However, an enhanced ozone amount over the free troposphere in June appears to have a different origin. A tongue-like structure in the time-height cross-section of ozone concentrations, which starts from the stratosphere and extends to the middle troposphere, suggests that the ozone enhancement occurs due to a gradual migration of ozone from the stratosphere. The high frequency of dry air with elevated ozone concentrations in the upper troposphere in June suggests that the air is transported from the stratosphere. HYSPLIT trajectory analysis supports the hypothesis that enhanced ozone in the free troposphere is not likely due to transport from sources of anthropogenic activity.

Ozone-vegetation interaction in the Earth system: implications for air quality, ecosystems and agriculture

NASA Astrophysics Data System (ADS)

Tai, A. P. K.; Lombardozzi, D.; Val Martin, M.; Heald, C. L.

2015-12-01

Surface ozone is one of the most significant air pollutants due to its damaging effects not only on human health, but also on vegetation and crop productivity. Chronic ozone exposure has been shown to reduce photosynthesis and interfere with gas exchange in plants, which in turn affect the surface energy balance, carbon sink and other biogeochemical fluxes. Ozone damage on vegetation can thus have major ramifications on climate and atmospheric composition, including possible feedbacks onto ozone itself (see figure) that are not well understood. The damage of ozone on crops has been well documented, but a mechanistic understanding is not well established. Here we present several results pertaining to ozone-vegetation interaction. Using the Community Earth System Model, we find that inclusion of ozone damage on plants reduces the global land carbon sink by up to 5%, while simulated ozone is modified by -20 to +4 ppbv depending on the relative importance of competing mechanisms in different regions. We also perform a statistical analysis of multidecadal global datasets of crop yields, agroclimatic variables and ozone exposures to characterize the spatial variability of crop sensitivity to ozone and temperature extremes, specifically accounting for the confounding effect of ozone-temperature covariation. We find that several crops exhibit stronger sensitivity to ozone than found by previous field studies, with a strong anticorrelation between the sensitivity and average ozone levels that reflects biological adaptive ozone resistance. Our results show that a more complete understanding of ozone-vegetation interaction is necessary to derive more realistic future projections of climate, air quality and agricultural production, and thereby to formulate optimal strategies to safeguard public health and food security.

Effects of Exposure to Ozone on the Ocular Surface in an Experimental Model of Allergic Conjunctivitis

PubMed Central

Lee, Hun; Kim, Eung Kweon; Kim, Hee Young; Kim, Tae-im

2017-01-01

Based on previous findings that ozone can induce an inflammatory response in the ocular surface of an animal model and in cultured human conjunctival epithelial cells, we investigated whether exposure to ozone exacerbates symptoms of allergic conjunctivitis. We evaluated the effects of exposure to ozone on conjunctival chemosis, conjunctival injection, corneal and conjunctival fluorescein staining scores, production of inflammatory cytokines in tears, and aqueous tear production in a mouse model of allergic conjunctivitis. To validate our in vivo results, we used interleukin (IL)-1α-pretreated conjunctival epithelial cells as an in vitro substitute for the mouse model. We evaluated whether exposure to ozone increased the inflammatory response and altered oxidative status and mitochondrial function in IL-1α-pretreated conjunctival epithelial cells. In the in vivo study, ozone induced increases in conjunctival chemosis, conjunctival injection, corneal and conjunctival fluorescein staining scores, and production of inflammatory cytokines, accompanied by a decrease in tear volume. In the in vitro study, exposure to ozone led to additional increases in IL-6 and tumor necrosis factor-α mRNA levels, which were already induced by treatment with IL-1α. Ozone did not induce any changes in cell viability. Pretreatment with IL-1α increased the expression of manganese superoxide dismutase, and exposure to ozone led to additional increments in the expression of this antioxidant enzyme. Ozone did not induce any changes in mitochondrial activity or expression of mitochondrial enzymes and proteins related to mitochondrial function, with the exception of phosphor-mammalian target of rapamycin. Treatment with butylated hydroxyanisole, a free radical scavenger, attenuated the ozone-induced increases in IL-6 expression in IL-1α-pretreated conjunctival epithelial cells. Therefore, we conclude that exposure to ozone exacerbates the detrimental effects on the integrity of the ocular surface caused by conjunctival allergic reactions, and further increases the inflammatory response in IL-1α-pretreated conjunctival epithelial cells. PMID:28046113

Ozonolysis at vegetation surfaces. a source of acetone, 4-oxopentanal, 6-methyl-5-hepten-2-one, and geranyl acetone in the troposphere

NASA Astrophysics Data System (ADS)

Fruekilde, P.; Hjorth, J.; Jensen, N. R.; Kotzias, D.; Larsen, B.

The present study gives a possible explanation for the ubiquitous occurrence of 6-methyl-5-hepten-2-one and acetone in ambient air and reports for the first time on a widespread occurrence of geranyl acetone and 4-oxopentanal. We have conducted a series of laboratory experiments in which it is demonstrated that significant amounts of geranyl acetone, 6-methyl-5-hepten-2-one (6-MHO), 4-oxopentanal (4-OPA), and acetone are formed by the reaction of ozone with foliage of common vegetation in the Mediterranean area ( Quercus ilex>Citrus sinensis>Quercus suber>Quercus freinetto>Pinus pinea). In order to rule out biological formation, epicuticular waxes were extracted from the leaves, dispersed on glass wool and allowed to react with a flow of artificial air. Significant amounts of 6-MHO and 4-OPA were formed at ozone concentrations of 50-100 ppbv, but not at zero ozone. A number of terpenoids common in vegetation contain the structural element necessary for ozonolytic formation of 6-MHO. Two sesquiterpenes (nerolidol; farnesol), and a triterpene (squalene) selected as representative test compounds were demonstrated to be strong precursors for acetone, 4-OPA, and 6-MHO. Squalene was also a strong precursor for geranyl acetone. The atmospheric lifetime of geranyl acetone and 6-MHO is less than 1 h under typical conditions. For the present study, we have synthesized 4-OPA and investigated the kinetics of its gas-phase reaction with OH, NO 3, and O 3. A tropospheric lifetime longer than 17 h under typical conditions was calculated from the measured reaction rate constants, which explains the tropospheric occurrence of 4-OPA. It is concluded that future atmospheric chemistry investigations should included geranyl acetone, 6-MHO, and 4-OPA. In a separate experiment it was demonstrated that human skin lipid which contains squalene as a major component is a strong precursor for the four above-mentioned compounds plus nonanal and decanal. The accidental touching of material which later comes into contact with ozone can lead to strong artifact formation of these carbonyl compounds. Previously published results on these compounds must be seen in this new light.

User's guide for SBUV/TOMS ozone derivative products

NASA Technical Reports Server (NTRS)

Fleig, A. J.; Wellemeyer, C.; Oslik, N.; Lee, D.; Miller, J.; Magatani, R.

1984-01-01

A series of products are available derived from the total-ozone and ozone vertical profile results for the Solar Backscattered Ultraviolet/Total-Ozone Mapping Spectrometer (SBUV/TOMS) Nimbus-7 operation. Products available are (1) orbital height-latitude cross sections of the SBUV profile data, (2) daily global total ozone contours in polar coordinates, (3) daily averages of total ozone in global 5x5 degree latitude-longitude grid, (4) daily, monthly and quarterly averages of total ozone and profile data in 10 degree latitude zones, (5) tabular presentation of zonal means, (6) daily global total ozone and profile contours in polar coordinates. The ""Derivative Products User's Guide'' describes each of these products in detail, including their derivation and presentation format. Information is provided on how to order the tapes and microfilm from the National Space Science Data Center.

Secondary organic aerosol and ozone formation from photo-oxidation of unburned diesel fuel in a surrogate atmospheric environment

NASA Astrophysics Data System (ADS)

Li, Weihua; Cocker, David R.

2018-07-01

Diesel fuel is a complex mixture of intermediate volatility organic compounds (IVOCs). Previous studies focused on secondary organic aerosol (SOA) and ozone formation from photo-oxidation of organic vapor from diesel exhaust and their components such as aromatics and heavy alkanes. However, there are few studies on atmospheric behavior of unburnt diesel. Therefore, in this study, ten unburnt #2 commercial diesel samples and one FACE9A research diesel fuel were photo-oxidized in the University of California Riverside, College of Engineering-Center for Environmental Research & Technology dual environmental chambers to investigate their SOA and ozone production potential. Photochemical aging rapidly produced significant SOA (yield ∼20.3-37.7%) in the presence of a surrogate reactive organic gas (ROG) mixture used to mimic urban atmospheric reactivity. SOA yields were consistent with n-Heptadecane yields under similar conditions. Doubling NOx concentrations within relevant urban concentration levels enhanced SOA formation by 33% and ozone formation by 48%. SOA formation in this study was approximately fourteen times higher than previously reported for very high NOx conditions. An SOA experiment designed to mimic the previous work achieved similar yields to the earlier work. SOA formed under urban relevant NOx concentrations were consistent with semi-volatile-oxygenated organic aerosol (SV-OOA) and underwent little further chemical processing once produced.

MARs Color Imager (MARCI) Daily Global Ozone Column Mapping from the Mars Reconnaissance Orbiter (MRO): A Survey of 2006-2010 Results

NASA Astrophysics Data System (ADS)

Clancy, R. T.; Wolff, M. J.; Malin, M. C.; Cantor, B. A.

2010-12-01

MARCI UV band imaging photometry within (260nm) and outside (320nm) the Hartley ozone band absorption supports daily global mapping of Mars ozone column abundances. Key retrieval issues include accurate UV radiometric calibrations, detailed specifications of surface and atmospheric background reflectance (surface albedo, atmospheric Raleigh and dust scattering/absorption), and simultaneous cloud retrievals. The implementation of accurate radiative transfer (RT) treatments of these processes has been accomplished (Wolff et al., 2010) such that daily global mapping retrievals for Mars ozone columns have been completed for the 2006-2010 period of MARCI global imaging. Ozone retrievals are most accurate for high column abundances associated with mid-to-high latitude regions during fall, winter, and spring seasons. We present a survey of these MARCI ozone column retrievals versus season, latitude, longitude, and year.

The Response of Tropical Tropospheric Ozone to ENSO

NASA Technical Reports Server (NTRS)

Oman, L. D.; Ziemke, J. R.; Douglass, A. R.; Waugh, D. W.; Lang, C.; Rodriguez, J. M.; Nielsen, J. E.

2011-01-01

We have successfully reproduced the Ozone ENSO Index (OEI) in the Goddard Earth Observing System (GEOS) chemistry-climate model (CCM) forced by observed sea surface temperatures over a 25-year period. The vertical ozone response to ENSO is consistent with changes in the Walker circulation. We derive the sensitivity of simulated ozone to ENSO variations using linear regression analysis. The western Pacific and Indian Ocean region shows similar positive ozone sensitivities from the surface to the upper troposphere, in response to positive anomalies in the Nino 3.4 Index. The eastern and central Pacific region shows negative sensitivities with the largest sensitivity in the upper troposphere. This vertical response compares well with that derived from SHADOZ ozonesondes in each region. The OEI reveals a response of tropospheric ozone to circulation change that is nearly independent of changes in emissions and thus it is potentially useful in chemistry-climate model evaluation.

Description of the surface water filtration and ozone treatment system at the Northeast Fishery Center

USDA-ARS?s Scientific Manuscript database

A water filtration and ozone disinfection system was installed at the U.S. Fish and Wildlife Service's Northeast Fishery Center in Lamar, Pennsylvania to treat a surface water supply that is used to culture sensitive and endangered fish. The treatment system first passes the surface water through dr...

Anthropogenic changes in the surface all-sky UV-B radiation through 1850-2005 simulated by an Earth system model

NASA Astrophysics Data System (ADS)

Watanabe, S.; Takemura, T.; Sudo, K.; Yokohata, T.; Kawase, H.

2012-06-01

The historical anthropogenic change in the surface all-sky UV-B (solar ultraviolet: 280-315 nm) radiation through 1850-2005 is evaluated using an Earth system model. Responses of UV-B dose to anthropogenic changes in ozone and aerosols are separately evaluated using a series of historical simulations including/excluding these changes. Increases in these air pollutants cause reductions in UV-B transmittance, which occur gradually/rapidly before/after 1950 in and downwind of industrial and deforestation regions. Furthermore, changes in ozone transport in the lower stratosphere, which is induced by increasing greenhouse gas concentrations, increase ozone concentration in the extratropical upper troposphere and lower stratosphere. These transient changes work to decrease the amount of UV-B reaching the Earth's surface, counteracting the well-known effect increasing UV-B due to stratospheric ozone depletion, which developed rapidly after ca. 1980. As a consequence, the surface UV-B radiation change between 1850 and 2000 is negative in the tropics and NH extratropics and positive in the SH extratropics. Comparing the contributions of ozone and aerosol changes to the UV-B change, the transient change in ozone absorption of UV-B mainly determines the total change in the surface UV-B radiation at most locations. On the other hand, the aerosol direct and indirect effects on UV-B play an equally important role to that of ozone in the NH mid-latitudes and tropics. A typical example is East Asia (25° N-60° N and 120° E-150° E), where the effect of aerosols (ca. 70%) dominates the total UV-B change.

Anthropogenic changes in the surface all-sky UV-B radiation through 1850-2005 simulated by an Earth system model

NASA Astrophysics Data System (ADS)

Watanabe, S.; Takemura, T.; Sudo, K.; Yokohata, T.; Kawase, H.

2012-02-01

The historical anthropogenic change in the surface all-sky UV-B (solar ultraviolet: 280-315 nm) radiation through 1850-2005 is evaluated using an Earth system model. Responses of UV-B dose to anthropogenic changes in ozone and aerosols are separately evaluated using a series of historical simulations including/excluding these changes. Increases in these air pollutants cause reductions in UV-B transmittance, which occur gradually/rapidly before/after 1950 in and downwind of industrial and deforestation regions. Furthermore, changes in ozone transport in the lower stratosphere, which is induced by increasing greenhouse gas concentrations, increase ozone concentration in the extratropical upper troposphere and lower stratosphere. These transient changes work to decrease the amount of UV-B reaching the Earth's surface, counteracting the well-known effect increasing UV-B due to stratospheric ozone depletion, which developed rapidly after ca. 1980. As a consequence, the surface all-sky UV-B radiation change between 1850 and 2000 is negative in the tropics and NH extratropics and positive in the SH extratropics. Comparing the contributions of ozone and aerosol changes to the UV-B change, the transient change in ozone absorption of UV-B mainly determines the total change in the surface all-sky UV-B radiation at most locations. On the other hand, the aerosol direct and indirect effects on UV-B play an equally important role to that of ozone in the NH mid-latitudes and tropics. A typical example is East Asia (25° N-60° N and 120° E-150° E), where the effect of aerosols (ca. 70%) dominates the total UV-B change.

Use of North American and European Air Quality Networks to Evaluate Global Chemistry-Climate Modeling of Surface Ozone

NASA Technical Reports Server (NTRS)

Schnell, J. L.; Prather, M. J.; Josse, B.; Naik, V.; Horowitz, L. W.; Cameron-Smith, P.; Bergmann, D.; Zeng, G.; Plummer, D. A.; Sudo, K.;

Factors affecting ozone removal rates in a simulated aircraft cabin environment

NASA Astrophysics Data System (ADS)

Tamás, Gyöngyi; Weschler, Charles J.; Bakó-Biró, Zsolt; Wyon, David P.; Strøm-Tejsen, Peter

Ozone concentrations were measured concurrently inside a simulated aircraft cabin and in the airstream providing ventilation air to the cabin. Ozone decay rates were also measured after cessation of ozone injection into the supply airstream. By systematically varying the presence or absence of people, soiled T-shirts, aircraft seats and a used HEPA filter, we have been able in the course of 24 experiments to isolate the contributions of these and other factors to the removal of ozone from the cabin air. In the case of this simulated aircraft, people were responsible for almost 60% of the ozone removal occurring within the cabin and recirculation system; respiration can only have been responsible for about 4% of this removal. The aircraft seats removed about 25% of the ozone; the loaded HEPA filter, 7%; and the other surfaces, 10%. A T-shirt that had been slept in overnight removed roughly 70% as much ozone as a person, indicating the importance of skin oils in ozone removal. The presence of the used HEPA filter in the recirculated airstream reduced the perceived air quality. Over a 5-h period, the overall ozone removal rate by cabin surfaces decreased at ˜3% h -1. With people present, the measured ratio of ozone's concentration in the cabin versus that outside the cabin was 0.15-0.21, smaller than levels reported in the literature. The results reinforce the conclusion that the optimal way to reduce people's exposure to both ozone and ozone oxidation products is to efficiently remove ozone from the air supply system of an aircraft.

Feedbacks between Climate and Fire Emissions

DTIC Science & Technology

2011-11-29

CH4 2. Direct emission of short-lived climate forcers - Black Carbon - Particulate organic matter 3. Production of tropospheric ozone and secondary... tropospheric ozone and secondary organic particulate matter 4. Changes in land surface properties - Black carbon on snow - Albedo Radiative Forcing of Black...lived  climate forcers:  particles 3.  Ozone   production 4. Change in  surface properties Fires Impacts on the Climate System 1. Emission of long lived

Surface ozone in the Southern Hemisphere: 20 years of data from a site with a unique setting in El Tololo, Chile

NASA Astrophysics Data System (ADS)

Anet, Julien G.; Steinbacher, Martin; Gallardo, Laura; Velásquez Álvarez, Patricio A.; Emmenegger, Lukas; Buchmann, Brigitte

2017-05-01

The knowledge of surface ozone mole fractions and their global distribution is of utmost importance due to the impact of ozone on human health and ecosystems and the central role of ozone in controlling the oxidation capacity of the troposphere. The availability of long-term ozone records is far better in the Northern than in the Southern Hemisphere, and recent analyses of the seven accessible records in the Southern Hemisphere have shown inconclusive trends. Since late 1995, surface ozone is measured in situ at "El Tololo", a high-altitude (2200 m a.s.l.) and pristine station in Chile (30° S, 71° W). The dataset has been recently fully quality controlled and reprocessed. This study presents the observed ozone trends and annual cycles and identifies key processes driving these patterns. From 1995 to 2010, an overall positive trend of ˜ 0.7 ppb decade-1 is found. Strongest trends per season are observed in March and April. Highest mole fractions are observed in late spring (October) and show a strong correlation with ozone transported from the stratosphere down into the troposphere, as simulated with a model. Over the 20 years of observations, the springtime ozone maximum has shifted to earlier times in the year, which, again, is strongly correlated with a temporal shift in the occurrence of the maximum of simulated stratospheric ozone transport at the site. We conclude that background ozone at El Tololo is mainly driven by stratospheric intrusions rather than photochemical production from anthropogenic and biogenic precursors. The major footprint of the sampled air masses is located over the Pacific Ocean. Therefore, due to the negligible influence of local processes, the ozone record also allows studying the influence of El Niño and La Niña episodes on background ozone levels in South America. In agreement with previous studies, we find that, during La Niña conditions, ozone mole fractions reach higher levels than during El Niño conditions.

The effect of pre-oxidation on NDMA formation and the influence of pH.

PubMed

Selbes, Meric; Kim, Daekyun; Karanfil, Tanju

2014-12-01

N-nitrosodimethylamine (NDMA), a probable human carcinogen, is a disinfection by-product that has been detected in chloraminated drinking water systems. Pre-oxidation of the NDMA precursors prior to chloramination can be a viable approach for water utilities to control the NDMA levels. This study examined the effects of (i) commonly used oxidants (i.e., chlorine, chlorine dioxide and ozone) in water treatment, (ii) oxidant concentration and contact time (CT), and (iii) pre-oxidation pH on the formation of NDMA from subsequent chloramination. Fifteen model precursors with NDMA molar yields ranging from approximately 0.1%-90% were examined. Pre-chlorination reduced NDMA formation from most precursors by 10%-50% except quaternary amine polymers (i.e., PolyDADMAC, PolyACRYL, PolyAMINE). Pre-oxidation with chlorine dioxide and ozone achieved the same or higher deactivation of NDMA precursors (e.g., ranitidine) while increasing NDMA formation for some other precursors (e.g., daminozid). The increases with chlorine dioxide exposure were attributed to the release of oxidation products with dimethylamine (DMA) moiety, which may form more NDMA upon chloramination than the unoxidizied parent compound. On the other hand, chlorine dioxide was effective, if a precursors NDMA yield were higher than DMA. The ozone-triggered increases could be related to direct NDMA formation from DMA which are released by ozonation of amines with DMA moiety, amides or hydrazines. However, hydroxyl radicals formed from the decomposition of ozone would be also involved in decomposition of formed NDMA, reducing the overall NDMA levels at longer contact times. pH conditions influenced significantly the effectiveness of deactivation of precursors depending on the type of precursor and oxidant used. Copyright © 2014 Elsevier Ltd. All rights reserved.

Probabilistic Forecasting of Surface Ozone with a Novel Statistical Approach

NASA Technical Reports Server (NTRS)

Balashov, Nikolay V.; Thompson, Anne M.; Young, George S.

2017-01-01

The recent change in the Environmental Protection Agency's surface ozone regulation, lowering the surface ozone daily maximum 8-h average (MDA8) exceedance threshold from 75 to 70 ppbv, poses significant challenges to U.S. air quality (AQ) forecasters responsible for ozone MDA8 forecasts. The forecasters, supplied by only a few AQ model products, end up relying heavily on self-developed tools. To help U.S. AQ forecasters, this study explores a surface ozone MDA8 forecasting tool that is based solely on statistical methods and standard meteorological variables from the numerical weather prediction (NWP) models. The model combines the self-organizing map (SOM), which is a clustering technique, with a step wise weighted quadratic regression using meteorological variables as predictors for ozone MDA8. The SOM method identifies different weather regimes, to distinguish between various modes of ozone variability, and groups them according to similarity. In this way, when a regression is developed for a specific regime, data from the other regimes are also used, with weights that are based on their similarity to this specific regime. This approach, regression in SOM (REGiS), yields a distinct model for each regime taking into account both the training cases for that regime and other similar training cases. To produce probabilistic MDA8 ozone forecasts, REGiS weighs and combines all of the developed regression models on the basis of the weather patterns predicted by an NWP model. REGiS is evaluated over the San Joaquin Valley in California and the northeastern plains of Colorado. The results suggest that the model performs best when trained and adjusted separately for an individual AQ station and its corresponding meteorological site.

On the origin of regional spring time ozone episodes in the Western Mediterranean

NASA Astrophysics Data System (ADS)

Kalabokas, Pavlos; Hjorth, Jens; Foret, Gilles; Dufour, Gaëlle; Eremenko, Maxim; Siour, Guillaume; Cuesta, Juan; Beekmann, Matthias

2017-04-01

For the identification of regional spring time ozone episodes, rural EMEP ozone measurements from countries surrounding the Western Mediterranean (Spain, France, Switzerland, Italy, Malta) have been examined with emphasis on periods of high ozone, according to the daily variation of the afternoon (12:00 - 18:00) ozone. For two selected high ozone episodes in April-May 2008, composite NCEP/NCAR reanalysis maps of various meteorological parameters and/or their anomalies (geopotential height, specific humidity, vertical velocity omega, vector wind speed and temperature) at various tropospheric pressure levels have been examined together with the corresponding satellite IASI ozone measurements (at 3 and 10 km), CHIMERE simulations, vertical ozone soundings and HYSPLIT back trajectories (Kalabokas et al., 2016). The results show that high surface ozone is measured at several countries simultaneously over several days. Also, the examined spring ozone episodes in Western Mediterranean and Central Europe are linked to synoptic meteorological conditions very similar to those recently observed in summertime ozone episodes over the Eastern Mediterranean (Doche et al., 2014; Kalabokas et al., 2015 and references therein), where the transport of tropospheric ozone-rich air masses through atmospheric subsidence influences significantly the boundary layer and surface ozone concentrations. In particular, the geographic areas with observed tropospheric subsidence seem to be the transition regions between high pressure and low pressure systems. IASI satellite measurements show extended areas of high tropospheric ozone over the low pressure systems adjacent to the anticyclones, which influence significantly the boundary layer and surface ozone concentrations within the anticyclones by subsidence and advection, in addition to the photochemically produced ozone there, resulting to exceedances of the 60 ppb standard for human health protection over extended geographical areas. References Doche, C., Dufour, G., Foret, G., Eremenko, M., Cuesta, J., Beekmann, M., and Kalabokas, P., 2014. Summertime tropospheric-ozone variability over the Mediterranean basin observed with IASI, Atmos. Chem. Phys., 14, 10589-10600. Kalabokas P. D., Thouret V., Cammas J.-P., Volz-Τhomas A., Boulanger D., Repapis C.C., 2015. The geographical distribution of meteorological parameters associated with high and low summer ozone levels in the lower troposphere and the boundary layer over the eastern Mediterranean (Cairo case), Tellus B, 67, 27853, http://dx.doi.org/10.3402/tellusb.v67.27853. Kalabokas P., J. Hjorth, G. Foret, G. Dufour, M. Eremenko, G. Siour, J. Cuesta, M. Beekmann, 2016. An investigation on the origin of regional spring time ozone episodes in the Western Mediterranean and Central Europe. Atmos. Chem. Phys. Discuss., doi:10.5194/acp-2016-615.

Photochemical production of ozone in the upper troposphere in association with cumulus convection over Indonesia

NASA Astrophysics Data System (ADS)

Kita, K.; Kawakami, S.; Miyazaki, Y.; Higashi, Y.; Kondo, Y.; Nishi, N.; Koike, M.; Blake, D. R.; Machida, T.; Sano, T.; Hu, W.; Ko, M.; Ogawa, T.

2002-02-01

The Biomass Burning and Lightning Experiment phase A (BIBLE-A) aircraft observation campaign was conducted from 24 September to 10 October 1998, during a La Niña period. During this campaign, distributions of ozone and its precursors (NO, CO, and nonmethane hydrocarbons (NMHCs)) were observed over the tropical Pacific Ocean, Indonesia, and northern Australia. Mixing ratios of ozone and its precursors were very low at altitudes between 0 and 13.5 km over the tropical Pacific Ocean. The mixing ratios of ozone precursors above 8 km over Indonesia were often significantly higher than those over the tropical Pacific Ocean, even though the prevailing easterlies carried the air from the tropical Pacific Ocean to over Indonesia within several days. For example, median NO and CO mixing ratios in the upper troposphere were 12 parts per trillion (pptv) and 72 parts per billion (ppbv) over the tropical Pacific Ocean and were 83 pptv and 85 ppbv over western Indonesia, respectively. Meteorological analyses and high ethene (C2H4) mixing ratios indicate that the increase of the ozone precursors was caused by active convection over Indonesia through upward transport of polluted air, mixing, and lightning all within the few days prior to observation. Sources of ozone precursors are discussed by comparing correlations of some NMHCs and CH3Cl concentrations with CO between the lower and upper troposphere. Biomass burning in Indonesia was nearly inactive during BIBLE-A and was not a dominant source of the ozone precursors, but urban pollution and lightning contributed importantly to their increases. The increase in ozone precursors raised net ozone production rates over western Indonesia in the upper troposphere, as shown by a photochemical model calculation. However, the ozone mixing ratio (˜20 ppbv) did not increase significantly over Indonesia because photochemical production of ozone did not have sufficient time since the augmentation of ozone precursors. Backward trajectories show that many air masses sampled over the ocean south of Indonesia and over northern Australia passed over western Indonesia 4-9 days prior to being measured. In these air masses the mixing ratios of ozone precursors, except for short-lived species, were similar to those over western Indonesia. In contrast, the ozone mixing ratio was higher by about 10 ppbv than that over Indonesia, indicating that photochemical production of ozone occurred during transport from Indonesia. The average rate of ozone increase (1.8 ppbv/d) during this transport is similar to the net ozone formation rate calculated by the photochemical model. This study shows that active convection over Indonesia carried polluted air upward from the surface and had a discernable influence on the distribution of ozone in the upper troposphere over the Indian Ocean, northern Australia, and the south subtropical Pacific Ocean, combined with NO production by lightning.

Photochemical production of ozone in the upper troposphere in association with cumulus convection over Indonesia

NASA Astrophysics Data System (ADS)

Kita, K.; Kawakami, S.; Miyazaki, Y.; Higashi, Y.; Kondo, Y.; Nishi, N.; Koike, M.; Blake, D. R.; Machida, T.; Sano, T.; Hu, W.; Ko, M.; Ogawa, T.

2003-02-01

The Biomass Burning and Lightning Experiment phase A (BIBLE-A) aircraft observation campaign was conducted from 24 September to 10 October 1998, during a La Niña period. During this campaign, distributions of ozone and its precursors (NO, CO, and nonmethane hydrocarbons (NMHCs)) were observed over the tropical Pacific Ocean, Indonesia, and northern Australia. Mixing ratios of ozone and its precursors were very low at altitudes between 0 and 13.5 km over the tropical Pacific Ocean. The mixing ratios of ozone precursors above 8 km over Indonesia were often significantly higher than those over the tropical Pacific Ocean, even though the prevailing easterlies carried the air from the tropical Pacific Ocean to over Indonesia within several days. For example, median NO and CO mixing ratios in the upper troposphere were 12 parts per trillion (pptv) and 72 parts per billion (ppbv) over the tropical Pacific Ocean and were 83 pptv and 85 ppbv over western Indonesia, respectively. Meteorological analyses and high ethene (C2H4) mixing ratios indicate that the increase of the ozone precursors was caused by active convection over Indonesia through upward transport of polluted air, mixing, and lightning all within the few days prior to observation. Sources of ozone precursors are discussed by comparing correlations of some NMHCs and CH3Cl concentrations with CO between the lower and upper troposphere. Biomass burning in Indonesia was nearly inactive during BIBLE-A and was not a dominant source of the ozone precursors, but urban pollution and lightning contributed importantly to their increases. The increase in ozone precursors raised net ozone production rates over western Indonesia in the upper troposphere, as shown by a photochemical model calculation. However, the ozone mixing ratio (~20 ppbv) did not increase significantly over Indonesia because photochemical production of ozone did not have sufficient time since the augmentation of ozone precursors. Backward trajectories show that many air masses sampled over the ocean south of Indonesia and over northern Australia passed over western Indonesia 4-9 days prior to being measured. In these air masses the mixing ratios of ozone precursors, except for short-lived species, were similar to those over western Indonesia. In contrast, the ozone mixing ratio was higher by about 10 ppbv than that over Indonesia, indicating that photochemical production of ozone occurred during transport from Indonesia. The average rate of ozone increase (1.8 ppbv/d) during this transport is similar to the net ozone formation rate calculated by the photochemical model. This study shows that active convection over Indonesia carried polluted air upward from the surface and had a discernable influence on the distribution of ozone in the upper troposphere over the Indian Ocean, northern Australia, and the south subtropical Pacific Ocean, combined with NO production by lightning.

Global ozone and air quality: a multi-model assessment of risks to human health and crops

NASA Astrophysics Data System (ADS)

Ellingsen, K.; Gauss, M.; van Dingenen, R.; Dentener, F. J.; Emberson, L.; Fiore, A. M.; Schultz, M. G.; Stevenson, D. S.; Ashmore, M. R.; Atherton, C. S.; Bergmann, D. J.; Bey, I.; Butler, T.; Drevet, J.; Eskes, H.; Hauglustaine, D. A.; Isaksen, I. S. A.; Horowitz, L. W.; Krol, M.; Lamarque, J. F.; Lawrence, M. G.; van Noije, T.; Pyle, J.; Rast, S.; Rodriguez, J.; Savage, N.; Strahan, S.; Sudo, K.; Szopa, S.; Wild, O.

2008-02-01

Within ACCENT, a European Network of Excellence, eighteen atmospheric models from the U.S., Europe, and Japan calculated present (2000) and future (2030) concentrations of ozone at the Earth's surface with hourly temporal resolution. Comparison of model results with surface ozone measurements in 14 world regions indicates that levels and seasonality of surface ozone in North America and Europe are characterized well by global models, with annual average biases typically within 5-10 nmol/mol. However, comparison with rather sparse observations over some regions suggest that most models overestimate annual ozone by 15-20 nmol/mol in some locations. Two scenarios from the International Institute for Applied Systems Analysis (IIASA) and one from the Intergovernmental Panel on Climate Change Special Report on Emissions Scenarios (IPCC SRES) have been implemented in the models. This study focuses on changes in near-surface ozone and their effects on human health and vegetation. Different indices and air quality standards are used to characterise air quality. We show that often the calculated changes in the different indices are closely inter-related. Indices using lower thresholds are more consistent between the models, and are recommended for global model analysis. Our analysis indicates that currently about two-thirds of the regions considered do not meet health air quality standards, whereas only 2-4 regions remain below the threshold. Calculated air quality exceedances show moderate deterioration by 2030 if current emissions legislation is followed and slight improvements if current emissions reduction technology is used optimally. For the "business as usual" scenario severe air quality problems are predicted. We show that model simulations of air quality indices are particularly sensitive to how well ozone is represented, and improved accuracy is needed for future projections. Additional measurements are needed to allow a more quantitative assessment of the risks to human health and vegetation from changing levels of surface ozone.

Atmospheric carbon dioxide and chlorofluoromethanes - Combined effects on stratospheric ozone, temperature, and surface temperature

NASA Technical Reports Server (NTRS)

Callis, L. B.; Natarajan, M.

1981-01-01

The effects of combined CO2 and CFCl3 and CF2Cl2 time-dependent scenarios on atmospheric O3 and temperature are described; the steady-state levels of O3 and surface temperature, to which the chlorofluoromethane scenario tends in the presence of twice and four time ambient CO2, are examined; and surface temperature changes, caused by the combined effects, are established. A description of the model and of the experiments is presented. Results indicate that (1) the total ozone time history is significantly different from that due to the chlorofluoromethane alone; (2) a local ozone minimum occurs in the upper stratosphere about 45 years from the present with a subsequent ozone increase, then decline; and (3) steady-state solutions indicate that tropospheric temperature and water vapor increases, associated with increased infrared opacity, cause significant changes in tropospheric ozone levels for 2 x CO2 and 4 x CO2, without the addition of chlorofluoromethanes.

Ozone destruction through heterogeneous chemistry following the eruption of El Chichon

NASA Technical Reports Server (NTRS)

Hofmann, David J.; Solomon, Susan

1989-01-01

The results of ozone observations at northern midlatitudes in late 1982 through 1983, following the eruption of El Chichon are discussed, together with the observations of other trace gases which may be linked to possible variations in ozone chemistry. These results are related to the in situ aerosol observations following the El Chicon eruption, with particular attention given to data relevant to heterogeneous reactions, such as the aerosol surface area and weight percent H2SO4. It is shown that, at midlatitudes, the observed volcanic-particle surface area reached a maximum of about 50 sq microns/cu m (above a typical background value of about 0.75) at an altitude of 18-20 km in early 1983; this enhancement of surface area is about the same as that encountered in stratospheric clouds in the Antarctic, suggesting a possible basis for ozone depletion through heterogeneous chemistry. The fraction of ozone reduction that may have occurred as a result of heterogeneous chemicl effects is estimated.

CAMx Ozone Source Attribution in the Eastern United States using Guidance from Observations during DISCOVER-AQ Maryland

PubMed Central

Goldberg, Daniel L.; Vinciguerra, Timothy P.; Anderson, Daniel C.; Hembeck, Linda; Canty, Timothy P.; Ehrman, Sheryl H.; Martins, Douglas K.; Stauffer, Ryan M.; Thompson, Anne M.; Salawitch, Ross J.; Dickerson, Russell R.

2018-01-01

A Comprehensive Air-Quality Model with Extensions (CAMx) version 6.10 simulation was assessed through comparison with data acquired during NASA’s 2011 DISCOVER-AQ Maryland field campaign. Comparisons for the baseline simulation (CB05 chemistry, EPA 2011 National Emissions Inventory) show a model overestimate of NOy by +86.2% and an underestimate of HCHO by −28.3%. We present a new model framework (CB6r2 chemistry, MEGAN v2.1 biogenic emissions, 50% reduction in mobile NOx, enhanced representation of isoprene nitrates) that better matches observations. The new model framework attributes 31.4% more surface ozone in Maryland to electric generating units (EGUs) and 34.6% less ozone to on-road mobile sources. Surface ozone becomes more NOx-limited throughout the eastern United States compared to the baseline simulation. The baseline model therefore likely underestimates the effectiveness of anthropogenic NOx reductions as well as the current contribution of EGUs to surface ozone. PMID:29618849

CAMx Ozone Source Attribution in the Eastern United States using Guidance from Observations during DISCOVER-AQ Maryland.

PubMed

Goldberg, Daniel L; Vinciguerra, Timothy P; Anderson, Daniel C; Hembeck, Linda; Canty, Timothy P; Ehrman, Sheryl H; Martins, Douglas K; Stauffer, Ryan M; Thompson, Anne M; Salawitch, Ross J; Dickerson, Russell R

2016-03-16

A Comprehensive Air-Quality Model with Extensions (CAMx) version 6.10 simulation was assessed through comparison with data acquired during NASA's 2011 DISCOVER-AQ Maryland field campaign. Comparisons for the baseline simulation (CB05 chemistry, EPA 2011 National Emissions Inventory) show a model overestimate of NO y by +86.2% and an underestimate of HCHO by -28.3%. We present a new model framework (CB6r2 chemistry, MEGAN v2.1 biogenic emissions, 50% reduction in mobile NO x , enhanced representation of isoprene nitrates) that better matches observations. The new model framework attributes 31.4% more surface ozone in Maryland to electric generating units (EGUs) and 34.6% less ozone to on-road mobile sources. Surface ozone becomes more NO x -limited throughout the eastern United States compared to the baseline simulation. The baseline model therefore likely underestimates the effectiveness of anthropogenic NO x reductions as well as the current contribution of EGUs to surface ozone.

78 FR 11583 - Approval and Promulgation of Implementation Plans Tennessee: Revisions to Volatile Organic...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-02-19

... exclusion list for VOC on the basis that they have a negligible effect on tropospheric ozone formation. Tropospheric ozone, commonly known as smog, occurs when VOC and nitrogen oxide (NO X ) react in the atmosphere. Because of the harmful health effects of ozone, EPA limits the amount of VOC and NO X that can be released...

Interface Properties of Atomic-Layer-Deposited Al2O3 Thin Films on Ultraviolet/Ozone-Treated Multilayer MoS2 Crystals.

PubMed

Park, Seonyoung; Kim, Seong Yeoul; Choi, Yura; Kim, Myungjun; Shin, Hyunjung; Kim, Jiyoung; Choi, Woong

2016-05-11

We report the interface properties of atomic-layer-deposited Al2O3 thin films on ultraviolet/ozone (UV/O3)-treated multilayer MoS2 crystals. The formation of S-O bonds on MoS2 after low-power UV/O3 treatment increased the surface energy, allowing the subsequent deposition of uniform Al2O3 thin films. The capacitance-voltage measurement of Au-Al2O3-MoS2 metal oxide semiconductor capacitors indicated n-type MoS2 with an electron density of ∼10(17) cm(-3) and a minimum interface trap density of ∼10(11) cm(-2) eV(-1). These results demonstrate the possibility of forming a high-quality Al2O3-MoS2 interface by proper UV/O3 treatment, providing important implications for their integration into field-effect transistors.

Low modeled ozone production suggests underestimation of precursor emissions (especially NOx) in Europe

NASA Astrophysics Data System (ADS)

Oikonomakis, Emmanouil; Aksoyoglu, Sebnem; Ciarelli, Giancarlo; Baltensperger, Urs; Prévôt, André Stephan Henry

2018-02-01

High surface ozone concentrations, which usually occur when photochemical ozone production takes place, pose a great risk to human health and vegetation. Air quality models are often used by policy makers as tools for the development of ozone mitigation strategies. However, the modeled ozone production is often not or not enough evaluated in many ozone modeling studies. The focus of this work is to evaluate the modeled ozone production in Europe indirectly, with the use of the ozone-temperature correlation for the summer of 2010 and to analyze its sensitivity to precursor emissions and meteorology by using the regional air quality model, the Comprehensive Air Quality Model with Extensions (CAMx). The results show that the model significantly underestimates the observed high afternoon surface ozone mixing ratios (≥ 60 ppb) by 10-20 ppb and overestimates the lower ones (< 40 ppb) by 5-15 ppb, resulting in a misleading good agreement with the observations for average ozone. The model also underestimates the ozone-temperature regression slope by about a factor of 2 for most of the measurement stations. To investigate the impact of emissions, four scenarios were tested: (i) increased volatile organic compound (VOC) emissions by a factor of 1.5 and 2 for the anthropogenic and biogenic VOC emissions, respectively, (ii) increased nitrogen oxide (NOx) emissions by a factor of 2, (iii) a combination of the first two scenarios and (iv) increased traffic-only NOx emissions by a factor of 4. For southern, eastern, and central (except the Benelux area) Europe, doubling NOx emissions seems to be the most efficient scenario to reduce the underestimation of the observed high ozone mixing ratios without significant degradation of the model performance for the lower ozone mixing ratios. The model performance for ozone-temperature correlation is also better when NOx emissions are doubled. In the Benelux area, however, the third scenario (where both NOx and VOC emissions are increased) leads to a better model performance. Although increasing only the traffic NOx emissions by a factor of 4 gave very similar results to the doubling of all NOx emissions, the first scenario is more consistent with the uncertainties reported by other studies than the latter, suggesting that high uncertainties in NOx emissions might originate mainly from the road-transport sector rather than from other sectors. The impact of meteorology was examined with three sensitivity tests: (i) increased surface temperature by 4 °C, (ii) reduced wind speed by 50 % and (iii) doubled wind speed. The first two scenarios led to a consistent increase in all surface ozone mixing ratios, thus improving the model performance for the high ozone values but significantly degrading it for the low ozone values, while the third scenario had exactly the opposite effects. Overall, the modeled ozone is predicted to be more sensitive to its precursor emissions (especially traffic NOx) and therefore their uncertainties, which seem to be responsible for the model underestimation of the observed high ozone mixing ratios and ozone production.

Seasonal prediction of US summertime ozone using statistical analysis of large scale climate patterns.

PubMed

Shen, Lu; Mickley, Loretta J

2017-03-07

We develop a statistical model to predict June-July-August (JJA) daily maximum 8-h average (MDA8) ozone concentrations in the eastern United States based on large-scale climate patterns during the previous spring. We find that anomalously high JJA ozone in the East is correlated with these springtime patterns: warm tropical Atlantic and cold northeast Pacific sea surface temperatures (SSTs), as well as positive sea level pressure (SLP) anomalies over Hawaii and negative SLP anomalies over the Atlantic and North America. We then develop a linear regression model to predict JJA MDA8 ozone from 1980 to 2013, using the identified SST and SLP patterns from the previous spring. The model explains ∼45% of the variability in JJA MDA8 ozone concentrations and ∼30% variability in the number of JJA ozone episodes (>70 ppbv) when averaged over the eastern United States. This seasonal predictability results from large-scale ocean-atmosphere interactions. Warm tropical Atlantic SSTs can trigger diabatic heating in the atmosphere and influence the extratropical climate through stationary wave propagation, leading to greater subsidence, less precipitation, and higher temperatures in the East, which increases surface ozone concentrations there. Cooler SSTs in the northeast Pacific are also associated with more summertime heatwaves and high ozone in the East. On average, models participating in the Atmospheric Model Intercomparison Project fail to capture the influence of this ocean-atmosphere interaction on temperatures in the eastern United States, implying that such models would have difficulty simulating the interannual variability of surface ozone in this region.

Does ozone enhance the remineralizing potential of nanohydroxyapatite on artificially demineralized enamel? A laser induced fluorescence study

NASA Astrophysics Data System (ADS)

Srinivasan, Samuelraj; Prabhu, Vijendra; Chandra, Subhash; Koshy, Shalini; Acharya, Shashidhar; Mahato, Krishna K.

2014-02-01

The present era of minimal invasive dentistry emphasizes the early detection and remineralization of initial enamel caries. Ozone has been shown to reverse the initial demineralization before the integrity of the enamel surface is lost. Nano-hydroxyapatite is a proven remineralizing agent for early enamel caries. In the present study, the effect of ozone in enhancing the remineralizing potential of nano-hydroxyapatite on artificially demineralized enamel was investigated using laser induced fluorescence. Thirty five sound human premolars were collected from healthy subjects undergoing orthodontic treatment. Fluorescence was recorded by exciting the mesial surfaces using 325 nm He-Cd laser with 2 mW power. Tooth specimens were subjected to demineralization to create initial enamel caries. Following which the specimens were divided into three groups, i.e ozone (ozonated water for 2 min), without ozone and artificial saliva. Remineralization regimen was followed for 3 weeks. The fluorescence spectra of the specimens were recorded from all the three experimental groups at baseline, after demineralization and remineralization. The average spectrum for each experimental group was used for statistical analysis. Fluorescence intensities of Ozone treated specimens following remineralization were higher than that of artificial saliva, and this difference was found to be statistically significant (P<0.0001). In a nutshell, ozone enhanced the remineralizing potential of nanohydroxyapatite, and laser induced fluorescence was found to be effective in assessing the surface mineral changes in enamel. Ozone can be considered an effective agent in reversing the initial enamel caries there by preventing the tooth from entering into the repetitive restorative cycle.

High Concentrations of Ozone Air Pollution on Mount Everest: Health Implications for Sherpa Communities and Mountaineers.

PubMed

Semple, John L; Moore, G W Kent; Koutrakis, Petros; Wolfson, Jack M; Cristofanelli, Paolo; Bonasoni, Paolo

2016-12-01

Semple, John L., G.W. Kent Moore, Petros Koutrakis, Jack M. Wolfson, Paolo Cristofanelli, and Paolo Bonasoni. High concentrations of ozone air pollution on Mount Everest: health implications for Sherpa communities and mountaineers. High Alt Med Biol. 17:365-369, 2016.-Introduction: Populations in remote mountain regions are increasingly vulnerable to multiple climate mechanisms that influence levels of air pollution. Few studies have reported on climate-sensitive health outcomes unique to high altitude ecosystems. In this study, we report on the discovery of high-surface ozone concentrations and the potential impact on health outcomes on Mount Everest and the high Himalaya. Surface ozone measurements were collected during ascending transects in the Mount Everest region of Nepal with passive nitrite-coated Ogawa filter samplers to obtain 8-hour personal exposures (2860-5364 m asl). In addition, the Nepal Climate Observatory-Pyramid, a GAW-WMO Global Station sited in the Khumbu Valley (5079 m asl), collected ozone mixing ratios with photometric gas analyzer. Surface ozone measurements increased with altitude with concentrations that exceed 100 ppb (8-hour exposure). Highest values were during the spring season and the result of diverse contributions: hemispheric background values, the descent of ozone-rich stratospheric air, and the transport of tropospheric pollutants occurring at different spatial scales. Multiple climate factors, including descending stratospheric ozone and imported anthropogenic air masses from the Indo-Gangetic Plain, contribute to ambient ozone exposure levels in the vicinity of Mount Everest that are similar to if not higher than those reported in industrialized cities.

Seasonal prediction of US summertime ozone using statistical analysis of large scale climate patterns

PubMed Central

Mickley, Loretta J.

2017-01-01

We develop a statistical model to predict June–July–August (JJA) daily maximum 8-h average (MDA8) ozone concentrations in the eastern United States based on large-scale climate patterns during the previous spring. We find that anomalously high JJA ozone in the East is correlated with these springtime patterns: warm tropical Atlantic and cold northeast Pacific sea surface temperatures (SSTs), as well as positive sea level pressure (SLP) anomalies over Hawaii and negative SLP anomalies over the Atlantic and North America. We then develop a linear regression model to predict JJA MDA8 ozone from 1980 to 2013, using the identified SST and SLP patterns from the previous spring. The model explains ∼45% of the variability in JJA MDA8 ozone concentrations and ∼30% variability in the number of JJA ozone episodes (>70 ppbv) when averaged over the eastern United States. This seasonal predictability results from large-scale ocean–atmosphere interactions. Warm tropical Atlantic SSTs can trigger diabatic heating in the atmosphere and influence the extratropical climate through stationary wave propagation, leading to greater subsidence, less precipitation, and higher temperatures in the East, which increases surface ozone concentrations there. Cooler SSTs in the northeast Pacific are also associated with more summertime heatwaves and high ozone in the East. On average, models participating in the Atmospheric Model Intercomparison Project fail to capture the influence of this ocean–atmosphere interaction on temperatures in the eastern United States, implying that such models would have difficulty simulating the interannual variability of surface ozone in this region. PMID:28223483

Rapid increase of ozone concentrations in Xi'an, China: Anthropogenically or naturally?

NASA Astrophysics Data System (ADS)

Wu, J.; Li, G.; Junji, C.

2017-12-01

The air quality in the Guanzhong basin, China has deteriorated recently caused by growing industries, city expansions, and increasing transportation activity. We report here a substantial increasing trend of ozone (O3) concentrations in Xi'an, the largest city of the basin, and the average observed O3 concentration in the afternoon during summertime has increased by 39% from 2013 to 2016. There are two main possible reasons for the rapid O3 increase. Motor vehicle has been reported to increase by 35% in Xi'an, which enhances the O3 precursors emissions to facilitate the O3 formation. In addition, the surface solar radiation at the meteorological site in Xi'an has been observed to intensify by 30%, which increases the photolysis rates to expedite the O3 production. A persistent high O3 episode from 16 to 22 June 2016 in Xi'an has been simulated using the WRF-CHEM model to evaluate the contribution of the transportation emission and solar radiation enhancement on the O3 trend. The model generally performs reasonably well in simulating the temporal variation and spatial distribution of near-surface O3 and NO2 concentrations against measurements in Xi'an. Sensitivity studies have revealed that the enhancement of transportation emissions and the solar radiation explains about 70% of the O3 trend from 2013 to 2016. Considering that large amounts of biogenic emissions are released over the Qinling Mountains on the south of Xi'an, which can be delivered to Xi'an under favorable meteorological conditions, enhancing O3 formation. Therefore, future studies need to be performed to evaluate impacts of the solar radiation enhancement on the biogenic emissions and further the O3 formation in Xi'an.

Forests and ozone: productivity, carbon storage, and feedbacks.

PubMed

Wang, Bin; Shugart, Herman H; Shuman, Jacquelyn K; Lerdau, Manuel T

2016-02-22

Tropospheric ozone is a serious air-pollutant, with large impacts on plant function. This study demonstrates that tropospheric ozone, although it damages plant metabolism, does not necessarily reduce ecosystem processes such as productivity or carbon sequestration because of diversity change and compensatory processes at the community scale ameliorate negative impacts at the individual level. This study assesses the impact of ozone on forest composition and ecosystem dynamics with an individual-based gap model that includes basic physiology as well as species-specific metabolic properties. Elevated tropospheric ozone leads to no reduction of forest productivity and carbon stock and to increased isoprene emissions, which result from enhanced dominance by isoprene-emitting species (which tolerate ozone stress better than non-emitters). This study suggests that tropospheric ozone may not diminish forest carbon sequestration capacity. This study also suggests that, because of the often positive relationship between isoprene emission and ozone formation, there is a positive feedback loop between forest communities and ozone, which further aggravates ozone pollution.

Comparing Model Ozone Loss during the SOLVE and SOLVE-2 Winters

NASA Technical Reports Server (NTRS)

Drdla, K.

2003-01-01

Model simulations have been used to analyze the factors influencing ozone loss during the 1999-2000 and 2002-2003 js. For both winters, the evolution of the Arctic vortex from November to April has been simulated using a trajectory-based microphysical and photochemical model. Extensive PSC formation and strong ozone depletion are evident in both winters. However, the ozone loss begins earlier in the 2002-2003 winter, with significant ozone depletion by early January. Analysis of the model results shows that during December 2002 not only cold temperatures but also the vortex structure was critical, allowing PSC-processed air parcels to experience significant solar exposure. The resultant ozone loss can be differentiated from ozone loss that occurs in the springtime, in particular because of the continued exposure to PSCs. For example, chlorine reactivation by the PSCs causes ozone loss to be insensitive to denitrification. Therefore, diagnosing the extent of ozone loss early in the winter is critical In understanding the overall winter-long ozone depletion.

Chemical effect on ozone deposition over seawater

EPA Science Inventory

Surface layer resistance plays an important role in determining ozone deposition velocity over seawater. Recent studies suggest that surface layer resistance over sea-water is influenced by wind-speed and chemical interaction at the air-water interface. Here, we investigate the e...

Chemical Controls of Ozone Dry Deposition to the Sea Surface Microlayer

NASA Astrophysics Data System (ADS)

Carpenter, L.; Chance, R.; Tinel, L.; Saint, A.; Sherwen, T.; Loades, D.; Evans, M. J.; Boxhall, P.; Hamilton, J.; Stolle, C.; Wurl, O.; Ribas-Ribas, M.; Pereira, R.

2017-12-01

Oceanic dry deposition of atmospheric ozone (O3) is both the largest and most uncertain O3 depositional sink, and is widely acknowledged to be controlled largely by chemical reactions in the sea surface microlayer (SML) involving iodide (I-) and dissolved organic material (DOM). These reactions not only determine how quickly O3 can be removed from the atmosphere, but also result in emissions of trace gases including volatile organic compounds and may constitute a source of secondary organic aerosols to the marine atmosphere. Iodide concentrations at the sea surface vary by approximately an order of magnitude spatially, leading to more than fivefold variation in ozone deposition velocities (and volatile iodine fluxes). Sea-surface temperature is a reasonable predictor of [I-], however two recent parameterisations for surface I- differ by a factor of two at low latitudes. The nature and reactivity of marine DOM to O3 is almost completely unknown, although studies have suggested approximately equivalent chemical control of I- and DOM on ozone deposition. Here we present substantial new measurements of oceanic I- in both bulk seawater and the overlying SML, and show improved estimates of the global sea surface iodide distribution. We also present analyses of water-soluble DOM isolated from the SML and bulk seawater, and corresponding laboratory studies of ozone uptake to bulk and SML seawater, with the aim of characterizing the reactivity of O3 towards marine DOM.

Bromine-Chlorine Coupling in the Antarctic Ozone Hole

NASA Technical Reports Server (NTRS)

Danilin, Michael Y.; Sze, Nien-Dak; Ko, Malcolm K. W.; Rodriquez, Jose M.; Prather, Michael J.

1996-01-01

The contribution from the chlorine and bromine species in the formation of the Antarctic ozone hole is evaluated. Since chlorine and bromine compounds are of different industrial origin, it is desirable, from a policy point of view, to be able to attribute chlorine-catalyzed loss of ozone with those reactions directly involving chlorine species, and likewise for bromine-catalyzed loss. In the stratosphere, however, most of the chemical families are highly coupled, and, for example, changes in the chlorine abundance will alter the partitioninig in other families and thus the rate of ozone loss. This modeling study examines formation of the Antarctic ozone hole for a wide range of bromine concentrations (5 - 25 pptv) and for chlorine concentrations typical of the last two decades (1.5, 2.5 and 3.5 ppbv). We follow the photochemical evolution of a single parcel of air, typical of the inner Antarctic vortex (50 mbar, 70 deg. S, NO(sub y) = 2 ppbv, with Polar Stratospheric Clouds(PSC)) from August 1 to November 1. For all of these ranges of chlorine and bromine loading, we would predict a substantial ozone hole (local depletion greater than 90%) within the de-nitrified, PSC- perturbed vortex. The contributions of the different catalytic cycles responsible for ozone loss are tabulated. The deep minimum in ozone is driven primarily by the chlorine abundance. As bromine levels decrease, the magnitude of the chlorine-catalyzed ozone loss increases to take up the slack. This is because bromine suppresses ClO by accelerating the conversion of ClO an Cl2O2 back to HCI. For this range of conditions, the local relative efficiency of ozone destruction per bromine atom to that per chlorine atom (alpha-factor) ranges from 33 to 55, decreasing with increase of bromine.

Removal of micropollutants from Sakarya River water by ozone and membrane processes.

PubMed

Yaman, Fatma Büşra; Çakmakcı, Mehmet; Yüksel, Ebubekir; Özen, İsmail; Gengeç, Erhan

2017-09-01

The removal of some pollutants in the Sakarya River was investigated in this study. Sakarya River located in Turkey flows from the northeast of Afyonkarahisar City to the Black Sea. Nineteen different micropollutants including trihalomethanes (THMs), haloacetic acids (HAAs), endocrine disrupting compound (EDC) and pharmaceuticals personal care product (PPCP) groups, and water quality parameters such as dissolved organic carbon (DOC), ultraviolet absorbance at 254 nm wavelength (UV 254 ), hardness, and conductivity values were examined. To remove the micropollutants and improve the water quality, the treatment was performed with ozone, microfiltration (MF), and ultra-filtration (UF) membranes. The highest treatment efficiency was obtained with 1 mg/L ozone dosage and UP005 UF membrane. The trihalomethan formation potential (THMFP) and haloacetic acid formation potential (HAAFP) decreased with ozone + membrane at a concentration of 79 and 75%, respectively. After the treatment with ozone + membrane, the concentration of the micropollutants in the EDC and PPCP group remained below the detection limit. It was found that by using only membrane and only ozone, the maximum DOC removal efficiency achieved was 46 and 18%, respectively; and with ozone + membrane, this efficiency increased up to 82%. The results from the High-Pressure Size Exclusion Chromatography (HPSEC) analyses pointed that the substances with high molecular weight were converted into substances with low molecular weight after the treatment. The Fourier Transform Infrared (FTIR) analysis results showed that the aromatic and aliphatic functional groups in water changed after the treatment with ozone and that the peak values decreased more after the ozone + membrane treatment.

Measurements of in situ chemical ozone (oxidant) production rates

NASA Astrophysics Data System (ADS)

Huang, Hao; Faloon, Kate; Najera, Juan; Bloss, William

2013-04-01

Tropospheric ozone is a major air pollutant, harmful to human health, agricultural crops and vegetation, the main precursor to the atmospheric oxidants which initiate the degradation of most reactive gases emitted to the atmosphere, and an important greenhouse gas in its own right. The capacity to understand and predict tropospheric ozone levels is a key goal for atmospheric science - but one which is challenging, as ozone is formed in the atmosphere from the complex oxidation of VOCs in the presence of NOx and sunlight, on a timescale such that in situ chemical processes, deposition and transport all affect ozone levels. Known uncertainties in emissions, chemistry, dynamics and deposition affect the accuracy of predictions of current and future ozone levels, and hinder development of optimal air quality policies to mitigate against ozone exposure. Recently new approaches to directly measure the local chemical ozone production rate, bypassing the many uncertainties in emissions and chemical schemes, have been developed (Cazorla & Brune, AMT 2010). Here, we describe the development of an analogous Ozone Production Rate (OPR) approach: Air is sampled into parallel reactors, within which ozone formation either occurs as in the ambient atmosphere, or is suppressed. Comparisons of ozone levels exiting a pair of such reactors determines the net chemical oxidant production rate, after correction for perturbation of the NOx-O3 photochemical steady state, and when operated under conditions such that wall effects are minimised. We report preliminary measurements of local chemical ozone production made during the UK NERC ClearfLo (Clean Air for London) campaign at an urban background location in London in January and July 2012. The OPR system was used to measure the local chemical oxidant formation rate, which is compared with observed trends in O3 and NOx and the prevailing meteorology, and with the predictions of a detailed zero-dimensional atmospheric chemistry model, constrained by observations of long-lived species.

Missing ozone-induced potential aerosol formation in a suburban deciduous forest

NASA Astrophysics Data System (ADS)

Nakayama, T.; Kuruma, Y.; Matsumi, Y.; Morino, Y.; Sato, K.; Tsurumaru, H.; Ramasamy, S.; Sakamoto, Y.; Kato, S.; Miyazaki, Y.; Mochizuki, T.; Kawamura, K.; Sadanaga, Y.; Nakashima, Y.; Matsuda, K.; Kajii, Y.

2017-12-01

As a new approach to investigating formation processes of secondary organic aerosol (SOA) in the atmosphere, ozone-induced potential aerosol formation was measured in summer at a suburban forest site surrounded by deciduous trees, near Tokyo, Japan. After passage through a reactor containing high concentrations of ozone, increases in total particle volume (average of 1.4 × 109 nm3/cm3, which corresponds to 17% that of pre-existing particles) were observed, especially during daytime. The observed aerosol formations were compared with the results of box model simulations using simultaneously measured concentrations of gaseous and particulate species. According to the model, the relative contributions of isoprene, monoterpene, and aromatic hydrocarbon oxidation to SOA formation in the reactor were 24, 21, and 55%, respectively. However, the model could explain, on average, only ∼40% of the observed particle formation, and large discrepancies between the observations and model were found, especially around noon and in the afternoon when the concentrations of isoprene and oxygenated volatile organic compounds were high. The results suggest a significant contribution of missing (unaccounted-for) SOA formation processes from identified and/or unidentified volatile organic compounds, especially those emitted during daytime. Further efforts should be made to explore and parameterize this missing SOA formation to assist in the improvement of atmospheric chemistry and climate models.

Productions of Volatile Organic Compounds (VOCs) in Surface Waters from Reactions with Atmospheric Ozone

NASA Astrophysics Data System (ADS)

Hopkins, Frances; Bell, Thomas; Yang, Mingxi

2017-04-01

Ozone (O3) is a key atmospheric oxidant, greenhouse gas and air pollutant. In marine environments, some atmospheric ozone is lost by reactions with aqueous compounds (e.g. dissolved organic material, DOM, dimethyl sulfide, DMS, and iodide) near the sea surface. These reactions also lead to formations of volatile organic compounds (VOCs). Removal of O3 by the ocean remains a large uncertainty in global and regional chemical transport models, hampering coastal air quality forecasts. To better understand the role of the ocean in controlling O3 concentrations in the coastal marine atmosphere, we designed and implemented a series of laboratory experiments whereby ambient surface seawater was bubbled with O3-enriched, VOC-free air in a custom-made glass bubble equilibration system. Gas phase concentrations of a range of VOCs were monitored continuously over the mass range m/z 33 - 137 at the outflow of the bubble equilibrator by a proton transfer reaction - mass spectrometer (PTR-MS). Gas phase O3 was also measured at the input and output of the equilibrator to monitor the uptake due to reactions with dissolved compounds in seawater. We observed consistent productions of a variety of VOCs upon reaction with O3, notably isoprene, aldehydes, and ketones. Aqueous DMS is rapidly removed from the reactions with O3. To test the importance of dissolved organic matter precursors, we added increasing (milliliter) volumes of Emiliania huxleyi culture to the equilibrator filled with aged seawater, and observed significant linear increases in gas phase concentrations of a number of VOCs. Reactions between DOM and O3 at the sea-air interface represent a potentially significant source of VOCs in marine air and a sink of atmospheric O3.

The Tropospheric Ozone Assessment Report (TOAR): A community-wide effort to quantify tropospheric ozone in a rapidly changing world

NASA Astrophysics Data System (ADS)

Cooper, O. R.; Schultz, M.; Paoletti, E.; Galbally, I. E.; Naja, M. K.; Tarasick, D. W.; Evans, M. J.; Thompson, A. M.

2017-12-01

Tropospheric ozone is a greenhouse gas and pollutant detrimental to human health and crop and ecosystem productivity. Since 1990 a large portion of the anthropogenic emissions that react in the atmosphere to produce ozone has shifted from North America and Europe to Asia. This rapid shift, coupled with limited ozone monitoring in developing nations, left scientists unable to answer the most basic questions: Which regions of the world have the greatest human and plant exposure to ozone pollution? Is ozone continuing to decline in nations with strong emissions controls? To what extent is ozone increasing in the developing world? How can the atmospheric sciences community facilitate access to the ozone metrics necessary for quantifying ozone's impact on human health and crop/ecosystem productivity? To answer these questions the International Global Atmospheric Chemistry Project (IGAC) initiated the Tropospheric Ozone Assessment Report (TOAR). With over 220 member scientists and air quality specialists from 36 nations, TOAR's mission is to provide the research community with an up-to-date scientific assessment of tropospheric ozone's global distribution and trends from the surface to the tropopause. TOAR has also built the world's largest database of surface ozone observations and generated ozone exposure and dose metrics at thousands of measurement sites around the world, freely accessible for research on the global-scale impact of ozone on climate, human health and crop/ecosystem productivity. Plots of these metrics show the regions of the world with the greatest ozone exposure for humans and crops/ecosystems, at least in areas where observations are available. The results also highlight regions where air quality is improving and where it has degraded. TOAR has also conducted the first intercomparison of tropospheric column ozone from ozonesondes and multiple satellite instruments, which provide similar estimates of the present-day tropospheric ozone burden.

Low temperature ozone oxidation of solid waste surrogates

NASA Astrophysics Data System (ADS)

Nabity, James A.; Lee, Jeffrey M.

2015-09-01

Solid waste management presents a significant challenge to human spaceflight and especially, long-term missions beyond Earth orbit. A six-month mission will generate over 300 kg of solid wastes per crewmember that must be dealt with to eliminate the need for storage and prevent it from becoming a biological hazard to the crew. There are several methods for the treatment of wastes that include oxidation via ozone, incineration, microbial oxidation or pyrolysis and physical methods such as microwave drying and compaction. In recent years, a low temperature oxidation process using ozonated water has been developed for the chemical conversion of organic wastes to CO2 and H2O. Experiments were conducted to evaluate the rate and effectiveness with which ozone oxidized several different waste materials. Increasing the surface area by chopping or shredding the solids into small pieces more than doubled the rate of oxidation. A greater flow of ozone and agitation of the ozonated water system also increased processing rates. Of the materials investigated, plastics have proven the most difficult to oxidize. The processing of plastics above the glass transition temperatures caused the plastics to clump together which reduced the exposed surface area, while processing at lower temperatures reduced surface reaction kinetics.

An analysis of the impacts of global climate and emissions changes on regional tropospheric ozone

NASA Technical Reports Server (NTRS)

John, Kuruvilla; Crist, Kevin C.; Carmichael, Gregory R.

1994-01-01

Many of the synergistic impacts resulting from future changes in emissions as well as changes in ambient temperature, moisture, and UV flux have not been quantified. A three-dimensional regional-scale photo-chemical model (STEM-2) is used in this study to evaluate these perturbations to trace gas cycles over the eastern half of the United States of America. The model was successfully used to simulate a regional-scale ozone episode (base case - June 1984) and four perturbations scenarios - viz., perturbed emissions, temperature, water vapor column, and incoming UV flux cases, and a future scenario (for the year 2034). The impact of these perturbation scenarios on the distribution of ozone and other major pollutants such as SO2 and sulfates were analyzed in detail. The spatial distribution and the concentration of ozone at the surface increased by about 5-15 percent for most cases except for the perturbed water vapor case. The regional scale surface ozone concentration distribution for the year 2034 (future scenario) showed an increase of non-attainment areas. The rural areas of Pennsylvania, West Virginia, and Georgia showed the largest change in the surface ozone field for the futuristic scenario when compared to the base case.

Climatic consequences of observed ozone loss in the 1980s: Relevance to the greenhouse problem

NASA Technical Reports Server (NTRS)

Molnar, G. I.; Ko, M. K. W.; Zhou, S.; Sze, N. D.

1994-01-01

Recently published findings using satellite and ground-based observations indicate a large winter and summertime decrease in the column abundance of ozone at high and middle latitudes during the last decade. Using a simple ozone depletion profile reflecting the observed decrease in ozone column abundance, Ramaswamy et al. (1992) showed that the negative radiative forcing that results from the ozone decrease between 1979 and 1990 approximately balanced the greenhouse climate forcing due to the chlorofluorocarbons emitted during the same period. Here, we extend the forcing analyses by calculating the equilibrium surface temperature response explicitly, using an updated version of the Atmospheric and Environmental Research two-dimensional radiative-dynamical seasonal model. The calculated steady state responses suggest that the surface cooling due to the ozone depletion in the lower stratosphere offsets about 30% of the surface warming due to greenhouse gases emitted during the same decade. The temperature offset is roughly a factor of 2 larger than the corresponding offset obtained from forcing intercomparisons. This result appears to be related to the climate feedback mechanisms operating in the model troposphere, most notably that associated with atmospheric meridional heat transport. Thus a comprehensive assessment of ozone change effects on the predicted greenhouse warming cannot be accomplished based on forcing evaluations alone. Our results also show that calculations adopting a seasonally and latitudinally dependent ozone depletion profile produce a negative forcing about 50% smaller than that calculated for the depletion profile used by Ramaswamy et al. (1992).

Interaction between isoprene and ozone fluxes in a poplar plantation and its impact on air quality at the European level

NASA Astrophysics Data System (ADS)

Zenone, Terenzio; Hendriks, Carlijn; Brilli, Federico; Fransen, Erik; Gioli, Beniamio; Portillo-Estrada, Miguel; Schaap, Martijn; Ceulemans, Reinhart

2016-09-01

The emission of isoprene and other biogenic volatile organic compounds from vegetation plays an important role in tropospheric ozone (O3) formation. The potentially large expansion of isoprene emitting species (e.g., poplars) for bioenergy production might, therefore, impact tropospheric O3 formation. Using the eddy covariance technique we have simultaneously measured fluxes isoprene, O3 and of CO2 from a poplar (Populus) plantation grown for bioenergy production. We used the chemistry transport model LOTOS-EUROS to scale-up the isoprene emissions associated with the existing poplar plantations in Europe, and we assessed the impact of isoprene fluxes on ground level O3 concentrations. Our findings suggest that isoprene emissions from existing poplar-for-bioenergy plantations do not significantly affect the ground level of O3 concentration. Indeed the overall land in Europe covered with poplar plantations has not significantly changed over the last two decades despite policy incentives to produce bioenergy crops. The current surface area of isoprene emitting poplars-for-bioenergy remains too limited to significantly enhance O3 concentrations and thus to be considered a potential threat for air quality and human health.

Interaction between isoprene and ozone fluxes in a poplar plantation and its impact on air quality at the European level.

PubMed

Zenone, Terenzio; Hendriks, Carlijn; Brilli, Federico; Fransen, Erik; Gioli, Beniamio; Portillo-Estrada, Miguel; Schaap, Martijn; Ceulemans, Reinhart

2016-09-12

The emission of isoprene and other biogenic volatile organic compounds from vegetation plays an important role in tropospheric ozone (O3) formation. The potentially large expansion of isoprene emitting species (e.g., poplars) for bioenergy production might, therefore, impact tropospheric O3 formation. Using the eddy covariance technique we have simultaneously measured fluxes isoprene, O3 and of CO2 from a poplar (Populus) plantation grown for bioenergy production. We used the chemistry transport model LOTOS-EUROS to scale-up the isoprene emissions associated with the existing poplar plantations in Europe, and we assessed the impact of isoprene fluxes on ground level O3 concentrations. Our findings suggest that isoprene emissions from existing poplar-for-bioenergy plantations do not significantly affect the ground level of O3 concentration. Indeed the overall land in Europe covered with poplar plantations has not significantly changed over the last two decades despite policy incentives to produce bioenergy crops. The current surface area of isoprene emitting poplars-for-bioenergy remains too limited to significantly enhance O3 concentrations and thus to be considered a potential threat for air quality and human health.

Enhanced formation of disinfection byproducts in shale gas wastewater-impacted drinking water supplies.

PubMed

Parker, Kimberly M; Zeng, Teng; Harkness, Jennifer; Vengosh, Avner; Mitch, William A

2014-10-07

The disposal and leaks of hydraulic fracturing wastewater (HFW) to the environment pose human health risks. Since HFW is typically characterized by elevated salinity, concerns have been raised whether the high bromide and iodide in HFW may promote the formation of disinfection byproducts (DBPs) and alter their speciation to more toxic brominated and iodinated analogues. This study evaluated the minimum volume percentage of two Marcellus Shale and one Fayetteville Shale HFWs diluted by fresh water collected from the Ohio and Allegheny Rivers that would generate and/or alter the formation and speciation of DBPs following chlorination, chloramination, and ozonation treatments of the blended solutions. During chlorination, dilutions as low as 0.01% HFW altered the speciation toward formation of brominated and iodinated trihalomethanes (THMs) and brominated haloacetonitriles (HANs), and dilutions as low as 0.03% increased the overall formation of both compound classes. The increase in bromide concentration associated with 0.01-0.03% contribution of Marcellus HFW (a range of 70-200 μg/L for HFW with bromide = 600 mg/L) mimics the increased bromide levels observed in western Pennsylvanian surface waters following the Marcellus Shale gas production boom. Chloramination reduced HAN and regulated THM formation; however, iodinated trihalomethane formation was observed at lower pH. For municipal wastewater-impacted river water, the presence of 0.1% HFW increased the formation of N-nitrosodimethylamine (NDMA) during chloramination, particularly for the high iodide (54 ppm) Fayetteville Shale HFW. Finally, ozonation of 0.01-0.03% HFW-impacted river water resulted in significant increases in bromate formation. The results suggest that total elimination of HFW discharge and/or installation of halide-specific removal techniques in centralized brine treatment facilities may be a better strategy to mitigate impacts on downstream drinking water treatment plants than altering disinfection strategies. The potential formation of multiple DBPs in drinking water utilities in areas of shale gas development requires comprehensive monitoring plans beyond the common regulated DBPs.

Kinetic assessment and modeling of an ozonation step for full-scale municipal wastewater treatment: micropollutant oxidation, by-product formation and disinfection.

PubMed

Zimmermann, Saskia G; Wittenwiler, Mathias; Hollender, Juliane; Krauss, Martin; Ort, Christoph; Siegrist, Hansruedi; von Gunten, Urs

2011-01-01

The kinetics of oxidation and disinfection processes during ozonation in a full-scale reactor treating secondary wastewater effluent were investigated for seven ozone doses ranging from 0.21 to 1.24 g O(3) g(-1) dissolved organic carbon (DOC). Substances reacting fast with ozone, such as diclofenac or carbamazepine (k(P, O3) > 10(4) M(-1) s(-1)), were eliminated within the gas bubble column, except for the lowest ozone dose of 0.21 g O(3) g(-1) DOC. For this low dose, this could be attributed to short-circuiting within the reactor. Substances with lower ozone reactivity (k(P, O3) < 10(4) M(-1) s(-1)) were only fully eliminated for higher ozone doses. The predictions of micropollutant oxidation based on coupling reactor hydraulics with ozone chemistry and reaction kinetics were up to a factor of 2.5 higher than full-scale measurements. Monte Carlo simulations showed that the observed differences were higher than model uncertainties. The overestimation of micropollutant oxidation was attributed to a protection of micropollutants from ozone attack by the interaction with aquatic colloids. Laboratory-scale batch experiments using wastewater from the same full-scale treatment plant could predict the oxidation of slowly-reacting micropollutants on the full-scale level within a factor of 1.5. The Rct value, the experimentally determined ratio of the concentrations of hydroxyl radicals and ozone, was identified as a major contribution to this difference. An increase in the formation of bromate, a potential human carcinogen, was observed with increasing ozone doses. The final concentration for the highest ozone dose of 1.24 g O(3) g(-1) DOC was 7.5 μg L(-1), which is below the drinking water standard of 10 μg L(-1). N-Nitrosodimethylamine (NDMA) formation of up to 15 ng L(-1) was observed in the first compartment of the reactor, followed by a slight elimination during sand filtration. Assimilable organic carbon (AOC) increased up to 740 μg AOC L(-1), with no clear trend when correlated to the ozone dose, and decreased by up to 50% during post-sand filtration. The disinfection capacity of the ozone reactor was assessed to be 1-4.5 log units in terms of total cell counts (TCC) and 0.5 to 2.5 log units for Escherichia coli (E. coli). Regrowth of up to 2.5 log units during sand filtration was observed for TCC while no regrowth occurred for E. coli. E. coli inactivation could not be accurately predicted by the model approach, most likely due to shielding of E. coli by flocs. Copyright © 2010 Elsevier Ltd. All rights reserved.

Chemical Data Assimilation Estimates of Continental US Ozone and Nitrogen Budgets during INTEX-A

NASA Technical Reports Server (NTRS)

Pierce, Robert B.; Schaack, Todd K.; Al-Saadi, Jassim A.; Fairlie, T. Duncan; Kittaka, Chieko; Lingenfelser, Gretchen; Natarajan, Murali; Olson, Jennifer; Soja, Amber; Zapotocny, Tom;

Surface ozone characterization at Larsemann Hills and Maitri, Antarctica.

PubMed

Ali, Kaushar; Trivedi, D K; Sahu, S K

2017-04-15

Data are analyzed in terms of daily average ozone, its diurnal variation and its relation with meteorological parameters like dry bulb temperature (T), wet bulb temperature (T w ), atmospheric pressure and wind speed based on measurement of these parameters at two Indian Antarctic stations (Larsemann Hills, and Maitri) during 28th Indian Scientific Expedition of Antarctica (ISEA) organized during Antarctic summer of the year 2008-09. The work has been carried out to investigate summer time ozone level and its day-to-day and diurnal variability at these coastal locations and to highlight possible mechanism of ozone production and destruction. The result of the analysis indicates that daily average ozone concentration at Larsemann Hills varied from ~13 and ~20ppb with overall average value of ~16ppb and at Maitri, it varied from ~16 and ~21ppb with overall average value of ~18ppb. Photochemistry is found to partially contribute occasionally to the surface layer ozone at both the stations. Lower concentration of ozone at Maitri during beginning of the observational days may be due to destruction of ozone through activated halogens, whereas higher ozone on latter days may be due to photochemistry and advective transport from east to south-east areas. Ozone concentration during blizzard episodes at both the stations is reduced due to slow photochemical production of ozone, its photochemical removal and removal through deposition of ozone molecules on precipitation particles. Diurnal variation of ozone at Larsemann Hills and Maitri has been found to be absent. Copyright © 2017 Elsevier B.V. All rights reserved.

Long-term Studies of Marine Halogen Release

NASA Astrophysics Data System (ADS)

Tschritter, J.; Holla, R.; Frieß, U.; Platt, U.

2009-04-01

Institute of Enviromental Physics, Heidelberg, Germany. Long term measurements of atmospheric trace gases using multi-axis DOAS instruments are pursued at the new SOLAS observatory on the island of Sao Vicente, (Cape Verde). This research is part of the SOPRAN (Surface Ocean Processes in the ANthropocene) project (Fördernummer:03F0462F). Reactive halogen species (RHS) such as bromine- and iodine- containing species play major roles in the chemistry of ozone in both the troposphere and lower stratosphere and thus possibly influence the ozone budget on a global scale. In addition iodine-species emitted from the ocean surface have been shown to be responsible for the production of new atmospheric particles in the marine boundary layer. This may have an effect on cloud formation and radiation transfer on local and global scales. Long term measurements of RHS abundances will help to identify their key regions and processes for formation. A new long term Multi-MAX-DOAS instrument has been installed at the SOLAS observatory on the island of Sao Vicente, (Cape Verde). The main focus of these unique measurements is the investigation of reactive halogen chemistry in the subtropical marine boundary layer based on measurements of BrO, IO, and possibly OIO. Because of its wide spectral range also the use for O4-retrievals to gain aerosol profiles is possible. IO has been detected with mixing ratios up to 1.3 ppt. For BrO an upper limit of 2 ppt could be determined.

DESIGN ARTIFACTS IN EULERIAN REGIONAL AIR QUALITY MODELS: EVALUATION OF THE EFFECTS OF LAYER THICKNESS AND VERTICAL PROFILE CORRECTION ON SURFACE OZONE CONCENTRATIONS

EPA Science Inventory

Evaluation studies of the Regional Acid Deposition Model (RADM) results have revealed that there exists high bias of surface SO2 and O3 concentrations by the model, especially during nighttime hours. omparison of the RADM results with surface measurements of hourly ozone concentr...

Camx Ozone Source Attribution in the Eastern United States Using Guidance from Observations During DISCOVER-AQ Maryland

NASA Technical Reports Server (NTRS)

Goldberg, Daniel L.; Vinciguerra, Timothy P.; Anderson, Daniel C.; Hembeck, Linda; Canty, Timothy P.; Ehrman, Sheryl H.; Martins, Douglas K.; Stauffer, Ryan M.; Thompson, Anne M.; Salawitch, Ross J.;

An improved parameterisation of ozone dry deposition to the ocean and its impact in a global climate-chemistry model

NASA Astrophysics Data System (ADS)

Luhar, Ashok K.; Galbally, Ian E.; Woodhouse, Matthew T.; Thatcher, Marcus

2017-03-01

Schemes used to parameterise ozone dry deposition velocity at the oceanic surface mainly differ in terms of how the dominant term of surface resistance is parameterised. We examine three such schemes and test them in a global climate-chemistry model that incorporates meteorological nudging and monthly-varying reactive-gas emissions. The default scheme invokes the commonly used assumption that the water surface resistance is constant. The other two schemes, named the one-layer and two-layer reactivity schemes, include the simultaneous influence on the water surface resistance of ozone solubility in water, waterside molecular diffusion and turbulent transfer, and a first-order chemical reaction of ozone with dissolved iodide. Unlike the one-layer scheme, the two-layer scheme can indirectly control the degree of interaction between chemical reaction and turbulent transfer through the specification of a surface reactive layer thickness. A comparison is made of the modelled deposition velocity dependencies on sea surface temperature (SST) and wind speed with recently reported cruise-based observations. The default scheme overestimates the observed deposition velocities by a factor of 2-4 when the chemical reaction is slow (e.g. under colder SSTs in the Southern Ocean). The default scheme has almost no temperature, wind speed, or latitudinal variations in contrast with the observations. The one-layer scheme provides noticeably better variations, but it overestimates deposition velocity by a factor of 2-3 due to an enhancement of the interaction between chemical reaction and turbulent transfer. The two-layer scheme with a surface reactive layer thickness specification of 2.5 µm, which is approximately equal to the reaction-diffusive length scale of the ozone-iodide reaction, is able to simulate the field measurements most closely with respect to absolute values as well as SST and wind-speed dependence. The annual global oceanic deposition of ozone determined using this scheme is approximately half of the original oceanic deposition obtained using the default scheme, and it corresponds to a 10 % decrease in the original estimate of the total global ozone deposition. The previously reported modelled estimate of oceanic deposition is roughly one-third of total deposition and with this new parameterisation it is reduced to 12 % of the modelled total global ozone deposition. Deposition parameterisation influences the predicted atmospheric ozone mixing ratios, especially in the Southern Hemisphere. For the latitudes 45-70° S, the two-layer scheme improves the prediction of ozone observed at an altitude of 1 km by 7 % and that within the altitude range 1-6 km by 5 % compared to the default scheme.

Heterogeneous nano-Fe/Ca/CaO catalytic ozonation for selective surface hydrophilization of plastics containing brominated and chlorinated flame retardants (B/CFRs): separation from automobile shredder residue by froth flotation.

PubMed

Mallampati, Srinivasa Reddy; Lee, Byoung Ho; Mitoma, Yoshiharu; Simion, Cristian

2017-02-01

One method of weakening the inherently hydrophobic surface of plastics relevant to flotation separation is heterogeneous nano-Fe/Ca/CaO catalytic ozonation. Nano-Fe/Ca/CaO-catalyzed ozonation for 15 min efficiently decreases the surface hydrophobicity of brominated and chlorinated flame retardant (B/CFR)-containing plastics (such as acrylonitrile-butadienestyrene (ABS), high-impact polystyrene (HIPS), and polyvinyl chloride (PVC)) in automobile shredder residue (ASR) to such an extent that their flotation ability is entirely depressed. Such a hydrophilization treatment also stimulates the ABS, HIPS, and PVC surface roughness, wetting of the surface, and the thermodynamic equilibrium conditions at the surface and ultimately changes surface polarity. SEM-EDS, AFM, and XPS analyses of the PVC and ABS surfaces demonstrated a marked decrease in [Cl/Br] and a significant increase in the number of hydrophilic groups, such as C-O, C=O, and (C=O)-O. Under froth flotation conditions at 50 rpm, about 99.5 % of ABS and 99.5 % of HIPS in ASR samples settled out, resulting in a purity of 98 and 98.5 % for ABS and HIPS in ASR samples, respectively. Furthermore, at 150 rpm, we also obtained 100 % PVC separation in the settled fraction, with 98 % purity in ASR. Total recovery of non-B/CFR-containing plastics reached nearly 100 % in the floating fraction. The amount of nano-Fe/Ca/CaO reagent employed during ozonation is very small, and additional removal of surface contaminants from the recycled ASR plastic surfaces by ozonation makes the developed process simpler, greener, and more effective.

Fate of Chloromethanes in the Atmospheric Environment: Implications for Human Health, Ozone Formation and Depletion, and Global Warming Impacts

PubMed Central

Tsai, Wen-Tien

2017-01-01

Among the halogenated hydrocarbons, chloromethanes (i.e., methyl chloride, CH3Cl; methylene chloride, CH2Cl2; chloroform, CHCl3; and carbon tetrachloride, CCl4) play a vital role due to their extensive uses as solvents and chemical intermediates. This article aims to review their main chemical/physical properties and commercial/industrial uses, as well as the environment and health hazards posed by them and their toxic decomposition products. The environmental properties (including atmospheric lifetime, radiative efficiency, ozone depletion potential, global warming potential, photochemical ozone creation potential, and surface mixing ratio) of these chlorinated methanes are also reviewed. In addition, this paper further discusses their atmospheric fates and human health implications because they are apt to reside in the lower atmosphere when released into the environment. According to the atmospheric degradation mechanism, their toxic degradation products in the troposphere include hydrogen chloride (HCl), carbon monoxide (CO), chlorine (Cl2), formyl chloride (HCOCl), carbonyl chloride (COCl2), and hydrogen peroxide (H2O2). Among them, COCl2 (also called phosgene) is a powerful irritating gas, which is easily hydrolyzed or thermally decomposed to form hydrogen chloride. PMID:29051455

Adsorption characteristics of trace levels of bromate in drinking water by modified bamboo-based activated carbons.

PubMed

Chen, Ho-Wen; Chuang, Yen Hsun; Hsu, Cheng-Feng; Huang, Winn-Jung

2017-09-19

This study was undertaken to investigate the adsorption kinetics and isotherms of bromate (BrO 3 - ) on bamboo charcoals that are activated with nitrogen and water vapor. Bamboo-based activated carbon (AC) was dipped in acid and oxidized in a mixture of potassium permanganate and sulfuric acid. Oxidation treatment considerably improved the physicochemical properties of AC, including purity, pore structure and surface nature, significantly enhancing BrO 3 - adsorption capacity. AC with many oxygenated groups and a high mesopore volume exhibited a particularly favorable tendency for BrO 3 - adsorption. Its adsorption of BrO 3 - is best fitted using Langmuir isotherm, and forms a monolayer. A kinetic investigation revealed that the adsorption of BrO 3 - by the ACs involved chemical sorption and was controlled by intra-particle diffusion. The competitive effects of natural organic matter (NOM) on AC were evaluated, and found to reduce the capacity of carbon to adsorb BrO 3 - . Residual dissolved ozone reacted with AC, reducing its capacity to absorb BrO 3 - . Proper dosing and staging of the ozonation processes can balance the ozone treatment efficiency, BrO 3 - formation, and the subsequent removal of BrO 3 - .

Ozone inhibits corrosion in cooling towers

NASA Technical Reports Server (NTRS)

French, K. R.; Howe, R. D.; Humphrey, M. F.

1980-01-01

Commercially available corona discharge ozone generator, fitted onto industrial cooling tower, significantly reduces formation of scales (calcium carbonate) and corrosion. System also controls growth of algae and other microorganisms. Modification lowers cost and improves life of cooling system.

Atmospheric Impacts of Emissions from Oil and Gas Development in the Uintah Basin, Utah, USA

NASA Astrophysics Data System (ADS)

Helmig, D.; Boylan, P. J.; Hueber, J.; Van Dam, B. A.; Mauldin, L.; Parrish, D. D.

2012-12-01

In the Uintah Basin in northeast Utah, USA, surface ozone levels during winter months have approached and on occasion exceeded the US National Ambient Air Quality Standard (NAAQS). Emissions from the extensive oil and gas exploration in this region are suspected to be the cause of these ozone episodes; however emission rates and photochemical processes are uncertain. During February 2012 continuous surface measurements and vertical profiling from a tethered balloon platform at the Horsepool site yielded high resolution boundary layer profile data on ozone and ozone precursor compounds, i.e. nitrogen oxides and volatile organic compounds as well as methane. Findings from this study were: 1. Surface ozone during the study period, which had no snow cover, did not exceed the NAAQS. 2. Nitrogen oxides varied from 1-50 ppbv pointing towards significant emission sources, likely from oil and gas operations. 3. Methane concentrations were elevated, reaching up to ~10 times its Northern Hemisphere (NH) atmospheric background. 3. Light non-methane hydrocarbons (NMHC) constituted the main fraction of volatile organic compounds. NMHC concentrations were highly elevated, exceeding levels seen in urban areas. 4. Ozone, methane, NOx and VOC showed distinct diurnal cycles, with large concentration increases seen at night, except for ozone, which showed the opposite behavior. 5. During nighttime concentrations of NOx, NMHC, and methane built up near the surface to levels that were much higher than their daytime concentrations. 6. Comparing NMHC to methane concentrations indicates a mass flux ratio of ~30% for total VOC/methane emissions for the Uintah Basin.

Ozone adsorption on carbon nanoparticles

NASA Astrophysics Data System (ADS)

Chassard, Guillaume; Gosselin, Sylvie; Visez, Nicolas; Petitprez, Denis

2014-05-01

Carbonaceous particles produced by incomplete combustion or thermal decomposition of hydrocarbons are ubiquitous in the atmosphere. On these particles are adsorbed hundreds of chemical species. Those of great concern to health are polycyclic aromatic hydrocarbons (PAHs). During atmospheric transport, particulate PAHs react with gaseous oxidants. The induced chemical transformations may change toxicity and hygroscopicity of these potentially inhalable particles. The interaction between ozone and carbon particles has been extensively investigated in literature. However ozone adsorption and surface reaction mechanisms are still ambiguous. Some studies described a fast catalytic decomposition of ozone initiated by an atomic oxygen chemisorption followed by a molecular oxygen release [1-3]. Others suggested a reversible ozone adsorption according to Langmuir-type behaviour [4,5]. The aim of this present study is a better understanding of ozone interaction with carbon surfaces. An aerosol of carbon nanoparticles was generated by flowing synthetic air in a glass tube containing pure carbon (primary particles < 50 nm), under magnetic stirring. The aerosol was then mixed with ozone in an aerosol flow tube. Ozone uptake experiments were performed with different particles concentrations with a fixed ozone concentration. The influence of several factors on kinetics was examined: initial ozone concentration, particle size (50 nm ≤ Dp ≤ 200 nm) and competitive adsorption (with probe molecule and water). The effect of initial ozone concentration was first studied. Accordingly to literature, it has been observed that the number of gas-phase ozone molecules lost per unit particle surface area tends towards a plateau for high ozone concentration suggesting a reversible ozone adsorption according to a Langmuir mechanism. We calculated the initial reaction probability between O3 and carbon particles.An initial uptake coefficient of 1.10-4 was obtained. Similar experiments were realized by selecting the particles size with a differential mobility analyser. We observed a strong size-dependent increase in reactivity with the decrease of particles size. This result is relevant for the health issues. Indeed the smallest particles are most likely to penetrate deep into the lungs. Competitive reactions between ozone and other species like H2O or atomic oxygen were also considered. Oxygen atoms were generated by photolysis of O3 (or O2) and were chosen because it is believed to form the same reactive oxygen intermediates than ozone. A weak water physisorption on soot was observed revealing hydrophobic properties of particles. Oxygen atoms were found to be strongly reactive. A Langmuir behavior was observed for oxygen atoms adsorption on carbon particles and we were able to determine an initial uptake coefficient of approximately 2.10-2. [1] Fenidel, W., et al., Interaction between carbon or iron aerosol particles and ozone. Atmospheric Environment, 1995. 29(9): p. 967-973. [2] Smith, D. and A. Chughtai, Reaction kinetics of ozone at low concentrations with n-hexane soot. Journal of geophysical research, 1996. 101(D14): p. 19607-19,620. [3] Kamm, S., et al., The heterogeneous reaction of ozone with soot aerosol. Atmospheric Environment, 1999. 33(28): p. 4651-4661. [4] Stephens, S., M.J. Rossi, and D.M. Golden, The heterogeneous reaction of ozone on carbonaceous surfaces. International journal of chemical kinetics, 1986. 18(10): p. 1133-1149. [5] Pöschl, U., et al., Interaction of ozone and water vapor with spark discharge soot aerosol particles coated with benzo [a] pyrene: O3 and H2O adsorption, benzo [a] pyrene degradation, and atmospheric implications. The Journal of Physical Chemistry A, 2001. 105(16): p. 4029-4041.

WRF-Chem simulated surface ozone over south Asia during the pre-monsoon: effects of emission inventories and chemical mechanisms

NASA Astrophysics Data System (ADS)

Sharma, Amit; Ojha, Narendra; Pozzer, Andrea; Mar, Kathleen A.; Beig, Gufran; Lelieveld, Jos; Gunthe, Sachin S.

2017-12-01

We evaluate numerical simulations of surface ozone mixing ratios over the south Asian region during the pre-monsoon season, employing three different emission inventories in the Weather Research and Forecasting model with Chemistry (WRF-Chem) with the second-generation Regional Acid Deposition Model (RADM2) chemical mechanism: the Emissions Database for Global Atmospheric Research - Hemispheric Transport of Air Pollution (EDGAR-HTAP), the Intercontinental Chemical Transport Experiment phase B (INTEX-B) and the Southeast Asia Composition, Cloud, Climate Coupling Regional Study (SEAC4RS). Evaluation of diurnal variability in modelled ozone compared to observational data from 15 monitoring stations across south Asia shows the model ability to reproduce the clean, rural and polluted urban conditions over this region. In contrast to the diurnal average, the modelled ozone mixing ratios during noontime, i.e. hours of intense photochemistry (11:30-16:30 IST - Indian Standard Time - UTC +5:30), are found to differ among the three inventories. This suggests that evaluations of the modelled ozone limited to 24 h average are insufficient to assess uncertainties associated with ozone buildup. HTAP generally shows 10-30 ppbv higher noontime ozone mixing ratios than SEAC4RS and INTEX-B, especially over the north-west Indo-Gangetic Plain (IGP), central India and southern India. The HTAP simulation repeated with the alternative Model for Ozone and Related Chemical Tracers (MOZART) chemical mechanism showed even more strongly enhanced surface ozone mixing ratios due to vertical mixing of enhanced ozone that has been produced aloft. Our study indicates the need to also evaluate the O3 precursors across a network of stations and the development of high-resolution regional inventories for the anthropogenic emissions over south Asia accounting for year-to-year changes to further reduce uncertainties in modelled ozone over this region.

On the role of ozone feedback in the ENSO amplitude response under global warming

NASA Astrophysics Data System (ADS)

Nowack, P. J.; Braesicke, P.; Abraham, N. L.; Pyle, J. A.

2017-12-01

The El Niño-Southern Oscillation (ENSO) in the tropical Pacific is of key importance to global climate and weather. However, climate models still disagree on the ENSO's response under climate change. Here we show that typical model representations of ozone can have a first-order impact on ENSO amplitude projections in climate sensitivity simulations (i.e. standard abrupt 4xCO2). We mainly explain this effect by the lapse rate adjustment of the tropical troposphere to ozone changes in the upper troposphere and lower stratosphere (UTLS) under 4xCO2. The ozone-induced lapse rate changes modify the Walker circulation response to the CO2 forcing and consequently tropical Pacific surface temperature gradients. Therefore, not including ozone feedbacks increases the number of extreme ENSO events in our model. In addition, we demonstrate that even if ozone changes in the tropical UTLS are included in the simulations, the neglect of the ozone response in the middle-upper stratosphere still leads to significantly larger ENSO amplitudes (compared to simulations run with a fully interactive atmospheric chemistry scheme). Climate modeling studies of the ENSO often neglect changes in ozone. Our results imply that this could affect the inter-model spread found in ENSO projections and, more generally, surface climate change simulations. We discuss the additional complexity in quantifying such ozone-related effects that arises from the apparent model dependency of chemistry-climate feedbacks and, possibly, their range of surface climate impacts. In conclusion, we highlight the need to understand better the coupling between ozone, the tropospheric circulation, and climate variability. Reference: Nowack PJ, Braesicke P, Abraham NL, and Pyle JA (2017), On the role of ozone feedback in the ENSO amplitude response under global warming, Geophys. Res. Lett. 44, 3858-3866, doi:10.1002/2016GL072418.

Biocidal action of ozone-treated polystyrene surfaces on vegetative and sporulated bacteria

NASA Astrophysics Data System (ADS)

Mahfoudh, Ahlem; Barbeau, Jean; Moisan, Michel; Leduc, Annie; Séguin, Jacynthe

2010-03-01

Surfaces of materials can be modified to ensure specific interaction features with microorganisms. The current work discloses biocidal properties of polystyrene (PS) Petri-dish surfaces that have been exposed to a dry gaseous-ozone flow. Such treated PS surfaces are able to inactivate various species of vegetative and sporulated bacteria on a relatively short contact time. Denaturation of proteins seems likely based on a significant loss of enzymatic activity of the lysozyme protein. Characterization of these surfaces by atomic-force microscopy (AFM), Fourier-transform infra-red (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS) reveals specific structural and chemical modifications as compared to untreated PS. Persistence of the biocidal properties of these treated surfaces is observed. This ozone-induced process is technically simple to achieve and does not require active precursors as in grafting.

Ozone production in remote oceanic and industrial areas derived from ship based measurements of peroxy radicals during TexAQS 2006

NASA Astrophysics Data System (ADS)

Sommariva, R.; Brown, S. S.; Roberts, J. M.; Brookes, D. M.; Parker, A. E.; Monks, P. S.; Bates, T. S.; Bon, D.; de Gouw, J. A.; Frost, G. J.; Gilman, J. B.; Goldan, P. D.; Herndon, S. C.; Kuster, W. C.; Lerner, B. M.; Osthoff, H. D.; Tucker, S. C.; Warneke, C.; Williams, E. J.; Zahniser, M. S.

2011-03-01

During the Texas Air Quality Study II (TexAQS 2006) campaign, a PEroxy Radical Chemical Amplifier (PERCA) was deployed on the NOAA research vessel R/V Brown to measure total peroxy radicals (HO2+Σ RO2). Day-time mixing ratios of HO2+Σ RO2 between 25 and 110 ppt were observed throughout the study area - the Houston/Galveston region and the Gulf coast of the US - and analyzed in relation to measurements of nitrogen oxides, volatile organic compounds (VOC) and photolysis rates to assess radical sources and sinks in the region. The measurements of HO2+Σ RO2 were used to calculate the in-situ net photochemical formation of ozone. Measured median values ranged from 0.6 ppb/h in clean oceanic air masses up to several tens of ppb/h in the most polluted industrial areas. The results are consistent with previous studies and generally agree with observations made during the previous TexAQS 2000 field campaign. The net photochemical ozone formation rates determined at Barbours Cut, a site immediately south of the Houston Ship Channel, were analyzed in relation to local wind direction and VOC reactivity to understand the relationship between ozone formation and local VOC emissions. The measurements of HO2+Σ RO2 made during the R/V Brown TexAQS 2006 cruise indicate that ozone formation is NOx-limited in the Houston/Galveston region and influenced by highly reactive hydrocarbons, especially alkenes from urban and industrial sources and their photo-oxidation products, such as formaldehyde.

Ozone production in remote oceanic and industrial areas derived from ship based measurements of peroxy radicals during TexAQS 2006

NASA Astrophysics Data System (ADS)

Sommariva, R.; Brown, S. S.; Roberts, J. M.; Brookes, D. M.; Parker, A. E.; Monks, P. S.; Bates, T. S.; Bon, D.; de Gouw, J. A.; Frost, G. J.; Gilman, J. B.; Goldan, P. D.; Herndon, S. C.; Kuster, W. C.; Lerner, B. M.; Osthoff, H. D.; Tucker, S. C.; Warneke, C.; Williams, E. J.; Zahniser, M. S.

2010-10-01

During the Texas Air Quality Study II (TexAQS 2006) campaign, a PEroxy Radical Chemical Amplifier (PERCA) was deployed on the NOAA research vessel R/V Brown to measure total peroxy radicals (HO2+ΣRO2). Day-time mixing ratios of HO2+ΣRO2 between 25 and 110 ppt were observed throughout the study area - the Houston/Galveston region and the Gulf coast of the U.S. - and analyzed in relation to measurements of nitrogen oxides, volatile organic compounds (VOC) and photolysis rates to assess radical sources and sinks in the region. The measurements of HO2+ΣRO2 were used to calculate the in-situ net photochemical formation of ozone. Measured median values ranged from 0.6 ppb/h in clean oceanic air masses up to several tens of ppb/h in the most polluted industrial areas. The results are consistent with previous studies and generally agree with observations made during the previous TexAQS 2000 field campaign. The net photochemical ozone formation rates determined at Barbours Cut, a site immediately south of the Houston Ship Channel, were analyzed in relation to local wind direction and VOC reactivity to understand the relationship between ozone formation and local VOC emissions. The measurements of HO2+ΣRO2 made during the R/V Brown TexAQS 2006 cruise indicate that ozone formation is NOx-limited in the Houston/Galveston region and influenced by highly reactive hydrocarbons, especially alkenes from urban and industrial sources and their photooxidation products, such as formaldehyde.

78 FR 23149 - Air Quality: Revision to Definition of Volatile Organic Compounds-Exclusion of trans 1-chloro-3,3...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-04-18

... contribution to tropospheric ozone formation. Because EPA received one adverse comment, we are withdrawing the... air quality standards (NAAQS) for ozone under title I of the Clean Air Act (CAA). The direct final... of preparing SIPs to attain the NAAQS for ozone under title I of the CAA. If it had become effective...

78 FR 4796 - Approval and Promulgation of Implementation Plans; South Carolina: New Source Review-Prevention...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-01-23

... on the basis that they have a negligible contribution to tropospheric formation of ozone.\\17\\ EPA has... changes. \\17\\ Tropospheric ozone, commonly known as smog, occurs when VOC and nitrogen oxide (NO X ) react... for PM 2.5, PM 10 , ozone and lead that are found at Regulation 61.62-5, Standard No. 2. The four SIP...

Mechanisms of impact of greenhouse gases on the Earth's ozone layer in the Polar Regions

NASA Astrophysics Data System (ADS)

Zadorozhny, Alexander; Dyominov, Igor

A numerical 2-D zonally averaged interactive dynamical radiative-photochemical model of the atmosphere including aerosol physics is used to examine the impact of the greenhouse gases CO2, CH4, and N2O on the future long-term changes of the Earth's ozone layer, in particular on its expected recovery after reduction of anthropogenic discharges of chlorine and bromine compounds into the atmosphere. The model allows calculating self-consistently diabatic circu-lation, temperature, gaseous composition of the troposphere and stratosphere at latitudes from the North to South Poles, as well as distribution of sulphate aerosol particles and polar strato-spheric clouds (PSCs) of types I and II. The scenarios of expected changes of the anthropogenic pollutants for the period from 1980 through 2050 are taken from Climate Change 2001. The processes, which determine the influence of anthropogenic growth of atmospheric abun-dance of the greenhouse gases on the long-term changes of the Earth's ozone layer in the Polar Regions, have been studied in details. Expected cooling of the stratosphere caused by increases of greenhouse gases, most importantly CO2, essentially influences the ozone layer by two ways: through temperature dependencies of the gas phase reaction rates and through enhancement of polar ozone depletion via increased PSC formation. The model calculations show that a weak-ness in efficiencies of all gas phase catalytic cycles of the ozone destruction due to cooling of the stratosphere is a dominant mechanism of the impact of the greenhouse gases on the ozone layer in Antarctic as well as at the lower latitudes. This mechanism leads to a significant acceleration of the ozone layer recovery here because of the greenhouse gases growth. On the contrary, the mechanism of the impact of the greenhouse gases on the ozone through PSC modification be-gins to be more effective in Arctic in comparison with the gas phase mechanism in springs after about 2020, which leads to retard the expected recovery of the ozone layer here. The difference in the impact of the greenhouse gases on the ozone layer at the southern and northern polar latitudes through PCS modification is determined by the difference in temperature regimes of the Polar Regions. The mechanism of the impact of the greenhouse gases on the polar ozone by means of modification of sulphate aerosol distribution in the atmosphere has been revealed and investigated, too. Numerical experiments show that enhancement of the surface area density of sulphate aerosol in the stratosphere caused by the growth of the greenhouse gases will reduce significantly the ozone depletion during the Antarctic ozone hole.

Air-quality in the mid-21st century for the city of Paris under two climate scenarios; from regional to local scale

NASA Astrophysics Data System (ADS)

Markakis, K.; Valari, M.; Colette, A.; Sanchez, O.; Perrussel, O.; Honore, C.; Vautard, R.; Klimont, Z.; Rao, S.

2014-01-01

Ozone and PM2.5 concentrations over the city of Paris are modeled with the CHIMERE air-quality model at 4 km × 4 km horizontal resolution for two future emission scenarios. High-resolution (1 km × 1 km) emission projection until 2020 for the greater Paris region is developed by local experts (AIRPARIF) and is further extended to year 2050 based on regional scale emission projections developed by the Global Energy Assessment. Model evaluation is performed based on a 10 yr control simulation. Ozone is in very good agreement with measurements while PM2.5 is underestimated by 20% over the urban area mainly due to a large wet bias in wintertime precipitation. A significant increase of maximum ozone relative to present time levels over Paris is modeled under the "business as usual" scenario (+7 ppb) while a more optimistic mitigation scenario leads to moderate ozone decrease (-3.5 ppb) in year 2050. These results are substantially different to previous regional scale projections where 2050 ozone is found to decrease under both future scenarios. A sensitivity analysis showed that this difference is due to the fact that ozone formation over Paris at the current, urban scale study, is driven by VOC-limited chemistry, whereas at the regional scale ozone formation occurs under NOx-sensitive conditions. This explains why the sharp NOx reductions implemented in the future scenarios have a different effect on ozone projections at different scales. In rural areas projections at both scales yield similar results showing that the longer time-scale processes of emission transport and ozone formation are less sensitive to model resolution. PM2.5 concentrations decrease by 78% and 89% under "business as usual" and "mitigation" scenarios respectively compared to present time period. The reduction is much more prominent over the urban part of the domain due to the effective reductions of road transport and residential emissions resulting in the smoothing of the large urban increment modelled in the control simulation.

Air quality in the mid-21st century for the city of Paris under two climate scenarios; from the regional to local scale

NASA Astrophysics Data System (ADS)

Markakis, K.; Valari, M.; Colette, A.; Sanchez, O.; Perrussel, O.; Honore, C.; Vautard, R.; Klimont, Z.; Rao, S.

2014-07-01

Ozone and PM2.5 concentrations over the city of Paris are modeled with the CHIMERE air-quality model at 4 km × 4 km horizontal resolution for two future emission scenarios. A high-resolution (1 km × 1 km) emission projection until 2020 for the greater Paris region is developed by local experts (AIRPARIF) and is further extended to year 2050 based on regional-scale emission projections developed by the Global Energy Assessment. Model evaluation is performed based on a 10-year control simulation. Ozone is in very good agreement with measurements while PM2.5 is underestimated by 20% over the urban area mainly due to a large wet bias in wintertime precipitation. A significant increase of maximum ozone relative to present-day levels over Paris is modeled under the "business-as-usual" scenario (+7 ppb) while a more optimistic "mitigation" scenario leads to a moderate ozone decrease (-3.5 ppb) in year 2050. These results are substantially different to previous regional-scale projections where 2050 ozone is found to decrease under both future scenarios. A sensitivity analysis showed that this difference is due to the fact that ozone formation over Paris at the current urban-scale study is driven by volatile organic compound (VOC)-limited chemistry, whereas at the regional-scale ozone formation occurs under NOx-sensitive conditions. This explains why the sharp NOx reductions implemented in the future scenarios have a different effect on ozone projections at different scales. In rural areas, projections at both scales yield similar results showing that the longer timescale processes of emission transport and ozone formation are less sensitive to model resolution. PM2.5 concentrations decrease by 78% and 89% under business-as-usual and mitigation scenarios, respectively, compared to the present-day period. The reduction is much more prominent over the urban part of the domain due to the effective reductions of road transport and residential emissions resulting in the smoothing of the large urban increment modeled in the control simulation.

Development of KRISS standard reference photometer (SRP) for ambient ozone measurement

NASA Astrophysics Data System (ADS)

Lee, S.; Lee, J.

2014-12-01

Surface ozone has adverse impacts on human health and ecosystem. Accurate measurement of ambient ozone concentration is essential for developing effective mitigation strategies and understanding atmospheric chemistry. Korea Research Institute of Standards and Science (KRISS) has developed new ozone standard reference photometers (SRPs) for the calibration of ambient ozone instruments. The basic principle of the KRISS ozone SRPs is to determine the absorption of ultraviolet radiation at a specific wavelength, 253.7 nm, by ozone in the atmosphere. Ozone concentration is calculated by converting UV transmittance through the Beer-Lambert Law. This study introduces the newly developed ozone SRPs and characterizes their performance through uncertainty analysis and comparison with BIPM (International Bureau of Weights and Measures) SRP.

Development of Compact Ozonizer with High Ozone Output by Pulsed Power

NASA Astrophysics Data System (ADS)

Tanaka, Fumiaki; Ueda, Satoru; Kouno, Kanako; Sakugawa, Takashi; Akiyama, Hidenori; Kinoshita, Youhei

Conventional ozonizer with a high ozone output using silent or surface discharges needs a cooling system and a dielectric barrier, and therefore becomes a large machine. A compact ozonizer without the cooling system and the dielectric barrier has been developed by using a pulsed power generated discharge. The wire to plane electrodes made of metal have been used. However, the ozone output was low. Here, a compact and high repetition rate pulsed power generator is used as an electric source of a compact ozonizer. The ozone output of 6.1 g/h and the ozone yield of 86 g/kWh are achieved at 500 pulses per second, input average power of 280 W and an air flow rate of 20 L/min.

Natural zeolite reactivity towards ozone: the role of compensating cations.

PubMed

Valdés, Héctor; Alejandro, Serguei; Zaror, Claudio A

2012-08-15

Among indoor pollutants, ozone is recognised to pose a threat to human health. Recently, low cost natural zeolites have been applied as alternative materials for ozone abatement. In this work, the effect of compensating cation content of natural zeolite on ozone removal is studied. A Chilean natural zeolite is used here as starting material. The amount of compensating cations in the zeolite framework was modified by ion exchange using an ammonium sulphate solution (0.1 mol L(-1)). Characterisation of natural and modified zeolites were performed by X-ray powder diffraction (XRD), nitrogen adsorption at 77K, elemental analysis, X-ray fluorescence (XRF), thermogravimetric analysis coupled with mass spectroscopy (TGA-MS), and temperature-programmed desorption of ammonia (NH(3)-TPD). Ozone adsorption and/or decomposition on natural and modified zeolites were studied by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Results show that the zeolite compensating cation content affects ozone interaction with zeolite active sites. Ammonium ion-exchange treatments followed by thermal out-gassing at 823 K, reduces ozone diffusion resistance inside the zeolite framework, increasing ozone abatement on zeolite surface active sites. Weak and strong Lewis acid sites of zeolite surface are identified here as the main active sites responsible of ozone removal. Copyright © 2012 Elsevier B.V. All rights reserved.

Ultraviolet-ozone treatment reduces levels of disease-associated prion protein and prion infectivity

USGS Publications Warehouse

Johnson, C.J.; Gilbert, P.; McKenzie, D.; Pedersen, J.A.; Aiken, Judd M.

2009-01-01

Background. Transmissible spongiform encephalopathies (TSEs) are a group of fatal neurodegenerative diseases caused by novel infectious agents referred to as prions. Prions appear to be composed primarily, if not exclusively, of a misfolded isoform of the cellular prion protein. TSE infectivity is remarkably stable and can resist many aggressive decontamination procedures, increasing human, livestock and wildlife exposure to TSEs. Findings. We tested the hypothesis that UV-ozone treatment reduces levels of the pathogenic prion protein and inactivates the infectious agent. We found that UV-ozone treatment decreased the carbon and prion protein content in infected brain homogenate to levels undetectable by dry-ashing carbon analysis or immunoblotting, respectively. After 8 weeks of ashing, UV-ozone treatment reduced the infectious titer of treated material by a factor of at least 105. A small amount of infectivity, however, persisted despite UV-ozone treatment. When bound to either montmorillonite clay or quartz surfaces, PrPTSE was still susceptible to degradation by UV-ozone. Conclusion. Our findings strongly suggest that UV-ozone treatment can degrade pathogenic prion protein and inactivate prions, even when the agent is associated with surfaces. Using larger UV-ozone doses or combining UV-ozone treatment with other decontaminant methods may allow the sterilization of TSE-contaminated materials. ?? 2009 Aiken et al; licensee BioMed Central Ltd.

Contribution of ozone to airborne aldehyde formation in Paris homes.

PubMed

Rancière, Fanny; Dassonville, Claire; Roda, Célina; Laurent, Anne-Marie; Le Moullec, Yvon; Momas, Isabelle

2011-09-15

Indoor aldehydes may result from ozone-initiated chemistry, mainly documented by experimental studies. As part of an environmental investigation included in the PARIS birth cohort, the aim of this study was to examine ozone contribution to airborne aldehyde formation in Paris homes. Formaldehyde, acetaldehyde and hexaldehyde levels, as well as styrene, nitrogen dioxide and nicotine concentrations, comfort parameters and carbon dioxide levels, were measured twice during the first year of life of the babies. Ambient ozone concentrations were collected from the closest background station of the regional air monitoring network. Traffic-related nitrogen oxide concentrations in front of the dwellings were estimated by an air pollution dispersion model. Home characteristics and families' way of life were described by questionnaires. Stepwise multiple linear regression models were used to link aldehyde levels with ambient ozone concentrations and a few aldehyde precursors involved in oxidation reactions, adjusting for other indoor aldehyde sources, comfort parameters and traffic-related nitrogen oxides. A 4 and 11% increase in formaldehyde and hexaldehyde levels was pointed out when 8-hour ozone concentrations increased by 20 μg/m(3). The influence of potential precursors such as indoor styrene level and frequent use of air fresheners, containing unsaturated volatile organic compounds as terpenes, was also found. Thus, our results suggest that ambient ozone can significantly impact indoor air quality, especially with regard to formaldehyde and hexaldehyde levels. Copyright © 2011 Elsevier B.V. All rights reserved.

Chemical composition of gas-phase organic carbon emissions from motor vehicles and implications for ozone production.

PubMed

Gentner, Drew R; Worton, David R; Isaacman, Gabriel; Davis, Laura C; Dallmann, Timothy R; Wood, Ezra C; Herndon, Scott C; Goldstein, Allen H; Harley, Robert A

2013-10-15

Motor vehicles are major sources of gas-phase organic carbon, which includes volatile organic compounds (VOCs) and other compounds with lower vapor pressures. These emissions react in the atmosphere, leading to the formation of ozone and secondary organic aerosol (SOA). With more chemical detail than previous studies, we report emission factors for over 230 compounds from gasoline and diesel vehicles via two methods. First we use speciated measurements of exhaust emissions from on-road vehicles in summer 2010. Second, we use a fuel composition-based approach to quantify uncombusted fuel components in exhaust using the emission factor for total uncombusted fuel in exhaust together with detailed chemical characterization of liquid fuel samples. There is good agreement between the two methods except for products of incomplete combustion, which are not present in uncombusted fuels and comprise 32 ± 2% of gasoline exhaust and 26 ± 1% of diesel exhaust by mass. We calculate and compare ozone production potentials of diesel exhaust, gasoline exhaust, and nontailpipe gasoline emissions. Per mass emitted, the gas-phase organic compounds in gasoline exhaust have the largest potential impact on ozone production with over half of the ozone formation due to products of incomplete combustion (e.g., alkenes and oxygenated VOCs). When combined with data on gasoline and diesel fuel sales in the U.S., these results indicate that gasoline sources are responsible for 69-96% of emissions and 79-97% of the ozone formation potential from gas-phase organic carbon emitted by motor vehicles.

EVALUATION OF OZONATION BY-PRODUCTS FROM TWO CALIFORNIA SURFACE WATERS

EPA Science Inventory

Ozonation by-products were analyzed for two surface water sources in Southern California--Los Angeles Aqueduct Water (LAAW) and State Project Water (SPW). ncluded are data obtained when LAAW was being treated at the Los Angeles Aqueduct Filtration Plant and similar data obtained ...