Science.gov

Sample records for photochemical ozone formation

  1. The history of ozone. Part VIII. Photochemical formation of ozone.

    PubMed

    Braslavsky, Silvia E; Rubin, Mordecai B

    2011-10-01

    The historical development of the photochemical formation of ozone in the atmosphere is outlined, starting from the discovery of ozone by Schönbein in 1843 and the postulation of its role as UV filter by Hartley in 1881. This journal is © The Royal Society of Chemistry and Owner Societies 2011

  2. 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

  3. Tropospheric Ozone and Photochemical Smog

    NASA Astrophysics Data System (ADS)

    Sillman, S.

    2003-12-01

    emitted species, in a process that is driven by sunlight and is accelerated by warm temperatures. This smog is largely the product of gasoline-powered engines (especially automobiles), although coal-fired industry can also generate photochemical smog. The process of photochemical smog formation was first identified by Haagen-Smit and Fox (1954) in association with Los Angeles, a city whose geography makes it particularly susceptible to this type of smog formation. Sulfate aerosols and organic particulates are often produced concurrently with ozone, giving rise to a characteristic milky-white haze associated with this type of air pollution.Today ozone and particulates are recognized as the air pollutants that are most likely to affect human health adversely. In the United States, most major metropolitan areas have periodic air pollution events with ozone in excess of government health standards. Violations of local health standards also occur in major cities in Canada and in much of Europe. Other cities around the world (especially Mexico City) also experience very high ozone levels. In addition to urban-scale events, elevated ozone occurs in region-wide events in the eastern USA and in Western Europe, with excess ozone extending over areas of 1,000 km2 or more. Ozone plumes of similar extent are found in the tropics (especially in Central Africa) at times of high biomass burning (e.g., Jenkins et al., 1997; Chatfield et al., 1998). In some cases ozone associated with biomass burning has been identified at distances up to 104 km from its sources (Schultz et al., 1999).Ozone also has a significant impact on the global troposphere, and ozone chemistry is a major component of global tropospheric chemistry. Global background ozone concentrations are much lower than urban or regional concentrations during pollution events, but there is evidence that the global background has increased as a result of human activities (e.g., Wang and Jacob, 1998; Volz and Kley, 1988). A rise in

  4. A photochemical theory of tropospheric ozone

    NASA Technical Reports Server (NTRS)

    Chameides, W.; Walker, J. C. G.

    1973-01-01

    We present a photochemical theory for tropospheric ozone in which the methane oxidation chain constitutes a large local source. This source produces about one trillion odd oxygen molecules per square centimeter per second and implies a photochemical lifetime for ozone of about 1 day, much shorter than characteristic mixing times. The photochemical model reproduces the altitude and seasonal dependence of ozone at 30 deg N. It also gives qualitative agreement with observed day-to-day variations of the ozone density.

  5. Stratospheric Ozone: Transport, Photochemical Production and Loss

    NASA Technical Reports Server (NTRS)

    Douglass, A. R.; Kawa, S. R.; Jackman, C. H.

    2003-01-01

    Observations from various satellite instruments (e.g., Total Ozone Mapping Spectrometer (TOMS), Halogen Occultation Experiment (HALOE), Microwave Limb Sounder (MLS)) specify the latitude and seasonal variations of total ozone and ozone as a function of altitude. These seasonal variations change with latitude and altitude partly due to seasonal variation in transport and temperature, partly due to differences in the balance between photochemical production and loss processes, and partly due to differences in the relative importance of the various ozone loss processes. Comparisons of modeled seasonal ozone behavior with observations test the following: the seasonal dependence of dynamical processes where these dominate the ozone tendency; the seasonal dependence of photochemical processes in the upper stratosphere; and the seasonal change in the balance between photochemical and dynamical processes.

  6. Investigating ambient ozone formation regimes in neighboring cities of shale plays in the Northeast United States using photochemical modeling and satellite retrievals

    NASA Astrophysics Data System (ADS)

    Chang, Chih-Yuan; Faust, Eric; Hou, Xiangting; Lee, Pius; Kim, Hyun Cheol; Hedquist, Brent C.; Liao, Kuo-Jen

    2016-10-01

    This study investigates long-term (i.e., 2007-2014) fluctuations in ambient ozone formation regimes for cities adjacent to shale plays in the Northeast United States (U.S.). Ozone air quality in many cities of the Northeast U.S. does not meet the U.S. National Ambient Air Quality Standards (NAAQS), and understanding ambient ozone formation regimes is essential to develop effective air pollution mitigation strategies for cities violating the air quality standards. Since 2013, the U.S. has become the world's largest producer of tight oil and natural gas from shale rock, and previous studies show that emissions of air pollutant precursors from shale oil and gas-related activities would have the potential to affect ambient ozone air quality in adjacent cities of shale plays. This work leveraged (1) satellite-retrieved column densities of formaldehyde (HCHO) and nitrogen dioxide (NO2) from multiple instruments (i.e., Ozone Monitoring Instrument (OMI) and Global Ozone Monitoring Experiment-2 (GOME-2)); (2) photochemical air quality modeling and sensitivity analysis; and (3) ratios of satellite-retrieved air pollutant column densities to investigate ambient ozone formation regimes in neighboring cities of shale plays (i.e., Marcellus Shale) in the Northeast U.S. from 2007 to 2014. Our results show that ambient ozone formation in Boston, Pittsburgh, Philadelphia and Washington, D.C. (which are close to Marcellus Shale) was in the NOx -limited or transition regime during the period of study. Ambient ozone formation in New York City was in the transition regime during 2010-2013 and VOC -limited regime during 2007-2009 and in 2014. Based on the result of this study, we conclude that controls NOx emissions would mitigate ozone air pollution from 2007 to 2014 in most of the cities examined in this study. Controls of local VOC emissions would ease ozone air pollution in New York City during the study period. With projected increases in oil and gas production from shale plays in

  7. Formation and inhibition of photochemical smog

    SciTech Connect

    Heicklen, J.

    1987-01-01

    Photochemical smog is caused by a free-radical chain mechanism which converts NO to NO/sub 2/. The NO/sub 2/ further reacts to produce ozone, nitric acid, and peracylnitrates. This chain mechanism can be inhibited by suitable free-radical scavengers. The chemistry and toxicology of one such free-radical scavenger, diethylhydroxylamine, has been studied in depth. It has been shown to be effective, safe, and practical for use in urban atmospheres to prevent photochemical smog formation. 42 references.

  8. Effect of nitric oxide on photochemical ozone formation in mixtures of air with molecular chlorine and with trichlorofluoromethane

    NASA Technical Reports Server (NTRS)

    Bittker, D. A.; Wong, E. L.

    1978-01-01

    Ozone formation in a reaction chamber at room temperature and atmospheric pressure were studied for the photolysis of mixtures of NO with either Cl2 or CFCl3 in air. Both Cl2 + NO and CFCl3 + NO in air strongly inhibited O3 formation during the entire 3 to 4 hour reaction. A chemical mechanism that explains the results was presented. An important part of this mechanism was the formation and destruction of chlorine nitrate. Computations were performed with this same mechanism for CFCl3-NO-air mixtures at stratospheric temperatures, pressures, and concentrations. Results showed large reductions in steady-state O3 concentrations in these mixtures as compared with pure air.

  9. 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.

  10. 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.

  11. 78 FR 11172 - Integrated Science Assessment for Ozone and Related Photochemical Oxidants

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-02-15

    ... AGENCY Integrated Science Assessment for Ozone and Related Photochemical Oxidants AGENCY: Environmental... final document titled, ``Integrated Science Assessment for Ozone and Related Photochemical Oxidants... ``Integrated Science Assessment for Ozone and Related Photochemical Oxidants'' will be made available...

  12. Demonstration of photochemical grid model usage for ozone control assessment

    SciTech Connect

    Layland, D.E.; Hugo, H.; Oliver, W.R.; Reynolds, S.D.

    1983-06-01

    This paper examines the application of a photochemical grid model to the problem of assessing the effect of emission control measures on the formation of photochemical smog in urban areas. Simulations are carried out using the Urban Airshed Model together with a data base for the city of Tulsa, Oklahoma. The model is first evaluated as an ozone predictive tool by comparing model predictions with air quality observations. The model is then employed to estimate ambient ozone concentrations associated with various projections of future emission levels. The Tulsa study is part of a larger EPA program for demonstrating and evaluating the use of photochemical grid models for air quality planning and management activities related to ozone. Other cities included in the program for which studies have been completed are St. Louis, and Denver. A data base has been assembled for Philadelphia and modeling efforts are now underway. Other groups have sponsored studies with the Urban Airshed Model in Los Angeles and with an earlier version of the model in Sacramento, Denver, and Los Angeles.

  13. 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...

  14. 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...

  15. 76 FR 72919 - Draft Integrated Science Assessment for Ozone and Related Photochemical Oxidants

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-11-28

    ... AGENCY Draft Integrated Science Assessment for Ozone and Related Photochemical Oxidants AGENCY..., ``Second External Review Draft Integrated Science Assessment for Ozone and Related Photochemical Oxidants... review of the national ambient air quality standards (NAAQS) for ozone. DATES: The public comment...

  16. 76 FR 17121 - Draft Integrated Science Assessment for Ozone and Related Photochemical Oxidants

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-03-28

    ... AGENCY Draft Integrated Science Assessment for Ozone and Related Photochemical Oxidants AGENCY..., ``First External Review Draft Integrated Science Assessment for Ozone and Related Photochemical Oxidants... review of the national ambient air quality standards (NAAQS) for ozone. DATES: The public comment...

  17. Air quality criteria for ozone and other photochemical oxidants. External Review Draft No. 2. Volume 5

    SciTech Connect

    Horstman, D.H.; Horvath, S.M.; Raub, J.A.

    1985-11-01

    Scientific information is presented and evaluated relative to the health and welfare effects associated with exposure to ozone and other photochemical oxidants. Although not intended as a complete and detailed literature review, the document covers pertinent literature through early 1985. Data on health and welfare effects are emphasized, but additional information is provided for understanding the nature of the oxidant pollution problem and for evaluating the reliability of effects data as well as their relevance to potential exposures to ozone and other oxidants at concentrations occurring in ambient air. Information is presented on the following exposure-related topics: nature, source, measurement, and concentrations of precursors to ozone and other photochemical oxidants; formation of ozone and other photochemical oxidants and their transport once formed; properties, chemistry, and measurement of ozone and other photochemical oxidants; and concentrations of ozone and other photochemical oxidants typically found in ambient air. Chapters on health and welfare effects address the toxicological effects of ozone and other oxidants; effects observed in controlled human exposures; effects observed in field and epidemiological studies; effects on vegetation seen in field and controlled exposures; effects on natural and agroecosystems; and effects on nonbiological materials observed in field and chamber studies.

  18. AIR QUALITY CRITERIA FOR OZONE AND RELATED PHOTOCHEMICAL OXIDANTS

    EPA Science Inventory

    The Clean Air Act requires periodic (5-year) update revision of criteria and National Ambient Air Quality Standards (NAAQS) for Ozone. The previous revision of the criteria contained in the Air Quality Criteria Document (AQCD) for Ozone and Related Photochemical Oxidants was co...

  19. AIR QUALITY CRITERIA FOR OZONE AND RELATED PHOTOCHEMICAL OXIDANTS

    EPA Science Inventory

    The Clean Air Act requires periodic (5-year) update revision of criteria and National Ambient Air Quality Standards (NAAQS) for Ozone. The previous revision of the criteria contained in the Air Quality Criteria Document (AQCD) for Ozone and Related Photochemical Oxidants was co...

  20. Photochemical modeling of emissions trading of highly reactive volatile organic compounds in Houston, Texas. 1. Reactivity based trading and potential for ozone hot spot formation.

    PubMed

    Wang, Linlin; Thompson, Tammy; McDonald-Buller, Elena C; Webb, Alba; Allen, David T

    2007-04-01

    As part of the State Implementation Plan for attaining the National Ambient Air Quality Standard for ozone, the Texas Commission of Environmental Quality has created a Highly Reactive Volatile Organic Compounds (HRVOC) Emissions Cap and Trade Program for industrial point sources in the Houston/Galveston/Brazoria area. This program has a number of unique features, including its focus on a limited group of ozone precursors and its provisions for trading emissions based on atmospheric reactivity. This series of papers examines the potential air quality impacts of this new emission trading program through photochemical modeling of potential trading scenarios; this first paper in the series describes the air quality modeling methods used to assess potential trades, the potential for localized increases in ozone concentrations (ozone "hot spots") due to HRVOC emission trading, and the use of reactivity scales in the trading. When HRVOC emissions are traded on a mass basis, the simulations indicate that trading of HRVOC allowances between facilities resulted in less than 0.15 ppb (<0.13%) and 0.06 ppb (<0.06%) increases in predicted maximum, area-wide 1-h averaged and 8-h averaged ozone concentrations, respectively. Maximum decreases in ozone concentrations associated with trading, as opposed to across-the-board reductions, were larger than the increases. All of these changes are small compared to the maximum changes in ozone concentrations due to the VOC emissions from these sources (up to 5-10 ppb for 8 h averages; up to 30 ppb for 1-h averages). When emissions of HRVOCs are traded for other, less reactive emissions, on a reactivity weighted basis, air quality simulations indicate that daily maximum ozone concentrations increased by less than 0.3%. Because these relatively small changes (< 1%) are for unlikely trading scenarios designed to produce a maximum change in ozone concentrations (all emissions traded into localized regions), the simulations indicate that the

  1. Air Quality Criteria for Ozone and Related Photochemical ...

    EPA Pesticide Factsheets

    In February 2006, EPA released the final document, Air Quality Criteria for Ozone and Other Photochemical Oxidants. Tropospheric or surface-level ozone (O3) is one of six major air pollutants regulated by National Ambient Air Quality Standards (NAAQS) under the U.S. Clean Air Act. As mandated by the Clean Air Act, the U.S. Environmental Protection Agency (EPA) must periodically review the scientific bases (or criteria) for the various NAAQS by assessing newly available scientific information on a given criteria air pollutant. This document, Air Quality Criteria for Ozone and Other Photochemical Oxidants, is an updated revision of the 1996 Ozone Air Quality Criteria Document (O3 AQCD) that provided scientific bases for the current O3 NAAQS set in 1997. The Clean Air Act mandates periodic review of the National Ambient Air Quality Standards (NAAQS) for six common air pollutants, also referred to as criteria pollutants, including ozone.

  2. Influence of humidity on photochemical ozone generation with 172nm xenon excimer lamps

    NASA Astrophysics Data System (ADS)

    Salvermoser, M. J.; Kogelschatz, U.; Murnick, D. E.

    2009-08-01

    The reaction kinetics of photochemical ozone (O{3}) generation in humid air and oxygen (O{2}) using efficient, narrow band vacuum ultra violet (VUV) 172 nm xenon excimer lamps is discussed. Trace amounts of water (H{2}O) vapor in the process gas leads to hydroxyl (OH) and hydroperoxy (HO{2}) radical formation. These radicals drive a catalytic O{3} destruction cycle limiting O{3} saturation concentration. This catalytic O{3} destruction cycle was included into a quantitative kinetic model describing photochemical O{3} production. Experimental O{3} saturation concentrations obtained with coaxial VUV driven photochemical O{3} generators compare satisfactorily with the models predictions.

  3. Source apportionment of VOCs and the contribution to photochemical ozone formation during summer in the typical industrial area in the Yangtze River Delta, China

    NASA Astrophysics Data System (ADS)

    Shao, Ping; An, Junlin; Xin, Jinyuan; Wu, Fangkun; Wang, Junxiu; Ji, Dongsheng; Wang, Yuesi

    2016-07-01

    Volatile organic compounds (VOCs) were continuously observated in a northern suburb of Nanjing, a typical industrial area in the Yangtze River Delta, in a summer observation period from 15th May to 31st August 2013. The average concentration of total VOCs was (34.40 ± 25.20) ppbv, including alkanes (14.98 ± 12.72) ppbv, alkenes (7.35 ± 5.93) ppbv, aromatics (9.06 ± 6.64) ppbv and alkynes (3.02 ± 2.01) ppbv, respectively. Source apportionment via Positive Matrix Factorization was conducted, and six major sources of VOCs were identified. The industry-related sources, including industrial emissions and industrial solvent usage, occupied the highest proportion, accounting for about 51.26% of the VOCs. Vehicular emissions occupied the second highest proportion, accounting for about 34.08%. The rest accounted for about 14.66%, including vegetation emission and liquefied petroleum gas/natural gas usage. Contributions of VOCs to photochemical O3 formation were evaluated by the application of a detailed chemical mechanism model (NCAR MM). Alkenes were the dominant contributors to the O3 photochemical production, followed by aromatics and alkanes. Alkynes had a very small impact on photochemical O3 formation. Based on the outcomes of the source apportionment, a sensitivity analysis of relative O3 reduction efficiency (RORE), under different source removal regimes such as using the reduction of VOCs from 10% to 100% as input, was conducted. The RORE was the highest (~ 20%-40%) when the VOCs from solvent-related sources decreased by 40%. The highest RORE values for vegetation emissions, industrial emissions, vehicle exhaust, and LPG/NG usage were presented in the scenarios of 50%, 80%, 40% and 40%, respectively.

  4. 76 FR 60820 - Draft Integrated Science Assessment for Ozone and Related Photochemical Oxidants

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-09-30

    ... AGENCY Draft Integrated Science Assessment for Ozone and Related Photochemical Oxidants AGENCY... titled, ``Second External Review Draft Integrated Science Assessment for Ozone and Related Photochemical... ambient air quality standards (NAAQS) for ozone. EPA is releasing this draft document to seek review...

  5. 77 FR 36534 - Third External Review Draft Integrated Science Assessment for Ozone and Related Photochemical...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-06-19

    ... AGENCY Third External Review Draft Integrated Science Assessment for Ozone and Related Photochemical... External Review Draft Integrated Science Assessment for Ozone and Related Photochemical Oxidants'' (EPA/600... Standards (NAAQS) for ozone. EPA is releasing this draft document to seek review by the Clean Air...

  6. 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

    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.

  7. 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

    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.

  8. Simulations of photochemical smog formation in complex urban areas

    NASA Astrophysics Data System (ADS)

    Muilwijk, C.; Schrijvers, P. J. C.; Wuerz, S.; Kenjereš, S.

    2016-12-01

    In the present study we numerically investigated the dispersion of photochemical reactive pollutants in complex urban areas by applying an integrated Computational Fluid Dynamics (CFD) and Computational Reaction Dynamics (CRD) approach. To model chemical reactions involved in smog generation, the Generic Reaction Set (GRS) approach is used. The GRS model was selected since it does not require detailed modeling of a large set of reactive components. Smog formation is modeled first in the case of an intensive traffic emission, subjected to low to moderate wind conditions in an idealized two-dimensional street canyon with a building aspect ratio (height/width) of one. It is found that Reactive Organic Components (ROC) play an important role in the chemistry of smog formation. In contrast to the NOx/O3 photochemical steady state model that predicts a depletion of the (ground level) ozone, the GRS model predicts generation of ozone. Secondly, the effect of direct sunlight and shadow within the street canyon on the chemical reaction dynamics is investigated for three characteristic solar angles (morning, midday and afternoon). Large differences of up to one order of magnitude are found in the ozone production for different solar angles. As a proof of concept for real urban areas, the integrated CFD/CRD approach is applied for a real scale (1 × 1 km2) complex urban area (a district of the city of Rotterdam, The Netherlands) with high traffic emissions. The predicted pollutant concentration levels give realistic values that correspond to moderate to heavy smog. It is concluded that the integrated CFD/CRD method with the GRS model of chemical reactions is both accurate and numerically robust, and can be used for modeling of smog formation in complex urban areas.

  9. 76 FR 10893 - Draft Integrated Science Assessment for Ozone and Related Photochemical Oxidants

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-02-28

    ... AGENCY Draft Integrated Science Assessment for Ozone and Related Photochemical Oxidants AGENCY... review draft of a document titled, ``First External Review Draft Integrated Science Assessment for Ozone... review of the national ambient air quality standards (NAAQS) for ozone. EPA is releasing this...

  10. Photo-chemical transport modelling of tropospheric ozone: A review

    NASA Astrophysics Data System (ADS)

    Sharma, Sumit; Sharma, Prateek; Khare, Mukesh

    2017-06-01

    Ground level ozone (GLO), a secondary pollutant having adverse impact on human health, ecology, and agricultural productivity, apart from being a major contributor to global warming, has been a subject matter of several studies. In order to identify appropriate strategies to control GLO levels, accurate assessment and prediction is essential, for which elaborate simulation and modelling is required. Several studies have been undertaken in the past to simulate GLO levels at different scales and for various applications. It is important to evaluate these studies, widely spread over in literature. This paper aims to critically review various studies that have been undertaken, especially in the past 15 years (2000-15) to model GLO. The review has been done of the studies that range over different spatial scales - urban to regional and continental to global. It also includes a review of performance evaluation and sensitivity analysis of photo-chemical transport models in order to assess the extent of application of these models and their predictive capability. The review indicates following major findings: (a) models tend to over-estimate the night-time GLO concentrations due to limited titration of GLO with NO within the model; (b) dominance of contribution from far-off regional sources to average ozone concentration in the urban region and higher contribution of local sources during days of high ozone episodes; requiring strategies for controlling precursor emissions at both regional and local scales; (c) greater influence of NOx over VOC in export of ozone from urban regions due to shifting of urban plumes from VOC-sensitive regime to NOx-sensitive as they move out from city centres to neighbouring rural regions; (d) models with finer resolution inputs perform better to a certain extent, however, further improvement in resolutions (beyond 10 km) did not show improvement always; (e) future projections show an increase in GLO concentrations mainly due to rise in

  11. Evidence for an increase in the ozone photochemical lifetime in the eastern United States using a regional air quality model

    NASA Astrophysics Data System (ADS)

    Goldberg, Daniel L.; Vinciguerra, Timothy P.; Hosley, Kyle M.; Loughner, Christopher P.; Canty, Timothy P.; Salawitch, Ross J.; Dickerson, Russell R.

    2015-12-01

    Measures to control surface ozone rely on quantifying production attributable to local versus regional (upwind) emissions. Here we simulate the relative contribution of local (i.e., within a particular state) and regional sources of surface ozone in the eastern United States (66-94°W longitude) for July 2002, 2011, and 2018 using the Comprehensive Air-quality Model with Extensions (CAMx). To determine how emissions and chemistry within the domain affect the production, loss, lifetime, and transport of trace gases, we initialize our model with identical boundary conditions in each simulation. We find that the photochemical lifetime of ozone has increased as emissions have decreased. The contribution of ozone from outside the domain (boundary condition ozone, BCO3) to local surface mixing ratios increases in an absolute sense by 1-2 ppbv between 2002 and 2018 due to the longer lifetime of ozone. The photochemical lifetime of ozone lengthens because the two primary gas phase sinks for odd oxygen (Ox ≈ NO2 + O3)—attack by hydroperoxyl radicals (HO2) on ozone and formation of nitrate—weaken with decreasing pollutant emissions. The relative role of BCO3 will also increase. For example, BCO3 represents 34.5%, 38.8%, and 43.6% of surface ozone in the Baltimore, MD, region during July 2002, 2011, and 2018 means, respectively. This unintended consequence of air quality regulation impacts attainment of the National Ambient Air Quality Standard for surface ozone because the spatial and temporal scales of photochemical smog increase; the influence of pollutants transported between states and into the eastern U.S. will likely play a greater role in the future.

  12. AIR QUALITY CRITERIA FOR OZONE AND OTHER PHOTOCHEMICAL OXIDANTS. EXTERNAL REVIEW DRAFT NO. 2. VOLUME V

    EPA Science Inventory

    Scientific information is presented and evaluated relative to the health and welfare effects associated with exposure to ozone and other photochemical oxidants. Although not intended as a complete and detailed literature review, the document covers pertinent literature through ea...

  13. Problem of photochemical equilibrium of ozone in planetary atmospheres: Ozone distribution in the lower atmosphere of Mars

    NASA Technical Reports Server (NTRS)

    Grams, G. W.; SHARDANAND

    1972-01-01

    The inherent errors of applying terrestrial atmospheric ozone distribution studies to the atmosphere of other planets are discussed. Limitations associated with some of the earlier treatments of photochemical equilibrium distributions of ozone in planetary atmospheres are described. A technique having more universal application is presented. Ozone concentration profiles for the Martian atmosphere based on the results of the Mariner 4 radio occultation experiment and the more recent results with Mariner 6 and Mariner 7 have been calculated using this approach.

  14. Photochemical ozone budget during the BIBLE A and B campaigns

    NASA Astrophysics Data System (ADS)

    Ko, Malcolm; Hu, Wenjie; RodríGuez, José M.; Kondo, Yutaka; Koike, Makoto; Kita, Kazuyuki; Kawakami, Shuji; Blake, Donald; Liu, Shaw; Ogawa, Toshihiro

    2002-02-01

    Using the measured concentrations of NO, O3, H2O, CO, CH4, and NMHCs along the flight tracks, a photochemical box model is used to calculate the concentrations of the Ox radicals, the HOx radicals, and the nitrogen species at the sampling points. The calculations make use of the measurements from radiometers to scale clear sky photolysis rates to account for cloud cover and ground albedo at the sampling time/point. The concentrations of the nitrogen species in each of the sampled air parcels are computed assuming they are in instantaneous equilibrium with the measured NO and O3. The diurnally varying species concentrations are next calculated using the box model and used to estimate the diurnally averaged production and removal rates of ozone for the sampled air parcels. Clear sky photolysis rates are used in the diurnal calculations. The campaign also provided measured concentration of NOy. The observed NO/NOy ratio is usually larger than the model calculated equilibrium value. There are several possible explanations. It could be a result of recent injection of NO into the air parcel, recent removal of HNO3 from the parcel, recent rapid transport of an air parcel from another location, or a combination of all processes. Our analyses suggest that the local production rate of O3 can be used as another indicator of recent NO injection. However, more direct studies using air trajectory analyses and other collaborative evidences are needed to ascertain the roles played by individual process.

  15. Photochemical ozone budget during the BIBLE A and B campaigns

    NASA Astrophysics Data System (ADS)

    Ko, Malcolm; Hu, Wenjie; Rodríguez, José M.; Kondo, Yutaka; Koike, Makoto; Kita, Kazuyuki; Kawakami, Shuji; Blake, Donald; Liu, Shaw; Ogawa, Toshihiro

    2003-02-01

    Using the measured concentrations of NO, O3, H2O, CO, CH4, and NMHCs along the flight tracks, a photochemical box model is used to calculate the concentrations of the Ox radicals, the HOx radicals, and the nitrogen species at the sampling points. The calculations make use of the measurements from radiometers to scale clear sky photolysis rates to account for cloud cover and ground albedo at the sampling time/point. The concentrations of the nitrogen species in each of the sampled air parcels are computed assuming they are in instantaneous equilibrium with the measured NO and O3. The diurnally varying species concentrations are next calculated using the box model and used to estimate the diurnally averaged production and removal rates of ozone for the sampled air parcels. Clear sky photolysis rates are used in the diurnal calculations. The campaign also provided measured concentration of NOy. The observed NO/NOy ratio is usually larger than the model calculated equilibrium value. There are several possible explanations. It could be a result of recent injection of NO into the air parcel, recent removal of HNO3 from the parcel, recent rapid transport of an air parcel from another location, or a combination of all processes. Our analyses suggest that the local production rate of O3 can be used as another indicator of recent NO injection. However, more direct studies using air trajectory analyses and other collaborative evidences are needed to ascertain the roles played by individual process.

  16. Air Quality Criteria for Ozone and Related Photochemical Oxidants (Final Report, 2006)

    EPA Science Inventory

    In February 2006, EPA released the final document, Air Quality Criteria for Ozone and Other Photochemical Oxidants. Tropospheric or surface-level ozone (O3) is one of six major air pollutants regulated by National Ambient Air Quality Standards (NAAQS) under the U.S...

  17. Air Quality Criteria for Ozone and Related Photochemical Oxidants (First External Review Draft)

    EPA Science Inventory

    This first external review draft of the Air Quality Criteria for Ozone and Related Photochemical Oxidants (Ozone Criteria Document) is being released in January 2005 for public comment and for review by EPA's Clean A...

  18. Air Quality Criteria for Ozone and Related Photochemical Oxidants (First External Review Draft)

    EPA Science Inventory

    This first external review draft of the Air Quality Criteria for Ozone and Related Photochemical Oxidants (Ozone Criteria Document) is being released in January 2005 for public comment and for review by EPA's Clean A...

  19. Air Quality Criteria for Ozone and Related Photochemical Oxidants (Second External Review Draft)

    EPA Science Inventory

    This second external review draft of the Air Quality Criteria for Ozone and Related Photochemical Oxidants, Volumes I-III (Ozone Criteria Document) is being released for public comment and for review by EPA's Clean Air Scientific Advisory Committee (CASAC) r...

  20. Air Quality Criteria for Ozone and Related Photochemical Oxidants (Second External Review Draft)

    EPA Science Inventory

    This second external review draft of the Air Quality Criteria for Ozone and Related Photochemical Oxidants, Volumes I-III (Ozone Criteria Document) is being released for public comment and for review by EPA's Clean Air Scientific Advisory Committee (CASAC) r...

  1. Air Quality Criteria for Ozone and Related Photochemical Oxidants (Final Report, 2006)

    EPA Science Inventory

    In February 2006, EPA released the final document, Air Quality Criteria for Ozone and Other Photochemical Oxidants. Tropospheric or surface-level ozone (O3) is one of six major air pollutants regulated by National Ambient Air Quality Standards (NAAQS) under the U.S...

  2. 2013 Final Report: Integrated Science Assessment of Ozone and Related Photochemical Oxidants

    EPA Science Inventory

    ozone_isa_cover.jpg" alt="Cover of the Integrated Science Assessment (ISA) for Ozone and Related Photochemical Oxidants" vspace = "5" hspace="5" align="right" border="1" /> EPA is announcing the availability of the <...

  3. Lagrangian photochemical modeling studies of the 1987 Antarctic spring vortex. II - Seasonal trends in ozone

    NASA Technical Reports Server (NTRS)

    Austin, J.; Jones, R. L.; Mckenna, D. S.; Buckland, A. T.; Anderson, J. G.; Fahey, D. W.; Farmer, C. B.; Heidt, L. E.; Proffitt, M. H.; Vedder, J. F.

    1989-01-01

    A photochemical model consisting of 40 species and 107 reactions is integrated along 80-day air parcel trajectories calculated in the lower stratosphere for the springtime Antarctic. For the trajectory starting at 58 deg S, which may be regarded as outside the circumpolar vortex, only a small change in O3 occurs in the model. In contrast, for the air parcel starting in the vortex at 74 deg S, the O3 concentration is reduced by 93 percent during the 80 days from the beginning of August to late October. The model results for several species are compared with measurements from the Airborne Antarctic Ozone Experiment and, in general, good agreement is obtained. In the model, the dentrification of the air parcels in polar stratospheric clouds increases the amount of chlorine present in active form. Heterogeneous reactions maintain high active chlorine which destroys O3 via the formation of the ClO dimer. Results of calculations with reduced concentrations of inorganic chlorine show considerably reduced O3 destruction rates and compare favorably with the behavior of total O3 since the late 1970s. The remaining major uncertainties in the photochemical aspects of the Antarctic ozone hole are highlighted.

  4. Lagrangian photochemical modeling studies of the 1987 Antarctic spring vortex. II - Seasonal trends in ozone

    NASA Technical Reports Server (NTRS)

    Austin, J.; Jones, R. L.; Mckenna, D. S.; Buckland, A. T.; Anderson, J. G.; Fahey, D. W.; Farmer, C. B.; Heidt, L. E.; Proffitt, M. H.; Vedder, J. F.

    1989-01-01

    A photochemical model consisting of 40 species and 107 reactions is integrated along 80-day air parcel trajectories calculated in the lower stratosphere for the springtime Antarctic. For the trajectory starting at 58 deg S, which may be regarded as outside the circumpolar vortex, only a small change in O3 occurs in the model. In contrast, for the air parcel starting in the vortex at 74 deg S, the O3 concentration is reduced by 93 percent during the 80 days from the beginning of August to late October. The model results for several species are compared with measurements from the Airborne Antarctic Ozone Experiment and, in general, good agreement is obtained. In the model, the dentrification of the air parcels in polar stratospheric clouds increases the amount of chlorine present in active form. Heterogeneous reactions maintain high active chlorine which destroys O3 via the formation of the ClO dimer. Results of calculations with reduced concentrations of inorganic chlorine show considerably reduced O3 destruction rates and compare favorably with the behavior of total O3 since the late 1970s. The remaining major uncertainties in the photochemical aspects of the Antarctic ozone hole are highlighted.

  5. Establishing a conceptual model for photochemical ozone pollution in subtropical Hong Kong

    NASA Astrophysics Data System (ADS)

    Ling, Z. H.; Guo, H.; Zheng, J. Y.; Louie, P. K. K.; Cheng, H. R.; Jiang, F.; Cheung, K.; Wong, L. C.; Feng, X. Q.

    2013-09-01

    Photochemical ozone (O3) formation is related to its precursors and meteorological conditions. A conceptual model of O3 air pollution is developed based on the analysis of data obtained at Tung Chung (TC) in Hong Kong. By comparing meteorological parameters between O3 and non-O3 episode days, it was found that high temperatures, strong solar radiation, low wind speeds and relative humidity, northeasterly and/or northwesterly prevailing winds were favorable for the O3 formation, while tropical cyclones were most conducive to the occurrence of O3 episodes. Backward trajectories simulation and graphical illustration of O3 pollution suggested that super-regional (i.e. central and eastern China) and regional (i.e. Pearl River Delta, southern China) transport was another factor that contributed to high O3 levels in Hong Kong. The photochemical O3 formation, generally VOC-limited in Hong Kong, was controlled by a small number of volatile organic compounds (VOCs). Furthermore, the positive matrix factorization (PMF) simulation suggested that solvent usage and vehicular emissions are the major contributors to ambient VOCs in Hong Kong. Finally, this paper presents recommendations for further O3 research and implementation of O3 control strategies.

  6. Photochemical organonitrate formation in wet aerosols

    NASA Astrophysics Data System (ADS)

    Lim, Yong Bin; Kim, Hwajin; Kim, Jin Young; Turpin, Barbara J.

    2016-10-01

    Water is the most abundant component of atmospheric fine aerosol. However, despite rapid progress, multiphase chemistry involving wet aerosols is still poorly understood. In this work, we report results from smog chamber photooxidation of glyoxal- and OH-containing ammonium sulfate or sulfuric acid particles in the presence of NOx and O3 at high and low relative humidity. Particles were analyzed using ultra-performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry (UPLC-Q-TOF-MS). During the 3 h irradiation, OH oxidation products of glyoxal that are also produced in dilute aqueous solutions (e.g., oxalic acids and tartaric acids) were formed in both ammonium sulfate (AS) aerosols and sulfuric acid (SA) aerosols. However, the major products were organonitrogens (CHNO), organosulfates (CHOS), and organonitrogen sulfates (CHNOS). These were also the dominant products formed in the dark chamber, indicating non-radical formation. In the humid chamber (> 70 % relative humidity, RH), two main products for both AS and SA aerosols were organonitrates, which appeared at m / z- 147 and 226. They were formed in the aqueous phase via non-radical reactions of glyoxal and nitric acid, and their formation was enhanced by photochemistry because of the photochemical formation of nitric acid via reactions of peroxy radicals, NOx and OH during the irradiation.

  7. Photochemical Ignition Studies. 3. Ignition by Efficient and Resonant Multiphoton Photochemical Formation of Microplasmas

    DTIC Science & Technology

    1987-06-01

    Security Ct14sfIcation) PHOTOCHEMICAL IGNITION STUDIES. I11. IGNITION BY EFFICIENT AND RESONANT MULTIPHOTON PHOTOCHEMICAL FORMATION OF MICROPLASMAS 12... Microplasmas 07 04ý 19. ABSTRACT (Coninu On 06 it= iP rwouiry and ikti n~jnilW) ;;is is the third of a series of reports concerning the activation...p--spectral studies were carried out on 02 and N 0 flows alone. These indicated a resonant formation of a microplasma with a fifetime on the order

  8. Photochemical Formation of Sulfur-Containing Aerosols

    NASA Astrophysics Data System (ADS)

    Kroll, Jay A.; Vaida, Veronica

    2017-06-01

    In order to understand planetary climate systems, modeling the properties of atmospheric aerosols is vital. Aerosol formation plays an important role in planetary climates and is tied to feedback loops that can either warm or cool a planet. Sulfur compounds are known to play an important role in new particle aerosol formation and have been observed in a number of planetary atmospheres throughout our solar system. Our current understanding of sulfur chemistry explains much of what we observe in Earth's atmosphere; however, several discrepancies arise when comparing observations of the Venusian atmosphere with model predictions. This suggests that there are still problems in our fundamental understanding of sulfur chemistry. This is concerning given recent renewed interest in sulfate injections in the stratosphere for solar radiation management geo-engineering schemes. We investigate the role of sunlight as a potential driver of the formation of sulfur-containing aerosols. I will present recent work investigating the generation of large quantities of aerosol from the irradiation of mixtures of SO_2 with water and organic species, using a solar simulator that mimics the light that is available in the Earth's troposphere and the Venusian middle atmosphere. I will present on recent work done in our lab suggesting the formation of sulfurous acid, H_2SO_3, and describe experimental work that supports this proposed mechanism. Additionally I will present on new work showing the highly reactive nature of electronically excited SO_2 with saturated alkane species. The implications of this photochemically induced sulfur aerosol formation in the atmosphere of Earth and other planetary atmospheres will be discussed.

  9. The impact of observing characteristics on the ability to predict ozone under varying polluted photochemical regimes

    NASA Astrophysics Data System (ADS)

    Hamer, P. D.; Bowman, K. W.; Henze, D.; Attié, J.-L.; Marécal, V.

    2015-02-01

    We conduct a variety of analyses to assess how the characteristics of observations of ozone and its precursors affect their ability to support air quality forecasting and research. To carry out this investigation we use a photochemical box model and its adjoint integrated with a Lagrangian 4-D-variational data assimilation system. Using this framework in conjunction with various sets of pseudo observations we perform a ozone precursor source inversion and estimate surface emissions. We then assess the resulting improvement in ozone air quality forecasting and prediction. We use an analytical model as our principle method of conducting uncertainty analyses, which is the primary focus of this work. Using this analytical tool we address some simple but key questions regarding how the characteristics of observations affect our framework's ability to constrain ozone precursor emissions and in turn to predict ozone. These questions include what the effect is of choosing which species to observe, of varying amounts of observation noise, of changing the observing frequency and the observation time during the diurnal cycle, and of how these different scenarios interact with different photochemical regimes. These questions are designed to examine how different types of observing platform, e.g., geostationary satellites or ground monitoring networks, could support future air quality research and forecasting. In our investigation we use three observed species scenarios: CO and NO2; ozone, CO, and NO2; and HCHO, CO and NO2. The photochemical model was setup to simulate a range of summertime polluted environments spanning NOx (NO and NO2) limited to volatile organic compound (VOC) limited conditions. We find that as the photochemical regime changes the relative importance of trace gas observations to constrain emission estimates and subsequent ozone forecasts varies. For example, adding ozone observations to an NO2 and CO observing system is found to decrease ozone prediction

  10. Photochemical Kinetics of Excited States of Ozone and Oxygen: Laboratory Studies and Atmospheric Implications

    NASA Astrophysics Data System (ADS)

    Shi, Jichun

    The photochemistry of O_3 has matured through the extensive research efforts of the last two decades, but its completeness has been questioned by several laboratory and atmospheric observations, including the unusually complex kinetics for the ozone three-body recombination reaction at high pressures, the unexplained heavy ozone isotope enhancement in the stratosphere, and the deficiencies of current chemical models at 90-120 km. The model deficiencies may be related to several of the excited states of O_3 and O_2 . In this dissertation, the photochemical kinetics of these excited species have been studied in a series of laboratory measurements, which are divided into two groups: (1) the study of the excited intermediates formed in the ozone recombination reaction, and (2) the investigation of the unusual odd oxygen formation in O_2 under laser irradiation at 248 nm. The ozone recombination reaction has been investigated at room temperature by monitoring the time-resolved infrared chemiluminescence of ozone at 9.6 mum, 4.7 mum, and 3.4 mu m. These studies have indicated that the recombination reaction (O+O_2+M) apparently proceeds through an intermediate complex OM, and, for M=O _2, the recombination also involves the participation of a metastable electronic state, O_3(E). The three infrared emissions have also been used to analyze the deactivation of vibrationally excited O_3 (v). The unusual odd oxygen formation in O _2 at 248 nm has been studied in both pure O_2 and O_2+N _2 and O_2+Ar mixtures at pressures between 200 and 1600 torr and at temperatures between 298 and 370^circ K. The results have indicated that this odd oxygen formation is initiated by O_2 absorption in the Herzberg continuum, and it is autocatalytically accelerated by the photodissociation of vibrationally excited O_2(v) at 248 nm. These kinetics results have been used to study the possible roles of excited O_3 and O_2 species in the sources and sinks of odd oxygen at 90-120 km, and in the

  11. Integrated Science Assessment (ISA) of Ozone and Related Photochemical Oxidants (Second External Review Draft, Sep 2011)

    EPA Science Inventory

    EPA has released the Integrated Science Assessment of Ozone and Related Photochemical Oxidants (Second External Review Draft) for independent peer review and public review. This draft document represents a concise synthesis and evaluation of the most policy-relevant scienc...

  12. Integrated Science Assessment (ISA) of Ozone and Related Photochemical Oxidants (First External Review Draft, Feb 2011)

    EPA Science Inventory

    EPA announced that the First External Review Draft of the Integrated Science Assessment for Ozone and Related Photochemical Oxidants has been made available for independent peer review and public review. This draft document represents a concise synthesis and evaluation of ...

  13. Integrated Science Assessment (ISA) of Ozone and Related Photochemical Oxidants (Third External Review Draft, Jun 2012)

    EPA Science Inventory

    EPA has released the Integrated Science Assessment of Ozone and Related Photochemical Oxidants (Third External Review Draft) for independent peer review and public review. This draft document represents a concise synthesis and evaluation of the most policy-relevant science...

  14. Integrated Science Assessment (ISA) of Ozone and Related Photochemical Oxidants (Final Report, Feb 2013)

    EPA Science Inventory

    EPA announced the availability of the final report, Integrated Science Assessment of Ozone and Related Photochemical Oxidants. This document represents a concise synthesis and evaluation of the most policy-relevant science and will ultimately provide the scientific bases f...

  15. Integrated Science Assessment (ISA) of Ozone and Related Photochemical Oxidants (Third External Review Draft, Jun 2012)

    EPA Science Inventory

    EPA has released the Integrated Science Assessment of Ozone and Related Photochemical Oxidants (Third External Review Draft) for independent peer review and public review. This draft document represents a concise synthesis and evaluation of the most policy-relevant science...

  16. Integrated Science Assessment (ISA) of Ozone and Related Photochemical Oxidants (Second External Review Draft, Sep 2011)

    EPA Science Inventory

    EPA has released the Integrated Science Assessment of Ozone and Related Photochemical Oxidants (Second External Review Draft) for independent peer review and public review. This draft document represents a concise synthesis and evaluation of the most policy-relevant scienc...

  17. Integrated Science Assessment (ISA) of Ozone and Related Photochemical Oxidants (First External Review Draft, Feb 2011)

    EPA Science Inventory

    EPA announced that the First External Review Draft of the Integrated Science Assessment for Ozone and Related Photochemical Oxidants has been made available for independent peer review and public review. This draft document represents a concise synthesis and evaluation of ...

  18. Integrated Science Assessment of Ozone and Related Photochemical Oxidants (First External Review Draft)

    EPA Science Inventory

    EPA announced that the First External Review Draft of the Integrated Science Assessment for Ozone and Related Photochemical Oxidants has been made available for independent peer review and public review. This draft document represents a concise synthesis and evaluation of ...

  19. Integrated Science Assessment of Ozone and Related Photochemical Oxidants (Second External Review Draft)

    EPA Science Inventory

    EPA has released the Integrated Science Assessment of Ozone and Related Photochemical Oxidants (Second External Review Draft) for independent peer review and public review. This draft document represents a concise synthesis and evaluation of the most policy-relevant scienc...

  20. Integrated Science Assessment of Ozone and Related Photochemical Oxidants (Third External Review Draft)

    EPA Science Inventory

    EPA has released the Integrated Science Assessment of Ozone and Related Photochemical Oxidants (Third External Review Draft) for independent peer review and public review. This draft document represents a concise synthesis and evaluation of the most policy-relevant science...

  1. Integrated Science Assessment (ISA) of Ozone and Related Photochemical Oxidants (Final Report, Feb 2013)

    EPA Science Inventory

    EPA announced the availability of the final report, Integrated Science Assessment of Ozone and Related Photochemical Oxidants. This document represents a concise synthesis and evaluation of the most policy-relevant science and will ultimately provide the scientific bases f...

  2. 2013 Final Report: Integrated Science Assessment of Ozone and Related Photochemical Oxidants

    EPA Science Inventory

    EPA announced the availability of the Integrated Science Assessment of Ozone and Related Photochemical Oxidants (Final Report). This document represents a concise synthesis and evaluation of the most policy-relevant science and will ultimately provide the scientific bases ...

  3. Comparison of measured ozone in southeastern Virginia with computer predictions from a photochemical model

    NASA Technical Reports Server (NTRS)

    Wakelyn, N. T.; Gregory, G. L.

    1980-01-01

    Data for one day of the 1977 southeastern Virginia urban plume study are compared with computer predictions from a traveling air parcel model using a contemporary photochemical mechanism with a minimal description of nonmethane hydrocarbon (NMHC) constitution and chemistry. With measured initial NOx and O3 concentrations and a current separate estimate of urban source loading input to the model, and for a variation of initial NMHC over a reasonable range, an ozone increase over the day is predicted from the photochemical simulation which is consistent with the flight path averaged airborne data.

  4. Comparison of measured ozone in southeastern Virginia with computer predictions from a photochemical model

    NASA Technical Reports Server (NTRS)

    Wakelyn, N. T.; Gregory, G. L.

    1980-01-01

    Data for one day of the 1977 southeastern Virginia urban plume study are compared with computer predictions from a traveling air parcel model using a contemporary photochemical mechanism with a minimal description of nonmethane hydrocarbon (NMHC) constitution and chemistry. With measured initial NOx and O3 concentrations and a current separate estimate of urban source loading input to the model, and for a variation of initial NMHC over a reasonable range, an ozone increase over the day is predicted from the photochemical simulation which is consistent with the flight path averaged airborne data.

  5. The impact of observing characteristics on the ability to predict ozone under varying polluted photochemical regimes

    NASA Astrophysics Data System (ADS)

    Hamer, P. D.; Bowman, K. W.; Henze, D. K.; Attié, J.-L.; Marécal, V.

    2015-09-01

    We conduct analyses to assess how characteristics of observations of ozone and its precursors affect air quality forecasting and research. To carry out this investigation, we use a photochemical box model and its adjoint integrated with a Lagrangian 4D-variational data assimilation system. Using this framework in conjunction with pseudo-observations, we perform an ozone precursor source inversion and estimate surface emissions. We then assess the resulting improvement in ozone air quality prediction. We use an analytical model to conduct uncertainty analyses. Using this analytical tool, we address some key questions regarding how the characteristics of observations affect ozone precursor emission inversion and in turn ozone prediction. These questions include what the effect is of choosing which species to observe, of varying amounts of observation noise, of changing the observing frequency and the observation time during the diurnal cycle, and of how these different scenarios interact with different photochemical regimes. In our investigation we use three observed species scenarios: CO and NO2; ozone, CO, and NO2; and HCHO, CO and NO2. The photochemical model was set up to simulate a range of summertime polluted environments spanning NOx-(NO and NO2)-limited to volatile organic compound (VOC)-limited conditions. We find that as the photochemical regime changes, here is a variation in the relative importance of trace gas observations to be able to constrain emission estimates and to improve the subsequent ozone forecasts. For example, adding ozone observations to an NO2 and CO observing system is found to decrease ozone prediction error under NOx- and VOC-limited regimes, and complementing the NO2 and CO system with HCHO observations would improve ozone prediction in the transitional regime and under VOC-limited conditions. We found that scenarios observing ozone and HCHO with a relative observing noise of lower than 33 % were able to achieve ozone prediction

  6. Improving Estimates of Entrainment Mixing, Subsidence, and Photochemical Ozone Production using Aircraft and Ozone lidar during the California Baseline Ozone Transport Study (CABOTS)

    NASA Astrophysics Data System (ADS)

    Trousdell, J.; Caputi, D.; Faloona, I. C.; Conley, S. A.; Langford, A. O.; Senff, C. J.

    2016-12-01

    In situ flight data collected in the San Joaquin Valley of California during the summer of 2016 is used to measure entrainment rates, ozone photochemical production, and regional methane and NOx emissions. The San Joaquin Valley is plagued with air quality issues including a high frequency of ozone exceedances in the summer and an aerosol issue in the winter exacerbated by a complex meso-scale environment. The flights were conducted during the California Baseline Ozone Transport Study (CABOTS), and span the valley between the cities of Fresno and Visalia with a thorough probing of the atmospheric boundary layer (ABL) including vertical profiling to diagnose the growth rate and horizontal gradients in ABL height. Entrainment velocities, which are the parameterized mixing of free tropospheric air into the boundary layer, are determined by a detailed budget equation of the inversion height. Subsidence, which is essential to our determination of entrainment velocity, is diagnosed by way of descending ozone laminae in the region above the ABL. The subsiding laminae are located within the flight data and corroborated by the Tunable Optical Profiler for Aerosol and oZone (TOPAZ) lidar measurements in Visalia. A novel scalar budgeting technique is then applied to expose residual terms of individual equations that amount to ozone photochemical production and emission rates. The budget equations are closed by our estimated entrainment velocities, in conjunction with the time rates of change (storage) and horizontal advection all determined via flight data.

  7. DNA bulky adducts in a Mediterranean population correlate with environmental ozone concentration, an indicator of photochemical smog.

    PubMed

    Palli, Domenico; Saieva, Calogero; Grechi, Daniele; Masala, Giovanna; Zanna, Ines; Barbaro, Antongiulio; Decarli, Adriano; Munnia, Armelle; Peluso, Marco

    2004-03-01

    Ozone (O(3)), the major oxidant component in photochemical smog, mostly derives from photolysis of nitrogen dioxide. O(3) may have biologic effects directly and/or via free radicals reacting with other primary pollutants and has been reported to influence daily mortality and to increase lung cancer risk. Although DNA damage may be caused by ozone itself, only other photochemical reaction products (as oxidised polycyclic aromatic hydrocarbons) may form bulky DNA adducts, a reliable biomarker of genotoxic damage and cancer risk, showing a seasonal trend. In a large series consisting of 320 residents in the metropolitan area of Florence, Italy, enrolled in a prospective study for the period 1993-1998 (206 randomly sampled volunteers, 114 traffic-exposed workers), we investigated the correlation between individual levels of DNA bulky adducts and a cumulative O(3) exposure score. The average O(3) concentrations were calculated for different time windows (0-5 to 0-90 days) prior to blood drawing for each participant, based on daily measurements provided by the local monitoring system. Significant correlations between DNA adduct levels and O3 cumulative exposure scores in the last 2-8 weeks before enrollment emerged in never smokers. Correlations were highest in the subgroup of never smokers residing in the urban area and not occupationally exposed to vehicle traffic pollution, with peak values for average concentrations 4-6 weeks before enrollment (r = 0.34). Our current findings indicate that DNA adduct formation may be modulated by individual characteristics and by the cumulative exposure to environmental levels of ozone in the last 4-6 weeks, possibly through ozone-associated reactive pollutants.

  8. Atmospheric photochemical transformations enhance 1,3-butadiene-induced inflammatory responses in human epithelial cells: The role of ozone and other photochemical degradation products.

    PubMed

    Doyle, Melanie; Sexton, Kenneth G; Jeffries, Harvey; Jaspers, Ilona

    2007-03-20

    Chemistry of hazardous air pollutants has been studied for many years, yet little is known about how these chemicals, once reacted within urban atmospheres, affect healthy and susceptible individuals. Once released into the atmosphere, 1,3-butadiene (BD) reacts with hydroxyl radicals and ozone (created by photochemical processes), to produce many identified and unidentified products. Once this transformation has occurred, the toxic potential of atmospheric pollutants such as BD in the ambient environment is currently unclear. During this study, environmental irradiation chambers (also called smog chambers), utilizing natural sunlight, were used to create photochemical transformations of BD. The smog chamber/in vitro exposure system was designed to investigate the toxicity of chemicals before and after photochemical reactions and to investigate interactions with the urban atmosphere using representative in vitro samples. In this study, we determined the relative toxicity and inflammatory gene expression induced by coupling smog chamber atmospheres with an in vitro system to expose human respiratory epithelial cells to BD, BDs photochemical degradation products, or the equivalent ozone generated within the photochemical mixture. Exposure to the photochemically generated products of BD (primarily acrolein, acetaldehyde, formaldehyde, furan and ozone) induced significant increases in cytotoxicity, IL-8, and IL-6 gene expression compared to a synthetic mixture of primary products that was created by injecting the correct concentrations of the detected products from the irradiation experiments. Interestingly, exposure to the equivalent levels of ozone generated during the photochemical transformation of BD did not induce the same level of inflammatory cytokine release for either exposure protocol, suggesting that the effects from ozone alone do not account for the entire response in the irradiation experiments. These results indicate that BDs full photochemical product

  9. An influence of solar activity on latitudinal distribution of atmospheric ozone and temperature in 2-D radiative-photochemical model

    NASA Technical Reports Server (NTRS)

    Dyominov, I. G.

    1989-01-01

    On the basis of the 2-D radiative-photochemical model of the ozone layer at heights 0 to 60 km in the Northern Hemisphere there are revealed and analyzed in detail the characteristic features of the season-altitude-latitude variations of ozone and temperature due to changes of the solar flux during the 11 year cycle, electron and proton precipitations.

  10. Applying model simulation and photochemical indicators to evaluate ozone sensitivity in southern Taiwan.

    PubMed

    Peng, Yen-Ping; Chen, Kang-Shin; Wang, Hsin-Kai; Lai, Chia-Hsiang; Lin, Ming-Hsun; Lee, Cheng-Haw

    2011-01-01

    Ozone sensitivity was investigated using CAMx simulations and photochemical indicator ratios at three sites (Pingtung City, Chao-Chou Town, and Kenting Town) in Pingtung County in southern Taiwan during 2003 and 2004. The CAMx simulations compared fairly well with the hourly concentrations of ozone. Simulation results also showed that Pingtung City was mainly a volatile organic compounds (VOC)-sensitive regime, while Chao-Chou Town was either a VOC-sensitive or a NOx-sensitive regime, depending on the seasons. Measurements of three photochemical indicators (H2O2, HNO3, and NOy) were conducted, and simulated three transition ranges of H2O2/HNO3 (0.5-0.8), O3/HNO3 (10.3-16.2) and O3/NOy (5.7-10.8) were adopted to assess the ozone sensitive regime at the three sites. The results indicated that the three transition ranges yield consistent results with CAMx simulations at most times at Pingtung City. However, both VOC-sensitive and NOx-sensitive regimes were important at the rural site Chao-Chou Town. Kenting Town, a touring site at the southern end of Taiwan, was predominated by a NOx-sensitive regime in four seasons.

  11. Quantitative photochemical formation of [Ru(tpy)(bpy)H]+.

    PubMed

    Matsubara, Yasuo; Konno, Hideo; Kobayashi, Atsuo; Ishitani, Osamu

    2009-11-02

    Quantitative photochemical production of [Ru(tpy)(bpy)H](+) (Ru-H(+)) was achieved by irradiation of [Ru(tpy)(bpy)(DMF)](2+) (Ru-DMF(2+); DMF = N,N-dimethylformamide) in a tetrahydrofuran (THF) solution containing excess triethylamine (NEt(3)). The mechanism of the Ru-H(+) formation was investigated in detail. A photochemical ligand substitution reaction of Ru-DMF(2+) in THF proceeded to give [Ru(tpy)(bpy)(THF)](2+) (Ru-THF(2+)) with a quantum yield of (7.6 +/- 0.7) x 10(-2). In the presence of NEt(3), a similar photochemical ligand substitution reaction also proceeded quickly, but the products were an equilibrium mixture of Ru-THF(2+) and [Ru(tpy)(bpy)(NEt(3))](2+) (Ru-NEt(3)(2+)) with a considerable amount of Ru-H(+) even in the first stage of the photochemical reaction. The equilibrium constant between Ru-THF(2+) and Ru-NEt(3)(2+) was determined as 6.9 +/- 2.1. Irradiation to Ru-NEt(3)(2+) gave Ru-H(+) with a quantum yield of (9.1 +/- 0.5) x 10(-3). An important intermediate, Ru-NEt(3)(2+), was isolated, and its properties were investigated in detail.

  12. 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…

  13. 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…

  14. Photochemical ozone creation potentials for volatile organic compounds: Rationalization and estimation

    NASA Astrophysics Data System (ADS)

    Jenkin, M. E.; Derwent, R. G.; Wallington, T. J.

    2017-08-01

    The Photochemical Ozone Creation Potential (POCP) scale quantifies the relative abilities of volatile organic compounds (VOCs) to produce ground level ozone. POCP values are usually calculated using atmospheric boundary layer models containing detailed representations of atmospheric VOC degradation chemistry. The sensitivity of POCP values to variation of a number of kinetic and mechanistic parameters has been investigated here. It is shown that POCP values for VOCs can be rationalized in terms of their molecular structure and OH reactivity. As a result, a simple method has been developed and optimized that allows POCP values for north-west European and USA urban reference conditions to be estimated for alkanes, alkenes, aromatic hydrocarbons, and several oxygenated VOC classes without the requirement to construct a detailed chemical mechanism or run an atmospheric model. The procedure for determining the estimated POCP value (POCPE) is described, and the results are presented and discussed.

  15. Ozone process insights from field experiments - Part III: extent of reaction and ozone formation

    NASA Astrophysics Data System (ADS)

    Blanchard, Charles L.

    The analysis of ambient data offers a means of developing a qualitative understanding of the sensitivity of ozone formation at specific times and places to changes in VOC and NO x concentrations. The Integrated Empirical Rate (IER) model (Johnson, 1984, Proceedings of the Eighth International Clean Air Conference, Melbourne, Australia, pp. 715-731) and two revisions known as the Smog Production (SP) algorithm (Blanchard et al., 1999, Atmospheric Environment 33, 369-381; Chang et al., 1997, Atmospheric Environment 31, 2787-2794) are reviewed. Applied to ambient data, the algorithm requires measurements of ozone, NO, and either NO x or NO y and computes a quantity known as the extent of reaction. The extent of reaction is shown to be related to photochemical age and serves as an indicator of the sensitivity of instantaneous ozone production to changes in VOC or NO x concentrations. Extent of reaction alone is insufficient as an indicator of the sensitivity of ozone concentration to a complex upwind history of emission changes. Consideration of daily, hourly, and spatial patterns of extent of reaction is needed to interpret applications of the SP algorithm.

  16. Contributions of biogenic and anthropogenic hydrocarbons to photochemical smog formation

    SciTech Connect

    Paulson, S.E.

    1991-01-01

    Photochemical oxidation of biogenic (Isoprene) and anthropogenic (1-octene) hydrocarbons are examined. Experiments studied the individual daylight reactions of both isoprene and 1-octene, including those of OH, O{sub 3}, O({sup 3}P), and NO{sub 2}. The O{sub 3} reactions are found to produce significant quantities of OH, O({sup 3}P), and carbonyl yields that total about 100%. Isomerization is found to be an important channel for both isoprene and 1-octene. O({sup 3}P) reactions are found to have relatively minor decomposition pathways, resulting instead in epoxide formation. Results from both the smog chamber experiments and computer kinetic modeling were then used to develop photochemical oxidation mechanisms for each hydrocarbon. Aerosol formed by isoprene and another biogenic, {beta}-pinene, are characterized.

  17. Photochemical formation of copper nanoparticles in poly( N-vinylpyrrolidone)

    NASA Astrophysics Data System (ADS)

    Kapoor, Sudhir; Mukherjee, Tulsi

    2003-03-01

    Copper metal nanoparticles have been formed by irradiation with 253.7 nm light from a low pressure Hg-arc lamp in the presence of a protective agent poly( N-vinylpyrrolidone). The role of a photo-sensitizer, benzophenone (BP), in the formation of Cu metal particles was studied. The nanoparticles have been characterized by their absorption maxima and transmission electron micrographs. The average particle size for Cu was 15 nm. It appears that the presence of BP is essential for the photochemical preparation of copper nanoparticles. Laser spectroscopic studies have revealed that BP ketyl radical does not participate in the formation of Cu metal nanoparticles.

  18. Photochemical modeling of the Antarctic stratosphere: Observational constraints from the airborne Antarctic ozone experiment and implications for ozone behavior

    NASA Technical Reports Server (NTRS)

    Rodriguez, Jose M.; Sze, Nien-Dak; Ko, Malcolm K. W.

    1988-01-01

    The rapid decrease in O3 column densities observed during Antarctic spring has been attributed to several chemical mechanisms involving nitrogen, bromine, or chlorine species, to dynamical mechanisms, or to a combination of the above. Chlorine-related theories, in particular, predict greatly elevated concentrations of ClO and OClO and suppressed abundances of NO2 below 22 km. The heterogeneous reactions and phase transitions proposed by these theories could also impact the concentrations of HCl, ClNO3 and HNO3 in this region. Observations of the above species have been carried out from the ground by the National Ozone Expedition (NOZE-I, 1986, and NOZE-II, 1987), and from aircrafts by the Airborne Antarctic Ozone Experiment (AAOE) during the austral spring of 1987. Observations of aerosol concentrations, size distribution and backscattering ratio from AAOE, and of aerosol extinction coefficients from the SAM-II satellite can also be used to deduce the altitude and temporal behavior of surfaces which catalyze heterogeneous mechanisms. All these observations provide important constraints on the photochemical processes suggested for the spring Antarctic stratosphere. Results are presented for the concentrations and time development of key trace gases in the Antarctic stratosphere, utilizing the AER photochemical model. This model includes complete gas-phase photochemistry, as well as heterogeneous reactions. Heterogeneous chemistry is parameterized in terms of surface concentrations of aerosols, collision frequencies between gas molecules and aerosol surfaces, concentrations of HCl/H2O in the frozen particles, and probability of reaction per collision (gamma). Values of gamma are taken from the latest laboratory measurements. The heterogeneous chemistry and phase transitions are assumed to occur between 12 and 22 km. The behavior of trace species at higher altitudes is calculated by the AER 2-D model without heterogeneous chemistry. Calculations are performed for

  19. 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

  20. Formation of fatty acids in photochemical conversions of saturated hydrocarbons

    NASA Technical Reports Server (NTRS)

    Telegina, T. A.; Pavlovskaya, T. Y.; Ladyzhenskaya, A. I.

    1977-01-01

    Abiogenic synthesis of fatty acids was studied in photochemical conversions of saturated hydrocarbons. It was shown that, in a hydrocarbon water CaCO3 suspension, the action of 254 nm UV rays caused the formation of fatty acids with a maximum number of carbon atoms in the chain not exceeding that in the initial hydrocarbon. Synthesis of acetic, propionic, butyric, valeric, caproic, enanthic and caprylic (in the case of octane) acids occurs in heptane water CaCO3 and octane water CaCO3 systems.

  1. Susceptibility of Diabetic Rats to Pulmonary and Systemic Effects of Inhaled Photochemically-Aged Atmosphere and Ozone (O3)

    EPA Science Inventory

    Susceptibility of Diabetic Rats to Pulmonary and Systemic Effects of Inhaled Photochemically-Aged Atmosphere and Ozone (O3)MC Schladweiler1, SJ Snow2, QT Krantz1, C King1, JD Krug2, N Modak2, A Henriquez3, V Bass4, DJ Miller3, JE Richards1, EH Boykin1, R Jaskot1, MI Gilmour1 and ...

  2. Susceptibility of Diabetic Rats to Pulmonary and Systemic Effects of Inhaled Photochemically-Aged Atmosphere and Ozone (O3)

    EPA Science Inventory

    Susceptibility of Diabetic Rats to Pulmonary and Systemic Effects of Inhaled Photochemically-Aged Atmosphere and Ozone (O3)MC Schladweiler1, SJ Snow2, QT Krantz1, C King1, JD Krug2, N Modak2, A Henriquez3, V Bass4, DJ Miller3, JE Richards1, EH Boykin1, R Jaskot1, MI Gilmour1 and ...

  3. Photochemical production of ozone in Beijing during the 2008 Olympic Games

    NASA Astrophysics Data System (ADS)

    Chou, C. C.-K.; Tsai, C.-Y.; Chang, C.-C.; Lin, P.-H.; Liu, S. C.; Zhu, T.

    2011-06-01

    As a part of the CAREBeijing-2008 campaign, observations of O3, oxides of nitrogen (NOx and NOy), CO, and hydrocarbons (NMHCs) were carried out at the air quality observatory of the Peking University in Beijing, China during August 2008, including the period of the 29th Summer Olympic Games. The measurements were compared to those of the CAREBeijing-2006 campaign to evaluate the effectiveness of the air pollution control measures, which were conducted for improving the air quality in Beijing during the Olympics. The results indicate that significant reduction in the emissions of primary air pollutants had been achieved; the monthly averages of NOx, NOy, CO, and NMHCs reduced by 42.2, 56.5, 27.8, and 49.7 %, respectively. In contrast to the primary pollutants, the averaged mixing ratio of O3 increased by 42.2 %. Nevertheless, it was revealed that the ambient levels of total oxidants (Ox=O3+NO2+1.5NOz) and NOz reduced by 21.3 and 77.4 %, respectively. The contradictions between O3 and Ox were further examined in two case studies. Ozone production rates of 30-70 ppbv hr-1 and OPEx of ~8 mole mole-1 were observed on a clear-sky day in spite of the reduced levels of precursors. In that case, it was found that the concentrations of O3 increased with the increasing NO2/NO ratio, whereas the NOz concentrations leveled off when NO2/NO>8. Consequently, the ratio of O3 to NOz increased to above 10, indicating the shift from VOC-sensitive regime to NOx-sensitive regime. However, in the other case, it was found that the O3 production was inhibited significantly due to substantial reduction in the ambient levels of NMHCs. According to the observations, it was suggested that the O3/Ox production rates in Beijing should have been reduced for the reduction in the emissions of precursors during the Olympic period; however, the nighttime O3 levels were increased for decline in the NO-O3 titration, and the midday O3 peak levels were elevated for the shift in the photochemical regime

  4. Photochemical production of ozone in Beijing during the 2008 Olympic Games

    NASA Astrophysics Data System (ADS)

    Chou, C. C.-K.; Tsai, C.-Y.; Chang, C.-C.; Lin, P.-H.; Liu, S. C.; Zhu, T.

    2011-09-01

    the photochemical regime and the inhibition of NOz formation.

  5. Secondary aerosol formation through photochemical reactions estimated by using air quality monitoring data in Taipei City from 1994 to 2003

    NASA Astrophysics Data System (ADS)

    Chang, Shuenn-Chin; Lee, Chung-Te

    Analyses of diurnal patterns of PM 10 in Taipei City have been performed in this study at different daily ozone maximum concentrations (O 3,max) from 1994 to 2003. In order to evaluate secondary aerosol formation at different ozone levels, CO was used as a tracer of primary aerosol, and O 3,max was used as an index of photochemical activity. Results show that when O 3,max exceeds 120 ppb, the highest photochemical formation of secondary aerosol can be found at 15:00 (local time). The produced secondary aerosol is estimated to contribute 30 μg m -3 (43%) of PM 10 concentration, and about 77% of the estimated secondary PM 10 is composed of PM 2.5. The estimated maximum concentration of secondary aerosol occurs 2-3 h later than the maximum ozone concentration. As revealed in an O 3 episode, PM 10 and PM 2.5 vary consistently with O 3 at daytime, which suggests that they are mostly secondary aerosols produced from photochemical reactions. Data collected from Taipei aerosol supersite in 2002 indicates that for all O 3 levels, summertime PM 2.5 is composed of 23%, 20%, 9%, and 7% of organic carbon, sulfate, nitrate, and elemental carbon, respectively. Aerosol number and volume size spectra are dominated by submicron particles either from pollution transport or photochemical reactions. Secondary PM 10 concentrations show increasing tendencies for the time between 15:00 and 19:00 from 1994-1996 to 2001-2003. This reveals that the abatement of secondary PM 10 becomes more important after pronounced primary PM 10 reduction in a metropolis.

  6. The Anatomy of Wintertime Photochemical Ozone Production Events in the Upper Green River, WY and Uintah, UT Natural Gas Fields

    NASA Astrophysics Data System (ADS)

    Schnell, R. C.; Oltmans, S. J.; Johnson, B. J.; Neely, R. R., III

    2012-12-01

    Rapid, cold temperature, wintertime photochemical ozone production events occur in rural Wyoming and Utah in regions of natural gas production. In December through March surface ozone concentrations of 10-30 ppb at sunrise may increase to 100-150 ppb soon after solar noon in below freezing (as low as -17oC) air temperatures. The key ingredients for this ozone production are gaseous effluents from local fossil fuel extraction activities, a strong temperature inversion, and snow cover. In the Upper Green River Basin, Wyoming (UGRB) events, elevated diurnal ozone events may occur for a few days to a week then cease when a new airmass sweeps into the basin. In the absence of extended snowcover such as in the winters of 2009 and 2010, no appreciable ozone production events were observed in the UGRB. But, in 2011 there was snow on the ground and record ozone concentrations (hourly averages up to 164 ppb) were measured in the UGRB. In the winter of 2009-2010 in the Uintah Basin (UB), elevated diurnal ozone events began when snow pack was established in mid-December, 2009 and persisted until the day the snow melted in mid-March, 2010. During this 3 month period, there were 521 hours with hourly ozone concentrations above 75 ppb. In the winter of 2011-2012, in the absence of snow cover, there was no excessive ozone production in the UB. Boundary layer zone measurements in the UGRB in 2011 showed that diurnal ozone production started at the surface and quickly spread vertically up to the top of the surface inversion capped at ~100 m above ground level. The elevated ozone decreased just as rapidly within a few hours after solar noon.hotochemical ozone production in the Uintah Basin, UT gas field in association with the presence of snow cover.

  7. Photochemical formation of hydroxyl radical from effluent organic matter.

    PubMed

    Dong, Mei Mei; Rosario-Ortiz, Fernando L

    2012-04-03

    The photochemical formation of hydroxyl radical (HO•) from effluent organic matter (EfOM) was evaluated using three bulk wastewater samples collected at different treatment facilities under simulated sunlight. For the samples studied, the formation rates of HO•(R(HO•)) were obtained from the formation rate of phenol following the hydroxylation of benzene. The values of R(HO•) ranged from 2.3 to 3.8 × 10(-10) M s(-1) for the samples studied. The formation rate of HO• from nitrate photolysis (R(NO3)(HO•)) was determined to be 3.0 × 10(-7) M(HO)• M(NO3)(-1) s(-1). The HO• production rate from EfOM (R(EfOM)(HO•)) ranged from 0.76 to 1.3 × 10(-10) M s(-1). For the wastewater samples studied, R(EfOM)(HO•) varied from 1.5 to 2.4 × 10(-7) M(HO)• M(C)(-1) (s-1) on molarcarbon basis, which was close to HO• production from nitrate photolysis. The apparent quantum yield for the formation of HO• from nitrate (Φ(NO3-HO•)(a)) was determined as 0.010 ± 0.001 for the wavelength range 290-400 nm in ultrapure water. The apparent quantum yield for HO• formation in EfOM (Φ(EfOM-HO•)(a)) ranged from 6.1 to 9.8 × 10(-5), compared to 2.99 to 4.56 × 10(-5) for organic matter (OM) isolates. The results indicate that wastewater effluents could produce significant concentrations of HO•, as shown by potential higher nitrate levels and relatively higher quantum yields of HO• formation from EfOM.

  8. Ozone and secondary organic aerosol formation potential from anthropogenic volatile organic compounds emissions in China.

    PubMed

    Wu, Wenjing; Zhao, Bin; Wang, Shuxiao; Hao, Jiming

    2017-03-01

    Volatile organic compounds (VOCs) are major precursors for ozone and secondary organic aerosol (SOA), both of which greatly harm human health and significantly affect the Earth's climate. We simultaneously estimated ozone and SOA formation from anthropogenic VOCs emissions in China by employing photochemical ozone creation potential (POCP) values and SOA yields. We gave special attention to large molecular species and adopted the SOA yield curves from latest smog chamber experiments. The estimation shows that alkylbenzenes are greatest contributors to both ozone and SOA formation (36.0% and 51.6%, respectively), while toluene and xylenes are largest contributing individual VOCs. Industry solvent use, industry process and domestic combustion are three sectors with the largest contributions to both ozone (24.7%, 23.0% and 17.8%, respectively) and SOA (22.9%, 34.6% and 19.6%, respectively) formation. In terms of the formation potential per unit VOCs emission, ozone is sensitive to open biomass burning, transportation, and domestic solvent use, and SOA is sensitive to industry process, domestic solvent use, and domestic combustion. Biomass stoves, paint application in industrial protection and buildings, adhesives application are key individual sources to ozone and SOA formation, whether measured by total contribution or contribution per unit VOCs emission. The results imply that current VOCs control policies should be extended to cover most important industrial sources, and the control measures for biomass stoves should be tightened. Finally, discrepant VOCs control policies should be implemented in different regions based on their ozone/aerosol concentration levels and dominant emission sources for ozone and SOA formation potential. Copyright © 2016. Published by Elsevier B.V.

  9. Photochemical formation of hydroxyl radical by constituents of natural waters

    SciTech Connect

    Vaughan, P.P.; Blough, N.V.

    1998-10-01

    A new method is employed to determine the rates of photochemical hydroxyl radical (OH) formation in aqueous solutions and in natural waters under both aerobic and anaerobic conditions. Quantum yields for OH formation from the photolysis of nitrate and nitrite obtained by this method are in good agreement with previous measurements. Photolysis of Suwannee River fulvic acid (SRFA) solutions produced the hydroxyl radical under anaerobic conditions in proportion to the SRFA concentration. Under aerobic conditions, the quantum yields for OH formation were slightly higher and exhibited a different wavelength dependence than those obtained under anaerobic conditions. Experiments employing catalase indicate that Fenton chemistry can account for at most 50% of the total signal under aerobic conditions for SRFA irradiated at 310 and 320 nm. These results indicate the presence of a dioxygen-independent pathway of hydroxyl radical production that cannot be assigned to nitrate/nitrite photolysis or to Fenton chemistry. Results from the preliminary application of this method to natural waters are also presented.

  10. Stratospheric photochemical studies using Nimbus 7 data. I - Ozone photochemistry. II - Development of inferred trace specie distributions

    NASA Astrophysics Data System (ADS)

    Natarajan, M.; Lambeth, J. D.; Callis, L. B.; Boughner, R. E.; Russell, J. M., III

    1986-01-01

    The present investigation has the objective to make use of the limb infrared monitor of the stratosphere (LIMS) data set in conducting stratospheric photochemical studies. A description of the data is provided. The data are utilized in a zero-dimensional model incorporating the relevant chemistry. The chemical reaction scheme considered is a subset of the scheme used in the Langley one-dimensional model discussed by Callis et al. (1983). Attention is given to a comparison of model results and data, a model uncertainty analysis, model response to modifications in rate data, the ozone-temperature relationship, and the diurnal variation in the upper stratospheric ozone.

  11. Stratospheric photochemical studies using Nimbus 7 data. I - Ozone photochemistry. II - Development of inferred trace specie distributions

    NASA Technical Reports Server (NTRS)

    Natarajan, M.; Lambeth, J. D.; Callis, L. B.; Boughner, R. E.; Russell, J. M., III

    1986-01-01

    The present investigation has the objective to make use of the limb infrared monitor of the stratosphere (LIMS) data set in conducting stratospheric photochemical studies. A description of the data is provided. The data are utilized in a zero-dimensional model incorporating the relevant chemistry. The chemical reaction scheme considered is a subset of the scheme used in the Langley one-dimensional model discussed by Callis et al. (1983). Attention is given to a comparison of model results and data, a model uncertainty analysis, model response to modifications in rate data, the ozone-temperature relationship, and the diurnal variation in the upper stratospheric ozone.

  12. On applicability of the photochemical-equilibrium approach for retrieval of O and H mesospheric distributions from the satellite-based measurements of the airglow emission and ozone concentration

    NASA Astrophysics Data System (ADS)

    Feigin, Alexander; Belikovich, Mikhail; Kulikov, Mikhail

    2016-04-01

    Atomic oxygen and hydrogen are known to be among key components for the photochemistry and energy balance of the Earth's atmosphere between approximately 80 and 100 km altitude (mesopause region). Therefore, obtaining information about the vertical distributions of O and H concentrations is an important task in studies of this region. Solving of this problem is rather difficult due to the absence of regular methods which allow one to direct measurements of distributions of these components in mesosphere. However, indirect methods used to retrieve O and H distributions from the satellite-based measurements of the OH and O2(1D) airglow emission, as well as the data of IR and microwave O3 measurements have a sufficiently long development history. These methods are rooted in the use of the condition of photochemical equilibrium of ozone density in the range of altitudes from 50 to 100 km. A significant factor is that an insufficient volume of such measurement data forces researchers to use approximate ("truncated") photochemical-equilibrium conditions. In particular, it is assumed that in the daytime the ozone production reaction is perfectly balanced by ozone photodissociation, whereas during the night the only ozone sink is the reaction of ozone with atomic hydrogen, which, in its turn, leads to formation of excited OH and airglow emission of the latter. The presentation analyzes applicability of the photochemical-equilibrium conditions both in the total and truncated forms for description of the spatio-temporal evolution of mesospheric ozone during a year. The analysis is based on year-long time series generated by a 3D chemical transport model, which reproduces correctly various types of atmosphere dynamics in the range of altitudes from 50 to 100 km. These data are used to determine statistics of the ratio between the correct (calculated dynamically) distributions of the O3 density and its uncontracted and truncated equilibrium values for the conditions of the

  13. The effect of clouds on photolysis rates and ozone formation in the unpolluted troposphere

    NASA Technical Reports Server (NTRS)

    Thompson, A. M.

    1984-01-01

    The photochemistry of the lower atmosphere is sensitive to short- and long-term meteorological effects; accurate modeling therefore requires photolysis rates for trace gases which reflect this variability. As an example, the influence of clouds on the production of tropospheric ozone has been investigated, using a modification of Luther's two-stream radiation scheme to calculate cloud-perturbed photolysis rates in a one-dimensional photochemical transport model. In the unpolluted troposphere, where stratospheric inputs of odd nitrogen appear to represent the photochemical source of O3, strong cloud reflectance increases the concentration of NO in the upper troposphere, leading to greatly enhanced rates of ozone formation. Although the rate of these processes is too slow to verify by observation, the calculation is useful in distinguishing some features of the chemistry of regions of differing mean cloudiness.

  14. Dynamic aspects of the ozone anomalies formation in the Antarctic region

    NASA Astrophysics Data System (ADS)

    Lapo, Palina; Svetashev, Alexander; Krasouski, Alexander; Barodka, Siarhei

    2013-04-01

    The ozone layer is a unique shield protecting all living creatures on our planet. However, it has become subject of active research only after the first ozone hole was discovered over Antarctica. Ozone layer depletion over Antarctica is an even more acute problem, since Antarctica is the only continent having a very endemic, rich nature with least human impact. It has been shown that extreme temperature conditions in polar stratosphere and polar stratospheric clouds formation in addition to photochemical reactions involving ozone and ozone-depleting substances act as a primary cause of ozone-layer depletion. In the present study we review the dynamic aspects of ozone anomalies formation in the Antarctic region by numerical simulation. For that purpose we consider the ozone hole which formed over Antarctica in the period of September-October 2011. Using the WRF modelling system and its PolarWRF modification, we simulate meteorological situation over Antarctica in the time periods of ozone hole formation and destruction, and also in the time period when the ozone hole is absent. Based on the modelling results, we argue that a cold air mass (anticyclone) formed over the territory of Antarctica during the formation of the ozone hole. Absence of solar irradiation and strong cooling of the atmosphere contribute to formation of such meteorological conditions during the Antarctic winter. In the stratosphere there is a region of low atmospheric pressure, which is clearly visible on a pressure topography map. Under the effect of the tropospheric and the stratospheric vortices, air patches movement leads to ozone concentration decrease and formation of the ozone anomalies. From the WRF system modelling results we calculate several basic meteorological characteristics and analyze surface maps and aerological (skew-T) diagrams for atmospheric variables with the NCL scripting language. We conclude that atmospheric dynamics has an impact on ozone depression. Also, we evaluate the

  15. A two-dimensional photochemical model of the atmosphere. I Chlorocarbon emissions and their effect on stratospheric ozone

    NASA Technical Reports Server (NTRS)

    Gidel, L. T.; Crutzen, P. J.; Fishman, J.

    1983-01-01

    A two-dimensional photochemical model is used to examine changes to the ozone layer caused by emissions of CFCl3, CF2Cl2, CH3CCl3 and CCl4. The influence of a possible secular increase in tropospheric methane up to 2 percent per year was found to be small, although it acts to mask decreases in total ozone caused by the chlorocarbons. Increasing NO(x) emissions caused by industralization also tend to mask decreases in total ozone and may have caused total ozone to increase by about 1 percent. The model-calculated ozone decreases are estimated to be about 3 percent by 1980. This estimate is higher than estimates by similar models, although it is noted that CCl4 and CH3CCl3 emissions are included in the model in addition to CFCl3 and CF2Cl2. This is significant because the model indicates that CCl4 has dominated the ozone depletions so far, and knowledge of the historical emission rate of CCl4 to the atmosphere is incomplete. There remain sufficient significant disagreements between theoretical and observed concentrations and variabilities, particularly for odd nitrogen and ClO, to caution against assigning too much confidence in the calculated ozone depletion.

  16. Evidence for an unidentified non-photochemical ground-level source of formaldehyde in the Po Valley with potential implications for ozone production

    NASA Astrophysics Data System (ADS)

    Kaiser, J.; Wolfe, G. M.; Bohn, B.; Broch, S.; Fuchs, H.; Ganzeveld, L. N.; Gomm, S.; Häseler, R.; Hofzumahaus, A.; Holland, F.; Jäger, J.; Li, X.; Lohse, I.; Lu, K.; Prévôt, A. S. H.; Rohrer, F.; Wegener, R.; Wolf, R.; Mentel, T. F.; Kiendler-Scharr, A.; Wahner, A.; Keutsch, F. N.

    2015-02-01

    Ozone concentrations in the Po Valley of northern Italy often exceed international regulations. As both a source of radicals and an intermediate in the oxidation of most volatile organic compounds (VOCs), formaldehyde (HCHO) is a useful tracer for the oxidative processing of hydrocarbons that leads to ozone production. We investigate the sources of HCHO in the Po Valley using vertical profile measurements acquired from the airship Zeppelin NT over an agricultural region during the PEGASOS 2012 campaign. Using a 1-D model, the total VOC oxidation rate is examined and discussed in the context of formaldehyde and ozone production in the early morning. While model and measurement discrepancies in OH reactivity are small (on average 3.4 ± 13%), HCHO concentrations are underestimated by as much as 1.5 ppb (45%) in the convective mixed layer. A similar underestimate in HCHO was seen in the 2002-2003 FORMAT Po Valley measurements, though the additional source of HCHO was not identified. Oxidation of unmeasured VOC precursors cannot explain the missing HCHO source, as measured OH reactivity is explained by measured VOCs and their calculated oxidation products. We conclude that local direct emissions from agricultural land are the most likely source of missing HCHO. Model calculations demonstrate that radicals from degradation of this non-photochemical HCHO source increase model ozone production rates by as much as 0.6 ppb h-1 (12%) before noon.

  17. The Sensitivity of Model Ozone to Advective and Photochemical Processes in the High Latitude Winter Lower Stratosphere

    NASA Technical Reports Server (NTRS)

    Douglass, A.; Kawa, S. R.; Einaudi, Franco (Technical Monitor)

    2000-01-01

    Three dimensional chemistry and transport models (CTMs) contain a set of coupled continuity equations which describe the evolution of constituents such as ozone and other minor species which affect ozone. Both advection and photochemical processes contribute to constituent evolution, and a CTM provides a means to evaluate these contributions separately. Such evaluation is particularly useful when both terms are important to the modeled tendency. An example is the ozone tendency in the high latitude winter lower stratosphere, where advection tends to increase ozone, and catalytic processes involving chlorine radicals tend to decrease ozone. The Goddard three dimensional chemistry and transport model uses meteorological fields from the Goddard Earth Observing System Data Assimilation System, thus the modeled ozone evolution may reproduce the observed evolution and provide a test of the model representation of photochemical processes if the transport is shown to be modeled appropriately. We have investigated the model advection further using diabatic trajectory calculations. For long lived constituents such as N2O, the model field for a particular time on a potential temperature surface is compared with a field produced by calculating 15 day back trajectories for a fixed latitude longitude grid, and mapping model N2O at the terminus of the back trajectories onto the initial grid. This provides a quantitative means to evaluate two aspects of the CTM transport: one, the model horizontal gradient between middle latitudes and the polar vortex is compared with the gradient produced using the non-diffusive trajectory calculation; two, the model vertical advection, which is produced by the divergence of the horizontal winds, is compared with the vertical transport expected from diabatic cooling.

  18. The Sensitivity of Model Ozone to Advective and Photochemical Processes in the High Latitude Winter Lower Stratosphere

    NASA Technical Reports Server (NTRS)

    Douglass, A.; Kawa, S. R.; Einaudi, Franco (Technical Monitor)

    2000-01-01

    Three dimensional chemistry and transport models (CTMs) contain a set of coupled continuity equations which describe the evolution of constituents such as ozone and other minor species which affect ozone. Both advection and photochemical processes contribute to constituent evolution, and a CTM provides a means to evaluate these contributions separately. Such evaluation is particularly useful when both terms are important to the modeled tendency. An example is the ozone tendency in the high latitude winter lower stratosphere, where advection tends to increase ozone, and catalytic processes involving chlorine radicals tend to decrease ozone. The Goddard three dimensional chemistry and transport model uses meteorological fields from the Goddard Earth Observing System Data Assimilation System, thus the modeled ozone evolution may reproduce the observed evolution and provide a test of the model representation of photochemical processes if the transport is shown to be modeled appropriately. We have investigated the model advection further using diabatic trajectory calculations. For long lived constituents such as N2O, the model field for a particular time on a potential temperature surface is compared with a field produced by calculating 15 day back trajectories for a fixed latitude longitude grid, and mapping model N2O at the terminus of the back trajectories onto the initial grid. This provides a quantitative means to evaluate two aspects of the CTM transport: one, the model horizontal gradient between middle latitudes and the polar vortex is compared with the gradient produced using the non-diffusive trajectory calculation; two, the model vertical advection, which is produced by the divergence of the horizontal winds, is compared with the vertical transport expected from diabatic cooling.

  19. In Vivo Effects of Ozone Exposure on Protein Adduct Formation by 1-Nitronaphthalene in Rat Lung

    PubMed Central

    Wheelock, Åsa M.; Boland, Bridget C.; Isbell, Margaret; Morin, Dexter; Wegesser, Teresa C.; Plopper, Charles G.; Buckpitt, Alan R.

    2005-01-01

    The incidence of serious photochemical smog events is steadily growing in urban environments around the world. The electrophilic metabolites of 1-nitronaphthalene (1-NN), a common air pollutant in urban areas, have been shown to bind covalently to proteins. 1-NN specifically targets the airway epithelium, and the toxicity is synergized by prior long-term ozone exposure in rat. In this study we investigated the formation of 1-NN protein adducts in the rat airway epithelium in vivo and examined how prior long-term ozone exposure affects adduct formation. Eight adducted proteins, several involved in cellular antioxidant defense, were identified. The extent of adduction of each protein was calculated, and two proteins, peroxiredoxin 6 and biliverdin reductase, were adducted at high specific activities (0.36–0.70 and 1.0 nmol adduct/nmol protein). Furthermore, the N-terminal region of calreticulin, known as vasostatin, was adducted only in ozone-exposed animals. Although vasostatin was adducted at relatively low specific activity (0.01 nmol adduct/nmol protein), the adduction only in ozone-exposed animals makes it a candidate protein for elucidating the synergistic toxicity between ozone and 1-NN. These studies identified in vivo protein targets for reactive 1-NN metabolites that are potentially associated with the mechanism of 1-NN toxicity and the synergistic effects of ozone. PMID:15845863

  20. In vivo effects of ozone exposure on protein adduct formation by 1-nitronaphthalene in rat lung.

    PubMed

    Wheelock, Asa M; Boland, Bridget C; Isbell, Margaret; Morin, Dexter; Wegesser, Teresa C; Plopper, Charles G; Buckpitt, Alan R

    2005-08-01

    The incidence of serious photochemical smog events is steadily growing in urban environments around the world. The electrophilic metabolites of 1-nitronaphthalene (1-NN), a common air pollutant in urban areas, have been shown to bind covalently to proteins. 1-NN specifically targets the airway epithelium, and the toxicity is synergized by prior long-term ozone exposure in rat. In this study we investigated the formation of 1-NN protein adducts in the rat airway epithelium in vivo and examined how prior long-term ozone exposure affects adduct formation. Eight adducted proteins, several involved in cellular antioxidant defense, were identified. The extent of adduction of each protein was calculated, and two proteins, peroxiredoxin 6 and biliverdin reductase, were adducted at high specific activities (0.36-0.70 and 1.0 nmol adduct/nmol protein). Furthermore, the N-terminal region of calreticulin, known as vasostatin, was adducted only in ozone-exposed animals. Although vasostatin was adducted at relatively low specific activity (0.01 nmol adduct/nmol protein), the adduction only in ozone-exposed animals makes it a candidate protein for elucidating the synergistic toxicity between ozone and 1-NN. These studies identified in vivo protein targets for reactive 1-NN metabolites that are potentially associated with the mechanism of 1-NN toxicity and the synergistic effects of ozone.

  1. The relationship between ozone formation and air temperature in the atmospheric surface layer

    NASA Astrophysics Data System (ADS)

    Belan, Boris D.; Savkin, Denis; Tolmachev, Gennadii

    2016-04-01

    Studying the formation and dynamics of ozone in the atmosphere is important due to several reasons. First, the contribution of tropospheric ozone to the global greenhouse effect is only slightly less than that of water vapor, carbon dioxide, and methane. Second, tropospheric ozone acts as a strong poison that has negative effects on human health, animals, and vegetation. Third, being a potent oxidizer, ozone destroys almost all materials, including platinum group metals and compounds. Fourthly, ozone is formed in situ from precursors as a result of photochemical processes, but not emitted into the atmosphere by any industrial enterprises directly. In this work, we present some results of the study aimed at the revealing relationship between ozone formation rate and surface air temperature in the background atmosphere. It has been found that this relationship is nonlinear. Analysis of the possible reasons showed that the nonlinear character of this relationship may be due to a nonlinear increase in the reaction constants versus air temperature and a quadratic increase in the concentration of hydrocarbons with increasing temperature. This work was supported by the Ministry of Education and Science contract no.14.613.21.0013 (ID: RFMEFI61314X0013).

  2. Application of photochemical indicators to evaluate ozone nonlinear chemistry and pollution control countermeasure in China

    NASA Astrophysics Data System (ADS)

    Xie, Min; Zhu, Kuanguang; Wang, Tijian; Yang, Haoming; Zhuang, Bingliang; Li, Shu; Li, Minggao; Zhu, Xinsheng; Ouyang, Yan

    2014-12-01

    Ozone sensitivity in China was investigated by using a comprehensive three-dimensional air quality model system WRF-CALGRID. A real case and two cases with 35% emission reduction for either NOx or VOC were conducted for the period of March in 2010. The simulation results of O3 agreed fairly well with the observation data. Based on the meaning of O3 sensitivity, the ratio Ra was defined, with the transition value of 1 to distinguish NOx-sensitive region from VOC-sensitive region. With the aid of Ra, VOC- and NOx-sensitive regions in China were preliminary located. The transition ranges for some photochemical indicators were quantified. Only those of H2O2/NOz and H2O2/HNO3 met the requirement that the 95th percentile VOC-sensitive value should be equal to or lower than the 5th percentile NOx-sensitive value. 0.16-0.40 for H2O2/HNO3 and 0.14-0.28 for H2O2/NOz were adopted to distinguish different O3 sensitivity in China. The results showed that the VOC-sensitive regions are primarily distributed over the urban centers and the developed industrial areas in eastern and southern China, while the NOx-sensitive regions are mainly located in the remote areas of northern and western China. High correlation between Ra and indicators was found, and a new approach to quantify the transition values of indicators was proposed. These indicators can play an important role in the air complex pollution control of urban clusters over East Asia.

  3. Chemical pathway analysis of the Martian atmosphere: The formation and destruction of ozone

    NASA Astrophysics Data System (ADS)

    Boxe, C.; Stock, J.; Lehmann, R.; Grenfell, L.; Patzer, A.; Rauer, H.; Yung, Y. L.

    2014-12-01

    Ozone is a species of major importance in the Martian atmosphere e.g. since it is involved in the stabilization of Mars' major atmospheric constituent carbon dioxide. Below XX km altitude, ozone acts as an atomic oxygen source, which is produced by photolysis and oxidizes carbon monoxide via catalytic cycles involving odd hydrogen (HOx=H+OH+HO2). Originating mainly from H2O photolysis, odd hydrogen destroys ozone resulting in the observed anti-correlation between water vapor and ozone. Compared with species from the HOx-family, ozone is relatively easy to detect by e.g. UV spectroscopy or IR heterodyne spectroscopy. Similar to carbon dioxide, the concentration of ozone can be critically influenced by chemical trace species acting as catalysts in chemical pathways. The identification of such chemical pathways in complex reaction networks and the quantification of their contribution is in general challenging. Therefore, we use an automated computer algorithm (PAP - Pathway Analysis Program), which is specifically designed to address such problems. In this work, we apply the PAP-algorithm to the results of the newly updated JPL/Caltech photochemical column model of the Martian atmosphere in order to investigate the Martian atmospheric ozone photochemistry. The efficiencies of individual ozone formation and destruction pathways are calculated for different atmospheric heights, by applying the algorithm to each vertical layer of the column model in turn. The results of our investigations suggest that ozone is primarily produced by a Chapman-like mechanism, whereby atomic oxygen is produced by carbon dioxide photolysis instead of molecular oxygen photolysis. In the ozone layer at approximately 40 km altitude, ozone formation is chiefly dominated by a chemical pathway where atomic oxygen is supplied by vertical transport. Ozone consumption pathways involving ozone photolysis are most efficient except for a layer around 40 km altitude where the reaction between ozone and

  4. Source Contribution of Volatile Organic Compounds to Ozone Formation in Southeast Texas

    NASA Astrophysics Data System (ADS)

    Ying, Q.

    2009-12-01

    The Houston-Galveston-Brazoria (HGB) and Beaumont-Port Arthur (BPA) areas in the southeast Texas are respectively in severe and moderate non-attainment status for the National Ambient Air Quality Standards for ozone (O3). In order to design effective emission control strategies to improve ozone air quality, it is necessary to understand the contribution of volatile organic compounds (VOCs) from different sources to O3 formation. In this study, a source-oriented SAPRC-99 gas phase photochemical mechanism was developed and incorporated into the Community Multiscale Air Quality (CMAQ) model to determine the contribution of volatile organic compounds (VOCs) from different sources to the predicted net ozone formation rate in southeast Texas during the Texas Air Quality Study (TexAQS) from 16 August - 6 September 2000. Contribution from eight different sources: biogenic, diesel engines, highway gasoline vehicles, off-highway gasoline engines, solvent utilization, petroleum industry, other industries and wildfire were resolved. This is the first time that the regional source contribution of VOCs to O3 formation has been quantified using a three-dimensional source oriented modeling approach in southeast Texas. Regional source contribution analysis indicates that the VOCs emitted from petrochemical industries are responsible to a large amount of O3 formation in the HGB and BPA area. The peak O3 formation rate due to petroleum industry and other industries combined is ~8 ppb hr(-1) in early afternoon hours, which rivals the O3 formation rate due to biogenic sources (~ 9 ppb hr(-1)). Gasoline vehicles also contribute significantly to the ozone formation, with a maximum contribution of ~3.5 ppb hr(-1). The spatial coverage of vehicle sources is larger that of industrial sources. Solvent utilization contributes ~1.2 ppb hr(-1) and has similar spatial coverage as gasoline vehicle sources. VOC emissions from reciprocating engines powered by natural gas are the most significant

  5. Laboratory studies of chemical and photochemical processes relevant to stratospheric ozone

    NASA Technical Reports Server (NTRS)

    Zahniser, Mark S.; Nelson, David D.; Worsnop, Douglas R.; Kolb, Charles E.

    1994-01-01

    The purpose of this project is to reduce the uncertainty in several key gas-phase kinetic processes which impact our understanding of stratospheric ozone. The main emphasis of this work is on measuring rate coefficients and product channels for reactions of HO(sub x) and NO(sub x) species in the temperature range 200 K to 240 K relevant to the lower stratosphere. Other areas of study have included infrared spectroscopic studies of the HO2 radical, measurements of OH radical reactions with alternative fluorocarbons, and determination of the vapor pressures of nitric acid hydrates under stratospheric conditions. The results of these studies will improve models of stratospheric ozone chemistry and predictions of perturbations due to human influences. In this annual report, we focus on our recent accomplishments in the quantitative spectroscopy of the HO2 radical. This report details the measurements of the broadening coefficients for the v(sub 2) vibrational band. Further measurements of the vapor pressures of nitric acid hydrates relevant to the polar stratospheric cloud formation indicate the importance of metastable crystalline phases of H2SO4, HNO3, and H2O. Large particles produced from these metastable phases may provide a removal mechanism for HNO3 in the polar stratosphere.

  6. Natural hydrocarbon emission estimates based on Landsat data as an input to a regional ozone photochemical model

    NASA Technical Reports Server (NTRS)

    Middleton, E. M.; Gervin, J. C.; Salop, J.

    1982-01-01

    Landsat-derived forest cover data were employed with non-methane hydrocarbon (NMHC) emission rates in a model to quantify summer forest ozone production for the Tidewater Region of Virginia. The areal extent of the three major forest types - coniferous, deciduous, and mixed - were determined from Landsat data on two adjacent scenes, using an unsupervised approach to spectral signature development. The forest type results from both data sets were verified in an extensive accuracy assessment and merged to provide regional statistics for total acreages, percent forest, and error rates. The Landsat statistics were incorporated into forest type emission factor equations to produce an estimated emission rate for natural hydrocarbons from forests. This estimate, along with measured rates for nitrogen oxides and NMHC from anthropogenic sources, was provided as input to computer simulations of atmospheric ozone generation for the Tidewater Region using a photochemical oxident model.

  7. Natural hydrocarbon emission estimates based on Landsat data as an input to a regional ozone photochemical model

    NASA Technical Reports Server (NTRS)

    Middleton, E. M.; Gervin, J. C.; Salop, J.

    1982-01-01

    Landsat-derived forest cover data were employed with non-methane hydrocarbon (NMHC) emission rates in a model to quantify summer forest ozone production for the Tidewater Region of Virginia. The areal extent of the three major forest types - coniferous, deciduous, and mixed - were determined from Landsat data on two adjacent scenes, using an unsupervised approach to spectral signature development. The forest type results from both data sets were verified in an extensive accuracy assessment and merged to provide regional statistics for total acreages, percent forest, and error rates. The Landsat statistics were incorporated into forest type emission factor equations to produce an estimated emission rate for natural hydrocarbons from forests. This estimate, along with measured rates for nitrogen oxides and NMHC from anthropogenic sources, was provided as input to computer simulations of atmospheric ozone generation for the Tidewater Region using a photochemical oxident model.

  8. Infrared matrix isolation study of the thermal and photochemical reactions of ozone with trimethylgallium.

    PubMed

    Sriyarathne, H Dushanee M; Gudmundsdottir, Anna D; Ault, Bruce S

    2015-03-26

    The thermal and photochemical reactions of (CH3)3Ga and O3 have been explored using a combination of matrix isolation, infrared spectroscopy, and theoretical calculations. Experimental data using twin jet deposition and theoretical calculations demonstrate the formation of multiple product species after deposition, annealing to 35 K, and UV irradiation of the matrices. The products were identified as (CH3)2GaOCH3, (CH3)2GaCH2OH, (CH3)(CH3O)Ga(OCH3), (CH3)2GaCHO, and (CH3)Ga(OCH3)(CH2OH). Product identifications were confirmed by annealing and irradiation behavior, (18)O substitution experiments, and high level theoretical calculations. Merged jet deposition led to a number of stable late reaction products, including C2H6, CH3OH, and H2CO. A white solid film was also noted on the walls of the merged (flow reactor) region of the deposition system, likely due to the formation of Ga2O3.

  9. Observing entrainment mixing, photochemical ozone production, and regional methane emissions by aircraft using a simple mixed-layer framework

    NASA Astrophysics Data System (ADS)

    Trousdell, Justin F.; Conley, Stephen A.; Post, Andy; Faloona, Ian C.

    2016-12-01

    In situ flight data from two distinct campaigns during winter and summer seasons in the San Joaquin Valley (SJV) of California are used to calculate boundary-layer entrainment rates, ozone photochemical production rates, and regional methane emissions. Flights near Fresno, California, in January and February 2013 were conducted in concert with the NASA DISCOVER-AQ project. The second campaign (ArvinO3), consisting of 11 days of flights spanning June through September 2013 and 2014, focused on the southern end of the SJV between Bakersfield and the small town of Arvin, California - a region notorious for frequent violations of ozone air quality standards. Entrainment velocities, the parameterized rates at which free tropospheric air is incorporated into the atmospheric boundary layer (ABL), are estimated from a detailed budget of the inversion base height. During the winter campaign near Fresno, we find an average midday entrainment velocity of 1.5 cm s-1, and a maximum of 2.4 cm s-1. The entrainment velocities derived during the summer months near Bakersfield averaged 3 cm s-1 (ranging from 0.9 to 6.5 cm s-1), consistent with stronger surface heating in the summer months. Using published data on boundary-layer heights we find that entrainment rates across the Central Valley of California have a bimodal annual distribution peaking in spring and fall when the lower tropospheric stability (LTS) is changing most rapidly.Applying the entrainment velocities to a simple mixed-layer model of three other scalars (O3, CH4, and H2O), we solve for ozone photochemical production rates and find wintertime ozone production (2.8 ± 0.7 ppb h-1) to be about one-third as large as in the summer months (8.2 ± 3.1 ppb h-1). Moreover, the summertime ozone production rates observed above Bakersfield-Arvin exhibit an inverse relationship to a proxy for the volatile organic compound (VOC) : NOx ratio (aircraft [CH4] divided by surface [NO2]), consistent with a NOx-limited photochemical

  10. Net ozone photochemical production over the eastern and central North Pacific as inferred from GTE/CITE 1 observations during fall 1983

    NASA Technical Reports Server (NTRS)

    Chameides, W. L.; Davis, D. D.; Rodgers, M. O.; Bradshaw, J.; Sandholm, S.; Sachse, G.; Hill, G.; Gregory, G.

    1987-01-01

    The role of photochemistry in the budget of tropospheric ozone is studied. Measurements of O3, NO, CO, H2O vapor, and temperature obtained during the fall of 1983 during the GTE/CITE project over the eastern and central North Pacific Ocean are analyzed. The effect of altitude on the measurements is discussed. The analysis reveals a correlation between ozone and NO levels; both increase in concentration and variability with altitude. It is observed that an additional source of secondary importance associated wih CO-rich air parcels exists. A photochemical model is utilized to calculate the net rate of ozone production by photochemical reactions. A net photochemical source of ozone in the free troposphere and a net sink in the boundary layer are detected. The relation between the ozone source in the free troposphere and NO is examined. It is estimated that photochemistry provides a net ozone source to the free troposphere overlying the eastern and central North Pacific Ocean of about 5 x 10 to the 10th molecules/sq cm sec and a net sink of ozone to the boundary layer overlying this region of about 3 x 10 to the 10th molecules/sq cm sec.

  11. Photochemical production and loss rates of ozone at Sable Island, Nova Scotia during the North Atlantic Regional Experiment (NARE) 1993 summer intensive

    NASA Astrophysics Data System (ADS)

    Duderstadt, K. A.; Carroll, M. A.; Sillman, S.; Wang, T.; Albercook, G. M.; Feng, L.; Parrish, D. D.; Holloway, J. S.; Fehsenfeld, F. C.; Blake, D. R.; Blake, N. J.; Forbes, G.

    1998-06-01

    Three weeks of summertime surface-based chemical and meteorological observations at Sable Island, Nova Scotia during the North Atlantic Regional Experiment (NARE) 1993 summer intensive are used to study instantaneous photochemical production and loss rates of ozone by means of a numerical photochemical model. Results are most sensitive to the averaging scheme of data used to constrain the model and the ambient variability of the measurements. Model simulations driven by a time series of 5 min averaged data, most representative of the chemistry at the site, yield an average net photochemical ozone production of 3.6 ppbv/d. Estimates of net ozone production designed to filter out local sources, by using 1000-1400 LT median values of observations to drive the model and by excluding short-lived hydrocarbons, give values ranging from 1 to 4 ppbv/d. These positive values of net ozone production within the marine boundary layer over Sable Island demonstrate the impact of polluted continental plumes on the background photochemistry of the region during the intensive. The dominant ambient variables controlling photochemical production and loss rates of ozone at the site during the measurement campaign appear to be levels of nitrogen oxides, ozone, nonmethane hydrocarbons, and solar intensity determined by cloud cover. The model partitioning of nitrogen oxides agrees for the most part with measurements, lending credence to calculated photochemical production and loss rates of ozone as well as inferred levels of peroxy radicals not measured at the site. Discrepancies, however, often occur during episodes of intermittent cloud cover, fog, and rain, suggesting the influence of cloud processes on air masses reaching the site.

  12. Ozone kinetics in low-pressure discharges: vibrationally excited ozone and molecule formation on surfaces

    NASA Astrophysics Data System (ADS)

    Marinov, Daniil; Guerra, Vasco; Guaitella, Olivier; Booth, Jean-Paul; Rousseau, Antoine

    2013-10-01

    A combined experimental and modeling investigation of the ozone kinetics in the afterglow of pulsed direct current discharges in oxygen is carried out. The discharge is generated in a cylindrical silica tube of radius 1 cm, with short pulse durations between 0.5 and 2 ms, pressures in the range 1-5 Torr and discharge currents ˜40-120 mA. Time-resolved absolute concentrations of ground-state atoms and ozone molecules were measured simultaneously in situ, by two-photon absorption laser-induced fluorescence and ultraviolet absorption, respectively. The experiments were complemented by a self-consistent model developed to interpret the results and, in particular, to evaluate the roles of vibrationally excited ozone and of ozone formation on surfaces. It is found that vibrationally excited ozone, O_3^{*} , plays an important role in the ozone kinetics, leading to a decrease in the ozone concentration and an increase in its formation time. In turn, the kinetics of O_3^{*} is strongly coupled with those of atomic oxygen and O2(a 1Δg) metastables. Ozone formation at the wall does not contribute significantly to the total ozone production under the present conditions. Upper limits for the effective heterogeneous recombination probability of O atoms into ozone are established.

  13. Atmospheric photochemical reactivity and ozone production at two sites in Hong Kong: Application of a Master Chemical Mechanism-photochemical box model

    NASA Astrophysics Data System (ADS)

    Ling, Z. H.; Guo, H.; Lam, S. H. M.; Saunders, S. M.; Wang, T.

    2014-09-01

    A photochemical box model incorporating the Master Chemical Mechanism (v3.2), constrained with a full suite of measurements, was developed to investigate the photochemical reactivity of volatile organic compounds at a semirural site (Mount Tai Mo Shan (TMS)) and an urban site (Tsuen Wan (TW)) in Hong Kong. The levels of ozone (O3) and its precursors, and the magnitudes of the reactivity of O3 precursors, revealed significant differences in the photochemistry at the two sites. Simulated peak hydroperoxyl radical (HO2) mixing ratios were similar at TW and TMS (p = 0.05), while the simulated hydroxyl radical (OH) mixing ratios were much higher at TW (p < 0.05), suggesting different cycling processes between OH and HO2 at the two sites. The higher OH at TW was due to high-NO mixing ratios, which shifted the HOx (OH + HO2) balance toward OH by the propagation of HO2 and alkyl peroxy radicals (RO2) with NO. HOx production was dominated by O3 photolysis at TMS, but at TW, both HCHO and O3 photolyses were found to be major contributors. By contrast, radical-radical reactions governed HOx radical losses at TMS, while at TW, the OH + NO2 reaction was found to dominate in the morning and the radical-radical reactions at noon. Overall, the conversion of NO to NO2 by HO2 dictated the O3 production at the two sites, while O3 destruction was dominated by the OH + NO2 reaction at TW, and at TMS, O3 photolysis and the O3 + HO2 reaction were the major mechanisms. The longer OH chain length at TMS indicated that more O3 was produced for each radical that was generated at this site.

  14. Anaerobic effluent disinfection using ozone: byproducts formation.

    PubMed

    Silva, G H R; Daniel, L A; Bruning, H; Rulkens, W H

    2010-09-01

    This research was aimed at studying oxidation processes, coliform inactivation effectiveness and disinfection byproducts (DBPs) associated with the disinfection of anaerobic sanitary wastewater effluent with ozone applied at doses of 5.0, 8.0 and 10.0mg O(3)L(-1) for contact times of 5, 10 and 15 min. The wastewater used in this research was generated by the wastewater treatment plant (WWTP), University of São Paulo - Brazil. The total coliform inactivation range was 2.00-4.06 log(10), and the inactivation range for Escherichia coli was 2.41-4.65 log(10). Mean chemical oxygen demand (COD) reductions were 37.6%, 48.8% and 42.4% for doses of 5.0, 8.0 and 10.0mg O(3)L(-1), respectively. Aldehyde formation varied with dosage only when the ozone dose was increased from 5.0 to 8.0mg O(3)L(-1) for acetaldehyde and from 5.0 to 8.0 and from 8.0 to 10.0mg O(3)L(-1) for glyoxal.

  15. Photochemical ozone production in tropical squall line convection during NASA Global Tropospheric Experiment/Amazon Boundary Layer Experiment 2A

    NASA Technical Reports Server (NTRS)

    Pickering, Kenneth E.; Thompson, Anne M.; Tao, Wei-Kuo; Simpson, Joanne; Scala, John R.

    1991-01-01

    The role of convection was examined in trace gas transport and ozone production in a tropical dry season squall line sampled on August 3, 1985, during NASA Global Tropospheric Experiment/Amazon Boundary Layer Experiment 2A (NASA GTE/ABLE 2A) in Amazonia, Brazil. Two types of analyses were performed. Transient effects within the cloud are examined with a combination of two-dimensional cloud and one-dimensional photochemical modeling. Tracer analyses using the cloud model wind fields yield a series of cross sections of NO(x), CO, and O3 distribution during the lifetime of the cloud; these fields are used in the photochemical model to compute the net rate of O3 production. At noon, when the cloud was mature, the instantaneous ozone production potential in the cloud is between 50 and 60 percent less than in no-cloud conditions due to reduced photolysis and cloud scavenging of radicals. Analysis of cloud inflows and outflows is used to differentiate between air that is undisturbed and air that has been modified by the storm. These profiles are used in the photochemical model to examine the aftereffects of convective redistribution in the 24-hour period following the storm. Total tropospheric column O3 production changed little due to convection because so little NO(x) was available in the lower troposphere. However, the integrated O3 production potential in the 5- to 13-km layer changed from net destruction to net production as a result of the convection. The conditions of the August 3, 1985, event may be typical of the early part of the dry season in Amazonia, when only minimal amounts of pollution from biomass burning have been transported into the region.

  16. Formation of the 1988 Antarctic ozone hole

    SciTech Connect

    Krueger, A.J.; Stolarski, R.S.; Schoeberl, M.R. )

    1989-05-01

    The 1988 Antarctic ozone hole, as observed with the Nimbus 7 TOMS instrument, formed in August but failed to deepen significantly during September. The structure of the surrounding total ozone maxima also differed from the prior year. The 1987 total ozone pattern was pole centered and symmetrical. During 1988 a persistent strong wavenumber 1 perturbation in total ozone developed in August which resulted in displacement of the polar ozone minimum to the base of the Antarctic Peninsula. Subsequently, a series of transient events diminished and a larger scale decrease in polar total ozone began. The decrease lasted less than two weeks, resulting in a net change of only 25 DU compared with the nearly 100 DU decline observed during the same period in 1987. The minimum values remained roughly constant until October 19, 1988 and then increased rapidly. The 1988 Antarctic ozone hole subsequently drifted off the Antarctic continent in late October and dissipated in mid-November.

  17. An Airborne Investigation of Boundary Layer Dynamics, Entrainment, and Ozone Photochemical Production During DISCOVER-AQ in California's Central Valley

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

    During the California deployment of NASA's DISCOVER-AQ project of January/February 2013, our team flew a Mooney TLS research aircraft instrumented with an in-house wind measurement system, a UV absorption ozone instrument, temperature probe, and a Picarro methane, carbon dioxide, and water vapor analyzer. Flights were focused on the lowest 1000 m across the Central Valley axis just north of Fresno in order to characterize the wintertime atmospheric boundary layer (ABL). For seven flights we report the observed ABL growth rates, and compare these with a simple mixed layer model driven by surface heat flux estimates from the North American Regional Reanalysis data set. By enforcing a mixed layer budget closure of the observed water vapor trend and the differential across the ABL top, we derive midday entrainment velocities for the region that average 1.2 (± 0.4) cm s-1. A similar budgeting method is used for ozone to estimate wintertime photochemical production rates that ranged from 0.5 to 7.0 ppb h-1, and exhibited a strong correlation with ambient temperature (see Figure) and total ozone abundance. Finally, the gross emissions of methane for this heavily agricultural region are estimated and compared to existing inventories. These results can provide important constraints on ABL growth and entrainment to aid surface studies of aerosol composition and other trace gases that are being conducted for DISCOVER-AQ.

  18. Modelling segregation effects of heterogeneous emissions on ozone levels in idealised urban street canyons: using photochemical box models.

    PubMed

    Zhong, Jian; Cai, Xiao-Ming; Bloss, William James

    2014-05-01

    Air quality models include representations of pollutant emissions, which necessarily entail spatial averaging to reflect the model grid size; such averaging may result in significant uncertainties and/or systematic biases in the model output. This study investigates such uncertainties, considering ozone concentrations in idealised street canyons within the urban canopy. A photochemical model with grid-averaged emissions of street canyons is compared with a multiple-box model considering each canyon independently. The results reveal that the averaged, 'one-box' model may significantly underestimate true (independent canyon mean) ozone concentrations for typical urban areas, and that the performance of the averaged model is improved for more 'green' and/or less trafficked areas. Our findings also suggest that the trends of 2005-2020 in emissions, in isolation, reduce the error inherent in the averaged-emissions treatment. These new findings may be used to evaluate uncertainties in modelled urban ozone concentrations when grid-averaged emissions are adopted. Copyright © 2014 Elsevier Ltd. All rights reserved.

  19. Photochemical smog effects in mixed conifer forests along a natural gradient of ozone and nitrogen deposition in the San Bernardino Mountains

    Treesearch

    Michael Arbaugh; Andrzej Bytnerowicz; Nancy Grulke; Mark Fenn; Mark Poth; Patrick Temple; Paul Miller

    2003-01-01

    Toxic effects of photochemical smog on ponderosa and Jeffrey pines in the San Bernardino Mountains were discovered in the 1950s. It was revealed that ozone is the main cause of foliar injury manifested as chlorotic mottle and premature needle senescence. Various morphological, physiological and biochemical alterations in the affected plants have been reported over a...

  20. Photochemical age of air pollutants, ozone, and secondary organic aerosol in transboundary air observed on Fukue Island, Nagasaki, Japan

    NASA Astrophysics Data System (ADS)

    Irei, Satoshi; Takami, Akinori; Sadanaga, Yasuhiro; Nozoe, Susumu; Yonemura, Seiichiro; Bandow, Hiroshi; Yokouchi, Yoko

    2016-04-01

    To better understand the secondary air pollution in transboundary air over westernmost Japan, ground-based field measurements of the chemical composition of fine particulate matter ( ≤ 1 µm), mixing ratios of trace gas species (CO, O3, NOx, NOy, i-pentane, toluene, and ethyne), and meteorological elements were conducted with a suite of instrumentation. The CO mixing ratio dependence on wind direction showed that there was no significant influence from primary emission sources near the monitoring site, indicating long- and/or mid-range transport of the measured chemical species. Despite the considerably different atmospheric lifetimes of NOy and CO, these mixing ratios were correlated (r2 = 0.67). The photochemical age of the pollutants, t[OH] (the reaction time × the mean concentration of OH radical during the atmospheric transport), was calculated from both the NOx / NOy concentration ratio (NOx / NOy clock) and the toluene / ethyne concentration ratio (hydrocarbon clock). It was found that the toluene / ethyne concentration ratio was significantly influenced by dilution with background air containing 0.16 ppbv of ethyne, causing significant bias in the estimation of t[OH]. In contrast, the influence of the reaction of NOx with O3, a potentially biasing reaction channel on [NOx] / [NOy], was small. The t[OH] values obtained with the NOx / NOy clock ranged from 2.9 × 105 to 1.3 × 108 h molecule cm-3 and were compared with the fractional contribution of the m/z 44 signal to the total signal in the organic aerosol mass spectra (f44, a quantitative oxidation indicator of carboxylic acids) and O3 mixing ratio. The comparison of t[OH] with f44 showed evidence for a systematic increase of f44 as t[OH] increased, an indication of secondary organic aerosol (SOA) formation. To a first approximation, the f44 increase rate was (1.05 ± 0.03) × 10-9 × [OH] h-1, which is comparable to the background-corrected increase rate observed during the New England Air Quality

  1. 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.

  2. 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.

  3. Spatial Distribution of Ozone Formation in China Derived from Emissions of Speciated Volatile Organic Compounds.

    PubMed

    Wu, Rongrong; Xie, Shaodong

    2017-03-07

    Ozone (O3) pollution is becoming increasingly severe in China. In addition, our limited understanding of the relationship between O3 and volatile organic compounds (VOCs), is an obstacle to improving air quality. By developing an improved source-oriented speciated VOC emission inventory in 2013, we estimated the ozone formation potential (OFP) and investigated its characteristics in China. Besides, a comparison was made between our estimates and space-based observations from the ozone monitoring instrument (OMI) on the National Aeronautics and Space Administration (NASA)'s Aura satellite. According to our estimates, m-/p-xylene, ethylene, formaldehyde, toluene, and propene were the five species that had the largest potential to form ozone, and on-road vehicles, industrial processes, biofuel combustion, and surface coating were the key contributing sectors. Among different regions of China, the North China Plain, Yangtze River Delta, and Pearl River Delta had the highest OFP values. Our results suggest that O3 formation is VOC-limited in major urban areas of China. Additionally, considering the different photochemical reactivities of various VOC species and the disparate energy and industry structures in the different regions of China, more efficient OFP-based and localized VOC control measures should be implemented, instead of the current mass-based and nationally uniform policies.

  4. The role of reactive nitrogen chemistry in the photochemical and haze pollution in China: WRF-Chem simulations of HONO and N2O5 processes and their impact on ozone and aerosol nitrate

    NASA Astrophysics Data System (ADS)

    Li, Qinyi; Zhang, Li; Wang, Tao; Fu, Xiao; Tham, Yee Jun; Wang, Weihao; Wang, Zhe; Zhang, Qiang

    2017-04-01

    Nitrous acid (HONO) is a major source of the hydroxyl radical in the polluted troposphere. The heterogeneous uptake of dinitrogen pentoxide (N2O5) produces the particulate nitrate and the nitryl chloride (ClNO2) hence the chlorine radical. The hydroxyl and chlorine radicals initiate the degradation of volatile organic compounds which leads to the production of ozone with the presence of nitrogen oxides (NOx). Photochemical (ozone) and haze (particulate) pollution has raised huge concerns in China in recent years. However, the collective role of HONO, N2O5 and ClNO2 chemistry in the formation of air pollution in China is yet to be quantified. Weather Research and Forecasting model coupled with Chemistry (WRF-Chem) has been incorporated with comprehensive reactive nitrogen oxides mechanism (ReNOM), including the latest HONO sources, the heterogeneous uptake of N2O5 and the subsequent ClNO2 production and chlorine chemistry. The revised WRF-Chem was adopted to simulate the spatial-temporal distribution of HONO, N2O5 and ClNO2, and to investigate the contribution of nitrogen chemistry to the production of ozone and secondary aerosol in China in summer when photochemical pollution is severe, and in winter season during which haze pollution is alarming in northern China. The simulations showed that the reactive nitrogen chemistry considerably increased the concentration of OH and Cl radical and hence the degradation of VOCs and the production of ozone; the chemistry altered the lifetime of NOx and enhanced the transformation of NOx into nitrate aerosol. Sensitivity simulations were conducted by reducing the NOx and/or VOCs emission, and the difference between the simulated ozone with original emission and that with reduced emission will be used to identify the ozone formation regime in different areas of China. The spatial pattern of the ozone formation regime in China suggested by original and revised WRF-Chem will be compared and analyzed to explore the potential role

  5. Simulation of the effects of critical factors on ozone formation and accumulation in the greater Athens area

    NASA Astrophysics Data System (ADS)

    Bossioli, Elissavet; Tombrou, Maria; Dandou, Aggeliki; Soulakellis, Nikos

    2007-01-01

    In the present study, the temporal and spatial dynamics of the ozone production in the greater Athens area (GAA) is examined by using the photochemical UAM-V model coupled with the meteorological MM5 model. Several numerical experiments were performed in order to investigate and to quantify the effect of critical factors that conduce to the ozone formation and accumulation during ozone episodes. The initial scenario is able to reproduce the observed ozone patterns, but it underestimates the observed peaks in most of the downwind suburban stations. Using process analysis, we demonstrate the contribution of chemical and physical processes to ozone formation and destruction. The inclusion of biogenic emissions and their distribution based on a satellite vegetation index, as well as the adjustment of the speciation of the anthropogenic NMVOC emissions according to specific characteristics measured in street and aged city plumes, lead to a more realistic description of the urban mixture and thus of the ozone production. The effect of the urban sector introduced via a simplified urbanized meteorological data set, provoke a differentiation of the spatial pattern attributed to the accumulation of the primary NOX pollutants inside the city center and to the consequent limited horizontal advection toward the peripheral zone. Finally, the ozone background turned out to be a key factor for the model performance. The statistical evaluation of the results reveals the importance and the necessity of implementing all the above modifications; the persistence of some discrepancies is associated with meteorological or modeling coupling limitations.

  6. 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

    /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.

  7. Photochemical model evaluation of the ground-level ozone impacts on ambient air quality and vegetation health in the Alberta oil sands region: Using present and future emission scenarios

    NASA Astrophysics Data System (ADS)

    Vijayaraghavan, Krish; Cho, Sunny; Morris, Ralph; Spink, David; Jung, Jaegun; Pauls, Ron; Duffett, Katherine

    2016-09-01

    One of the potential environmental issues associated with oil sands development is increased ozone formation resulting from NOX and volatile organic compound emissions from bitumen extraction, processing and upgrading. To manage this issue in the Athabasca Oil Sands Region (AOSR) in northeast Alberta, a regional multi-stakeholder group, the Cumulative Environmental Management Association (CEMA), developed an Ozone Management Framework that includes a modelling based assessment component. In this paper, we describe how the Community Multi-scale Air Quality (CMAQ) model was applied to assess potential ground-level ozone formation and impacts on ambient air quality and vegetation health for three different ozone precursor cases in the AOSR. Statistical analysis methods were applied, and the CMAQ performance results met the U.S. EPA model performance goal at all sites. The modelled 4th highest daily maximum 8-h average ozone concentrations in the base and two future year scenarios did not exceed the Canada-wide standard of 65 ppb or the newer Canadian Ambient Air Quality Standards of 63 ppb in 2015 and 62 ppb in 2020. Modelled maximum 1-h ozone concentrations in the study were well below the Alberta Ambient Air Quality Objective of 82 ppb in all three cases. Several ozone vegetation exposure metrics were also evaluated to investigate the potential impact of ground-level ozone on vegetation. The chronic 3-months SUM60 exposure metric is within the CEMA baseline range (0-2000 ppb-hr) everywhere in the AOSR. The AOT40 ozone exposure metric predicted by CMAQ did not exceed the United Nations Economic Commission for Europe (UN/ECE) threshold of concern of 3000 ppb-hr in any of the cases but is just below the threshold in high-end future emissions scenario. In all three emission scenarios, the CMAQ predicted W126 ozone exposure metric is within the CEMA baseline threshold of 4000 ppb-hr. This study outlines the use of photochemical modelling of the impact of an industry (oil

  8. Impact of dynamically induced ozone mini-hole events on PSC formation and chemical ozone destruction

    NASA Astrophysics Data System (ADS)

    Stenke, A.; Grewe, V.

    2004-01-01

    The impact of ozone mini-holes over the extra-tropics of the northern hemisphere on the heterogeneous ozone chemistry is investigated, based on simulations with the coupled climate-chemistry model ECHAM4.L39(DLR)/CHEM. Ozone mini-holes are synoptic-scale regions of strongly reduced total ozone, directly associated with upper troposphere high pressure systems. The simulated mini-hole events are validated with a mini-hole climatology based on daily ozone measurements with the total ozone mapping spectrometer (TOMS) instrument on the satellite Nimbus-7 between 1979 and 1993. Furthermore, the impact of mini-holes on the stratospheric heterogeneous ozone chemistry is investigated indirectly. For this purpose, polar stratospheric cloud formation inside mini-holes is suppressed during the model simulation. Heterogeneous processes inside mini-holes amount to one third of the heterogeneous ozone destruction in general over northern mid- and high-latitudes during winter (January-April). This ozone perturbation subsides and recovers during summer with an e-folding time of two months.

  9. The effect of magnesium sulphate on the photochemical formation of microstructures with properties of biological order.

    PubMed

    Bahadur, K; Ranganayaki, S; Maurya, H K

    1979-01-01

    The photochemical formation of microstructures in 1:2:1:1 mixture of ammonium molybdate, diammonium hydrogen phosphate, biological minerals, and formaldehyde showed better results at 9.6 x 10(-5) M concentration of magnesium sulphate in the mixture. The number of particles decreases with increasing concentration of magnesium sulphate.

  10. Partitioning of NOy and Implications for Ozone Formation in Western US Shale Plays

    NASA Astrophysics Data System (ADS)

    Thompson, C. R.; Sjostedt, S. J.; Peischl, J.; Ryerson, T. B.; Aikin, K. C.; Brown, S. S.; Gilman, J.; De Gouw, J. A.; Holloway, J. S.; Koss, A.; Lerner, B. M.; Neuman, J. A.; Veres, P. R.; Warneke, C.; Yuan, B.

    2015-12-01

    Air quality and ozone production within regions of oil and gas development has been a topic of intense research in recent years, due in part to the proliferation of domestic energy production from tight sands and shale formations. The Uintah and the Upper Green River Basins, for example, have been identified as regions with severe air pollution resulting from emissions associated with energy development. In the troposphere, ozone is produced photochemically from NOx (NO + NO2) and volatile organic compounds (VOCs), where the ozone production efficiency is controlled by both the absolute levels of these species and their relative abundances. NO, NO2, NOy and O3 were measured in conjunction with a full suite of atmospheric VOCs, methane, CO, and peroxy acyl nitrates from an instrumented aircraft in March and April of 2015 during the NOAA Shale Oil and Natural Gas Nexus (SONGNEX) campaign, which targeted emissions and photochemistry within the major shale plays in the Western United States. Here, we examine the reactive nitrogen budgets and NOy partitioning in the studied shale plays with particular emphasis on comparing those basins in close proximity to urban centers (e.g., Denver Julesburg, Barnett) to the more rural sites. The impacts of urban outflow intermixed with adjacent oil and gas emissions will be discussed in terms of ozone production and air quality.

  11. Atmospheric chemistry of short-chain haloolefins: photochemical ozone creation potentials (POCPs), global warming potentials (GWPs), and ozone depletion potentials (ODPs).

    PubMed

    Wallington, T J; Sulbaek Andersen, M P; Nielsen, O J

    2015-06-01

    Short-chain haloolefins are being introduced as replacements for saturated halocarbons. The unifying chemical feature of haloolefins is the presence of a CC double bond which causes the atmospheric lifetimes to be significantly shorter than for the analogous saturated compounds. We discuss the atmospheric lifetimes, photochemical ozone creation potentials (POCPs), global warming potentials (GWPs), and ozone depletion potentials (ODPs) of haloolefins. The commercially relevant short-chain haloolefins CF3CFCH2 (1234yf), trans-CF3CHCHF (1234ze(Z)), CF3CFCF2 (1216), cis-CF3CHCHCl (1233zd(Z)), and trans-CF3CHCHCl (1233zd(E)) have short atmospheric lifetimes (days to weeks), negligible POCPs, negligible GWPs, and ODPs which do not differ materially from zero. In the concentrations expected in the environment their atmospheric degradation products will have a negligible impact on ecosystems. CF3CFCH2 (1234yf), trans-CF3CHCHF (1234ze(Z)), CF3CFCF2 (1216), cis-CF3CHCHCl (1233zd(Z)), and trans-CF3CHCHCl (1233zd(E)) are environmentally acceptable.

  12. Formation and growth of photochemical aerosols in Titan's atmosphere

    NASA Astrophysics Data System (ADS)

    Cabane, M.; Chassefiere, E.; Israel, Guy

    1992-04-01

    Recent development in the understanding of the morphology of haze aerosols in Titan's atmosphere, aggregate particles, and their associated optical properties are considered in the flight of a microphysical model of aerosols. Two different phases of the formation process are identified: initial growth of aerosols near the formation altitude by accretion of very small elementary particles; and (2) settling during which particles of about the same size stock together, leading to the formation of aggregates which contain some tens to several hundred monomers. The first phase leads to the formation of nearly spherical 'monomers' (radius approximately equal to 0.05 micrometers). An eulerian microphysical model is used. It is shown that the monomer radius is extremely sensitive to the altitude where aerosols are created. The formation altitude of aerosols is found to lie in the range from 350 to 400 km.

  13. Oxidation of chlorfenvinphos in ultrapure and natural waters by ozonation and photochemical processes.

    PubMed

    Acero, Juan L; Real, Francisco J; Javier Benitez, F; González, Antonio

    2008-06-01

    The chemical oxidation of the organophosphorus insecticide chlorfenvinphos, a priority pollutant in aquatic environments, has been conducted in ultrapure water, by means of single degradation agents (ozone and UV radiation), and by the Advanced Oxidation Processes constituted by combinations of these oxidants (O(3)/H(2)O(2) and UV/H(2)O(2)). The influence of the operating variables was discussed, and the degradation rates were evaluated by determining the rate constants for the reactions with ozone (k(O)(3)=3.7+/-0.2 L mol(-1)s(-1)) and OH radicals (k(OH)=(3.2+/-0.2)x10(9) L mol(-1)s(-1)), as well as the quantum yield for the photodegradation (around 0.1 mol E(-1), depending on the pH). Additionally, the ozonation of chlorfenvinphos in a natural water system (a surface water from a reservoir) was studied. The influence of the operating conditions on the insecticide removal efficiency was established, and the R(ct) parameter was evaluated. A kinetic model was proposed for the prediction of the elimination rate of chlorfenvinphos in the ozonation process and the results obtained reveal a good agreement between experimental results and predicted values.

  14. Particulate matter formation from photochemical degradation of organophosphorus pesticides

    NASA Astrophysics Data System (ADS)

    Borrás, E.; Ródenas, M.; Vera, T.; Muñoz, A.

    2015-12-01

    Several experiments were performed in the European Photo-reactor - EUPHORE - for studying aerosol formation from organophosphorus pesticides such as diazinon, chlorpyrifos, chlorpyrifos-methyl and pirimiphos-methyl. The mass concentration yields obtained (Y) were in the range 5 - 44% for the photo-oxidation reactions in the presence and the absence of NOx. These results confirm the importance of studying pesticides as significant precursors of atmospheric particulate matter due to the serious risks associated to them. The studies based on the use of EUPHORE photoreactor provide useful data about atmospheric degradation processes of organophosphorus pesticides to the atmosphere. Knowledge of the specific degradation products, including the formation of secondary particulate matter, could complete the assessment of their potential impact, since the formation of those degradation products plays a significant role in the atmospheric chemistry, global climate change, radiative force, and are related to health effects.

  15. Observations of ozone formation in power plant plumes and implications for ozone control strategies.

    PubMed

    Ryerson, T B; Trainer, M; Holloway, J S; Parrish, D D; Huey, L G; Sueper, D T; Frost, G J; Donnelly, S G; Schauffler, S; Atlas, E L; Kuster, W C; Goldan, P D; Hubler, G; Meagher, J F; Fehsenfeld, F C

    2001-04-27

    Data taken in aircraft transects of emissions plumes from rural U.S. coal-fired power plants were used to confirm and quantify the nonlinear dependence of tropospheric ozone formation on plume NO(x) (NO plus NO(2)) concentration, which is determined by plant NO(x) emission rate and atmospheric dispersion. The ambient availability of reactive volatile organic compounds, principally biogenic isoprene, was also found to modulate ozone production rate and yield in these rural plumes. Differences of a factor of 2 or greater in plume ozone formation rates and yields as a function of NO(x) and volatile organic compound concentrations were consistently observed. These large differences suggest that consideration of power plant NO(x) emission rates and geographic locations in current and future U.S. ozone control strategies could substantially enhance the efficacy of NO(x) reductions from these sources.

  16. Impact of interannual variability (1979-1986) of transport and temperature on ozone as computed using a two-dimensional photochemical model

    NASA Technical Reports Server (NTRS)

    Jackman, Charles H.; Douglass, Anne R.; Chandra, Sushil; Stolarski, Richard S.; Rosenfield, Joan E.; Kaye, Jack A.

    1991-01-01

    Values of the monthly mean heating rates and the residual circulation characteristics were calculated using NMC data for temperature and the solar backscattered UV ozone for the period between 1979 and 1986. The results were used in a two-dimensional photochemical model in order to examine the effects of temperature and residual circulation on the interannual variability of ozone. It was found that the calculated total ozone was more sensitive to variations in interannual residual circulation than in the interannual temperature. The magnitude of the modeled ozone variability was found to be similar to the observed variability, but the observed and modeled year-to-year deviations were, for the most part, uncorrelated, due to the fact that the model did not account for most of the QBO forcing and for some of the observed tropospheric changes.

  17. Ozone formation in pulsed SDBD in a wide pressure range

    NASA Astrophysics Data System (ADS)

    Starikovskiy, Andrey; Nudnova, Maryia; mipt Team

    2011-10-01

    Ozone concentration in surface anode-directed DBD for wide pressure range (150 - 1300 torr) was experimentally measured. Voltage and pressure effect were investigated. Reduced electric field was measured for anode-directed and cathode-directed SDBD. E/n values in cathode-directed SDBD is higher than in cathode-directed on 50 percent at atmospheric pressure. E/n value increase leads to decrease the rate of oxygen dissociation and Ozone formation at lower pressures. Radiating region thickness of sliding discharge was measured. Typical thickness of radiating zone is 0.4-1.0 mm within pressure range 220-740 torr. It was shown that high-voltage pulsed nanosecond discharge due to high E/n value produces less Ozone with compare to other discharges. Kinetic model was proposed to describe Ozone formation in the pulsed nanosecond SDBD.

  18. Laboratory Studies of Chemical and Photochemical Processes Relevant to Stratospheric Ozone

    NASA Technical Reports Server (NTRS)

    Villalta, Peter W.; Zahniser, Mark S.; Nelson, David D.; Kolb, Charles E.

    1997-01-01

    The purpose of this project is to reduce the uncertainty in several key gas-phase kinetic processes which impact our understanding of stratospheric ozone. The main emphasis of this work is on measuring rate coefficients and product channels for reactions of HO(x) and NO(x) species in the temperature range 200 K to 240 K relevant to the lower stratosphere. The results of these studies will improve models of stratospheric ozone chemistry and predictions of perturbations due to human influences. The second year's effort has focussed the design and construction of the proposed high pressure flow reactor on three separate areas: (1) the construction of the high pressure flow reactor; (2) characterization of the turbulent flow profile; and (3) demonstration of the instrument by measuring HO2 + NO2 and HO2 + NO reaction rate coefficients.

  19. Laboratory Studies of Chemical and Photochemical Processes Relevant to Stratospheric Ozone

    NASA Technical Reports Server (NTRS)

    Zahniser, Mark S.; Nelson, David D.; Worsnop, Douglas R.; Kolb, Charles E.

    1996-01-01

    The purpose of this project is to reduce the uncertainty in several key gas-phase kinetic processes which impact our understanding of stratospheric ozone. The main emphasis of this work is on measuring rate coefficients and product channels for reactions of HOx and NOx species in the temperature range 200 K to 240 K relevant to the lower stratosphere. Other areas of study have included infrared spectroscopic studies of the HO radical, measurements of OH radical reactions with alternative fluorocarbons, and determination of the vapor pressures of nitric acid hydrates under stratospheric conditions. The results of these studies will improve models of stratospheric ozone chemistry and predictions of perturbations due to human influences.

  20. Effects of C60 on the Photochemical Formation of Reactive Oxygen Species from Natural Organic Matter.

    PubMed

    Yin, Lijuan; Zhou, Huaxi; Lian, Lushi; Yan, Shuwen; Song, Weihua

    2016-11-01

    Buckminsterfullerenes (C60) are widely used nanomaterials that are present in surface water. The combination of C60 and humic acid (HA) generates reactive oxygen species (ROS) under solar irradiation, but this process is not well understood. Thus, the present study focused on the photochemical formation of singlet oxygen ((1)O2), hydroxyl radical (HO(•))-like species, superoxide radicals (O2(•-)), hydrogen peroxide (H2O2), and triplet excited states ((3)C60*/(3)HA*) in solutions containing both C60 and HA. The quantum yield coefficients of excited triplet states (fTMP) and apparent quantum yields of ROS were measured and compared to the calculated values, which were based on the conservative mixing model. Although C60 proved to have only a slight impact on the (1)O2 formation from HA, C60 played a key role in the inhibition of O2(•-). The photochemical formation of H2O2 followed the conservative mixing model due to the reaction of C60(•-) with HO2(•)/O2(•-), and the biomolecular reaction rate constant has been measured as (7.4 ± 0.6) × 10(6) M(-1) s(-1). The apparent fTMP was significantly lower than the calculated value, indicating that the steric effect of HA was significant in the reaction of (3)C60* with the TMP probe. In contrast, C60 did not have an effect on the photochemical formation of HO(•) from HA, suggesting that HO(•) is elevated from the hydrophilic surface of HA. The aforementioned results may be useful for predicting the photochemical influence of C60 on aqueous environments.

  1. Reinvestigation of the nitrosamine-formation mechanism during ozonation.

    PubMed

    Yang, Lei; Chen, Zhonglin; Shen, Jimin; Xu, Zhenzhen; Liang, Heng; Tian, Jiayu; Ben, Yue; Zhai, Xu; Shi, Wenxin; Li, Guibai

    2009-07-15

    Previous studies have linked nitrosamine formation during ozonation to a nitrosation process in which nitrosation is catalyzed by formaldehyde, a normal byproduct of ozonation. This mechanism cannot explain the increase in N-nitrosodimethylamine (NDMA) formation with an increase of pH. This study reinvestigates the pathway of N-nitrosamine formation during ozonation. Our observations demonstrated the critical importance of some reactive inorganic nitrogenous intermediates, such as hydroxylamine and dinitrogen tetroxide (N2O4). We report two altemative pathways that possibly explain nitrosamine formation during ozonation at neutral and alkaline pH: (i) secondary amine precursors reacting with hydroxylamine to form unsymmetrical dialkylhydrazine intermediates, which are further oxidized to their relevant nitrosamines; and (ii) a nitrosation pathway in which N2O4 acts as the nitrosating reagent. The key variables of pathway (i) (including reaction time, pH, dissolved oxygen) were investigated. Since hydroxylamine is a common intermediate of dimethylamine oxidation, it is reasonable to assume that hydroxylamine is a possible inorganic precursor for NDMA formation during oxidation processes using strong oxidants. With an improved understanding of the pathway of nitrosamine formation, it should be apparent that the reactive nitrogenous intermediates play an important role in the N-nitrosamine-formation, so future studies of N-nitrosamine-formation control should be focused on the transformation of nitrogen in water treatment

  2. [Smog chamber simulation of ozone formation from atmospheric photooxidation of propane].

    PubMed

    Huang, Li-hua; Mo, Chuang-rong; Xu, Yong-fu; Jia, Long

    2012-08-01

    Atmospheric photochemical reactions of propane and NO, were simulated with a self-made smog chamber. The effects of relative humidity (RH) and [C3H8]0/[NOx]0 ratio on ozone formation were studied. The results showed that both the maximum ozone concentration and the maximum value of incremental reactivity (IRmax) of propane decreased linearly with increasing RH. Under lower RH conditions, the occurrence time of peak ozone concentration was about 22 h after the beginning of reaction, and IRmax varied from 0.0231 to 0.0391, while under higher RH conditions the occurrence time of peak ozone concentration was 16 h, and IRmax ranged from 0.0172 to 0.0320. During the 20 h of reaction, within the first 12 h RH did not significantly affect the yield of acetone, whereas after 12 h the lower RH condition could lead to relatively greater amount of acetone. During the first 4-20 h of experiments, acetone concentrations ranged from 153 x 10(-9) to 364 x 10(-9) at 17% RH and from 167 x 10(-9) to 302 x 10(-9) at 62% RH, respectively. Maximum ozone concentrations decreased with increasing [C3H8]0/[NOx]0 ratio and a better negative linear relationship between them was obtained under the lower RH conditions. The smog chamber data and the results from simulation of the C3H8-NOx reactions using the sub-mechanism of MCM were compared, and a significant deviation was found between these two results.

  3. Fine-scale photochemical modeling of ozone and ammonium nitrate over California during CalNex 2010

    NASA Astrophysics Data System (ADS)

    Kelly, J.; Baker, K.; Misenis, C.; Gilman, J.; De Gouw, J. A.; Lerner, B. M.; Neuman, J. A.; Nowak, J. B.; Pollack, I. B.; Roberts, J. M.; Ryerson, T. B.; Warneke, C.; Williams, E. J.; Veres, P. R.; Murphy, J. G.; Markovic, M. Z.; VandenBoer, T. C.; Weber, R.

    2013-12-01

    Multiple areas of California are designated as nonattainment of the ozone and PM2.5 National Ambient Air Quality Standards making air quality (AQ) modeling for California an important aspect of national-scale modeling for EPA rulemaking. Fine-scale AQ modeling for key population centers in California is also useful to inform health and exposure studies. However, AQ modeling is challenging in California due to complex emissions, terrain, meteorology, and chemistry, and understanding model performance is difficult using routine network observations alone. In May-June 2010, the CalNex field study was conducted in California to answer important scientific questions related to air quality and climate processes. The field study provides a rich observational dataset for probing the performance of fine-scale AQ simulations and identifying causes of model performance limitations. In this study, we conduct fine-scale (4-km horizontal resolution) photochemical model simulations for California during May-June 2010 using the Community Multiscale Air Quality model with the Carbon Bond 05 and SAPRC07 gas-phase chemical mechanisms. Model predictions are then evaluated using observations from the CalNex ground, aircraft, and ship platforms in addition routine network observations. Our model evaluations focus on understanding predictions of ammonium nitrate and ozone concentrations given the importance of these pollutants to California's air quality. Model predictions of ammonium and nitrate have a slight low bias but are strongly correlated with network observations in Riverside and Bakersfield. The model tends to under-predict NH3 concentrations observed on the NOAA P3 aircraft near large NH3 sources in the San Joaquin Valley (SJV) and South Coast Air Basin (SoCAB). At the SJV ground site, NH3 predictions are of similar magnitude as observations, while NH3 tends to be over-predicted at the Pasadena ground site. Nitric acid is over-predicted during the day at the SJV ground site

  4. The Impact of Oil and Natural Gas Activity on Ozone Formation in the Colorado Front Range

    NASA Astrophysics Data System (ADS)

    Hornbrook, R. S.; Apel, E. C.; Hills, A. J.; Blake, D. R.; Blake, N. J.; Schroeder, J.; Fried, A.; Weibring, P.; Richter, D.; Walega, J.; Mauldin, L.; Cantrell, C. A.; Hall, S. R.; Ullmann, K.; Weinheimer, A. J.; Montzka, D.; Orlando, J. J.; Tyndall, G. S.; Campos, T. L.; Stell, M. H.; Heikes, B.; Treadaway, V.; O'Sullivan, D. W.; Huey, L. G.; Tanner, D.; Cohen, R. C.; Flocke, F. M.; Pfister, G.; Knote, C. J.; Emmons, L. K.

    2014-12-01

    The 2014 Front Range Air Pollution and Photochemistry Experiment (FRAPPE) was a ground-based and airborne field study designed to characterize and understand air quality in the Colorado Front Range, where National Ambient Air Quality Standards (NAAQS) ozone levels are frequently exceeded during summertime. A primary goal of the study was to determine the factors controlling surface ozone in the Front Range. As part of the project, measurements of many trace gases were observed on board the NSF/NCAR C-130 by a suite of instrumentation, including the NCAR Trace Organic Gas Analyzer (TOGA), which made measurements of a set of volatile organic compounds (VOCs). VOCs are crucial for characterizing emissions and photochemical processing in the Front Range, as well as the air transported into the region. During recent years, oil and natural gas (O&NG) activity in the Front Range has been growing rapidly. Ratios of observed aromatic hydrocarbons, butanes and pentanes demonstrate distinct fingerprinting that can be used to distinguish both between different types of O&NG activities and between O&NG extraction regions in the FRAPPE study region and beyond. Using the observed hydrocarbon data along with other trace gas observations, we will compare contributions of O&NG emissions to OH reactivities in different regions in the Front Range, and present box model results demonstrating the impact of O&NG activities on ozone formation.

  5. The Impact of Oil and Natural Gas Activity on Ozone Formation in the Colorado Front Range

    NASA Astrophysics Data System (ADS)

    Hornbrook, R. S.; Apel, E. C.; Hills, A. J.; Blake, D. R.; Blake, N. J.; Schroeder, J.; Fried, A.; Weibring, P.; Richter, D.; Walega, J.; Mauldin, L.; Cantrell, C. A.; Hall, S. R.; Ullmann, K.; Weinheimer, A. J.; Montzka, D.; Orlando, J. J.; Tyndall, G. S.; Campos, T. L.; Stell, M. H.; Heikes, B.; Treadaway, V.; O'Sullivan, D. W.; Huey, L. G.; Tanner, D.; Cohen, R. C.; Flocke, F. M.; Pfister, G.; Knote, C. J.; Emmons, L. K.

    2015-12-01

    The 2014 Front Range Air Pollution and Photochemistry Experiment (FRAPPE) was a ground-based and airborne field study designed to characterize and understand air quality in the Colorado Front Range, where National Ambient Air Quality Standards (NAAQS) ozone levels are frequently exceeded during summertime. A primary goal of the study was to determine the factors controlling surface ozone in the Front Range. As part of the project, measurements of many trace gases were observed on board the NSF/NCAR C-130 by a suite of instrumentation, including the NCAR Trace Organic Gas Analyzer (TOGA), which made measurements of a set of volatile organic compounds (VOCs). VOCs are crucial for characterizing emissions and photochemical processing in the Front Range, as well as the air transported into the region. During recent years, oil and natural gas (O&NG) activity in the Front Range has been growing rapidly. Ratios of observed aromatic hydrocarbons, butanes and pentanes demonstrate distinct fingerprinting that can be used to distinguish both between different types of O&NG activities and between O&NG extraction regions in the FRAPPE study region and beyond. Using the observed hydrocarbon data along with other trace gas observations, we will compare contributions of O&NG emissions to OH reactivities in different regions in the Front Range, and present box model results demonstrating the impact of O&NG activities on ozone formation.

  6. Photochemical formation of hydroxyl radicals in tissue extracts of the coral Galaxea fascicularis.

    PubMed

    Higuchi, Tomihiko; Fujimura, Hiroyuki; Hitomi, Yuya; Arakaki, Takemitsu; Oomori, Tamotsu; Suzuki, Yoshimi

    2010-01-01

    Various stresses induce the formation of reactive oxygen species (ROS) in biological cells. In addition to stress-induced ROS, we studied the photochemical formation of hydroxyl radicals (˙OH), the most potent ROS, in coral tissues using phosphate buffer-extracted solutions and a simulated sunlight irradiation system. ˙OH formation was seen in extracts of both coral host and endosymbiont zooxanthellae. This study is the first to report quantitative measurements of ˙OH photoformation in coral tissue extracts. Our results indicated that whether or not coral bleaching occurred, coral tissues and symbiotic zooxanthellae have the potential to photochemically produce ˙OH under sunlight. However, no significant difference was found in the protein content-normalized formation rates of ˙OH between corals incubated under different temperatures and irradiance conditions. ˙OH formation rates were reduced by 40% by reducing the UV radiation in the illumination. It was indicated that UV radiation strongly affected ˙OH formation in coral tissue and zooxanthellae, in addition to its formation through photoinhibition processes.

  7. Diagnosis of Photochemical Ozone Production Rates and Limiting Factors based on Observation-based Modeling Approach over East Asia: Impact of Radical Chemistry Mechanism and Ozone-Control Implications

    NASA Astrophysics Data System (ADS)

    Kanaya, Y.

    2015-12-01

    Growth of tropospheric ozone, causing health and climate impacts, is concerned over East Asia, because emissions of precursors have dramatically increased. Photochemical production rates of ozone and limiting factors, primarily studied for urban locations, have been poorly assessed within a perspective of regional-scale air pollution over East Asia. We performed comprehensive observations of ozone precursors at several locations with regional representativeness and made such assessment based on the observation-based modeling approach. Here, diagnosis at Fukue Island (32.75°N, 128.68°E) remotely located in western Japan (May 2009) is highlighted, where the highest 10% of hourly ozone concentrations reached 72‒118 ppb during May influenced by Asian continental outflow. The average in-situ ozone production rate was estimated to be 6.8 ppb per day, suggesting that in-travel production was still active, while larger buildup must have occurred beforehand. Information on the chemical status of the air mass arriving in Japan is important, because it affects how further ozone production occurs after precursor addition from Japanese domestic emissions. The main limiting factor of ozone production was usually NOx, suggesting that domestic NOx emission control is important in reducing further ozone production and the incidence of warning issuance (>120 ppb). VOCs also increased the ozone production rate, and occasionally (14% of time) became dominant. This analysis implies that the VOC reduction legislation recently enacted should be effective. The uncertainty in the radical chemistry mechanism governing ozone production had a non-negligible impact, but the main conclusion relevant to policy was not altered. When chain termination was augmented by HO2-H2O + NO/NO2 reactions and by heterogeneous loss of HO2 on aerosol particle surfaces, the daily ozone production rate decreased by <24%, and the fraction of hours when the VOC-limited condition occurred varied from 14% to 13

  8. An Observational Based Assessment of In-situ Photochemical Ozone Productivity in the European Boundary Layer

    NASA Astrophysics Data System (ADS)

    Rickard, A. R.; Monks, P. S.; Jonson, J. E.

    2003-04-01

    Empirical observational-based indicator relationships have been used over the past decade in order to investigate ozone production sensitivities to different NO_x/VOC levels. If such relationships can be proven to show marked and consistently different values under different NO_x- and VOC-limited regimes over a broad variety of conditions and geographical locations, then O_3-NO_x-VOC sensitivities and ozone production trends can be determined relatively quickly and simply from measurements rather than from complex models. Such correlations would also provide invaluable measurement data to test the accuracy of model chemistry sensitivities. The tracer indicator relationships O_3/NO_z, H_2O_2/HCHO, H_2O_2/NO_z and O_3/2H_2O_2+NO_z have principally been investigated using data from the Eastern Atlantic Summer/Spring Experiments (EASE 96 and 97 respectively), which took place at Mace Head, on the west coast of Ireland. In order to study the chemistry occurring in the different air masses arriving at Mace Head, minute-averaged data were divided up into five wind sectors according to wind direction and speed. The measurements were additionally segregated using a back trajectory classification method in order to identify the pollution regimes encountered. Some of the calculated results have been compared and contrasted to those calculated from data measured under southern hemispheric "baseline" conditions, collected during the Southern Ocean Atmospheric Photochemistry EXperiment (SOAPEX 2), which took place at Cape Grim on the Tasmanian coast in the Austral summer of 1999 and from the Terrestrial Initiative in Global Environmental Research program (TIGER 95) which took place at Weybourne on the North Norfolk coast in summer 1995. Finally, the above observed indicator ratios, calculated from hourly values for EASE 97, have been compared to those calculated from model data from the EMEP-E regional model (DNMI) for May 1997.

  9. [Ozone source apportionment at urban area during a typical photochemical pollution episode in the summer of 2013 in the Yangtze River Delta].

    PubMed

    Li, Hao; Li, Li; Huang, Cheng; An, Jing-yu; Yan, Ru-sha; Huang, Hai-ying; Wang, Yang-jun; Lu, Qing; Wang, Qian; Lou, Sheng-rong; Wang, Hong-li; Zhou, Min; Tao, Shi-kang; Qiao, Li-ping; Chen, Ming-hua

    2015-01-01

    With the fast development of urbanization, industrialization and mobilization, the air pollutant emissions with photochemical reactivity become more obvious, causing a severe photochemical pollution with the characteristics of high ozone concentration. However, the ozone source identification is very complicated due to the high non linearity between ozone and its precursors. Thus, ways to reduce ozone is still not clear. A high ozone pollution episode occurred during July, 2013, which lasted for a long period, with large influence area and high intensity. In this paper, we selected this episode to do a case study with the application of ozone source apportionment technology(OSAT) coupled within the CAMx air quality model. In this study, 4 source regions(including Shanghai, north Zhejiang, South Jiangsu and long range transport), 7 source categories (including power plants, industrial process, industrial boilers and kilns, residential, mobile source, volatile source and biogenic emissions) are analyzed to study their contributions to surface O3 in Shanghai, Suzhou and Zhejiang. Results indicate that long range transport contribution to the surface ozone in the YRD is around 20 x 10(-9) - 40 x 10(-9) (volume fraction). The O3 concentrations can increased to 40 x 10(-9) - 100 x 10(-9) (volume fraction) due to precursors emissions in Shanghai, Jiangsu and Zhejiang. As for the regional contribution to 8 hour ozone, long range transport constitutes 42.79% +/- 10.17%, 48.57% +/- 9.97% and 60.13% +/- 7.11% of the surface ozone in Shanghai, Suzhou and Hangzhou, respectively. Regarding the high O3 in Shanghai, local contribution is 28.94% +/- 8.49%, north Zhejiang constitutes 19.83% +/- 10.55%. As for surface O3 in Suzhou, the contribution from south Jiangsu is 26.41% +/- 6.80%. Regarding the surface O3 in Hangzhou, the major regional contributor is north Zhejiang (29.56% +/- 8.33%). Contributions from the long range transport to the daily maximum O3 concentrations are

  10. TOLNet Data Format for Lidar Ozone Profile & Surface Observations

    NASA Astrophysics Data System (ADS)

    Chen, G.; Aknan, A. A.; Newchurch, M.; Leblanc, T.

    2015-12-01

    The Tropospheric Ozone Lidar Network (TOLNet) is an interagency initiative started by NASA, NOAA, and EPA in 2011. TOLNet currently has six Lidars and one ozonesonde station. TOLNet provides high-resolution spatio-temporal measurements of tropospheric (surface to tropopause) ozone and aerosol vertical profiles to address fundamental air-quality science questions. The TOLNet data format was developed by TOLNet members as a community standard for reporting ozone profile observations. The development of this new format was primarily based on the existing NDAAC (Network for the Detection of Atmospheric Composition Change) format and ICARTT (International Consortium for Atmospheric Research on Transport and Transformation) format. The main goal is to present the Lidar observations in self-describing and easy-to-use data files. The TOLNet format is an ASCII format containing a general file header, individual profile headers, and the profile data. The last two components repeat for all profiles recorded in the file. The TOLNet format is both human and machine readable as it adopts standard metadata entries and fixed variable names. In addition, software has been developed to check for format compliance. To be presented is a detailed description of the TOLNet format protocol and scanning software.

  11. 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.

  12. 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...

  13. 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...

  14. Conceptual Challenges in Learning Ozone Formation for Collegiate Students

    NASA Astrophysics Data System (ADS)

    Howard, K. E.; Chung, S. H.; Jobson, B. T.; Vanreken, T. M.; Brown, S. A.

    2010-12-01

    Atmospheric chemistry in general, and tropospheric ozone formation in particular, are complex processes that to be understood require students to learn several interrelated concepts. These systems are particularly difficult to grasp because they are inherently nonlinear and because they are abstract- students do not have an obvious tangible model for how gases behave in an unbounded atmosphere. To address perceived shortfalls in our students’ conceptualizations of atmospheric chemical processes, we have endeavored to develop, implement, and assess curricular materials that can be used from the freshmen to graduate level. Our goal was to both improve student understanding of the fundamental concepts of atmospheric chemistry while simultaneously reinforcing the scientific method and what it means to do science. Our approach for achieving this was to build student-friendly interfaces to adapt existing research models for use in the classroom and thereby provide students with a means of exploring the evolution of pollutants in the atmosphere. A major focus of the project was student understanding of ozone formation. In this presentation we provide insight regarding collegiate students’ conceptions of ozone formation and discuss possible explanations for student misconceptions in this and related environmental topics of concern. In order to extract student understanding and conceptions of ozone formation, qualitative interview and analysis methodologies were implemented. These qualitative procedures allowed us to gain a rich and detailed understanding of the specific nature of students’ mental models of these concepts. Forty-five participants were included in the study, all of which were collegiate students enrolled in a junior-level Introduction to Environmental Engineering course at Washington State University. Our results show that the students seemed to comprehend many individual concepts within ozone production cycle to some extent. However, there were very

  15. Photochemical Modeling Applications

    EPA Pesticide Factsheets

    Provides access to modeling applications involving photochemical models, including modeling of ozone, particulate matter (PM), and mercury for national and regional EPA regulations such as the Clean Air Interstate Rule (CAIR) and the Clean Air Mercury Rule

  16. Laboratory Studies of Chemical and Photochemical Processes Relevant to Stratospheric Ozone

    NASA Technical Reports Server (NTRS)

    Villalta, P. W.; Zahniser, M. S.; Nelson, D. D.; Kolb, C. E.

    1998-01-01

    This is the final report for this project. Its purpose is to reduce the uncertainty in rate coefficients for key gas-phase kinetic processes which impact our understanding of stratospheric ozone. The main emphasis of this work is on measuring the rate coefficients for the reactions of HO2 + O3, and HO2 + NO2 in the temperature range (200-240 K) relevant to the lower stratosphere. In order to accomplish this, a high pressure turbulent flow tube reactor was built and its flow characteristics were quantified. The instrument was coupled with tunable diode laser spectroscopy for HO2 detection. Room temperature measurements of the HO2 + NO2 rate coefficients over the pressure range of 50-300 torr agree well with previous measurements. Preliminary measurements of the HO2 + O, rate coefficients at 50 - 300 Torr over the temperature range of 208-294 K agree with the NASA evaluation from 294-225 K but deviate significantly (50 % higher) at approximately 210 K.

  17. Hydroxyl radical and ozone initiated photochemical reactions of 1,3-butadiene

    NASA Astrophysics Data System (ADS)

    Liu, Xiaoyu; Jeffries, Harvey E.; Sexton, Kenneth G.

    1,3-Butadiene, classified as hazardous in the 1990 Clean Air Act Amendments, is an important ambient air pollutant. Understanding its atmospheric transformation is useful for its own sake, and is also helpful for eliciting isoprene's fate in the atmosphere (isoprene dominates the biogenic emissions in US). In this paper, samples from both hydroxyl- and ozone-initiated photooxidation of 1,3-butadiene were analyzed by derivatization with O- (2,3,4,5,6-pentafluorobenzyl)-hydroxylamine followed by separation and detection by gas chromatography/ion trap mass spectrometry to detect and identify carbonyl compounds. The following carbonyls were observed: formaldehyde, acrolein, glycolaldehyde, glycidaldehyde, 3-hydroxy-propanaldehyde, hydroxy acetone, and malonaldehyde, which can be classified into three categories: epoxy carbonyls, hydroxyl carbonyls, and di-carbonyls. Three non-carbonyls, furan, 1,3-buatdiene monoxide, and 1,3-butadiene diepoxide, were also found. To confirm their identities, both commercially available and synthesized standards were used. To investigate the mechanism of 1,3-butadiene, separate batch reactor experiments for acrolein and 1,3-butadiene monoxide were carried out. Time series samples for several products were also taken. When necessary, computational chemistry methods were also employed. Based on these results, various schemes for the reaction mechanism are proposed.

  18. Bromoform formation in ozonated groundwater containing bromide and humic substances

    SciTech Connect

    Cooper, W.J.; Amy, G.L.; Moore, C.A.; Zika, R.G.

    1986-01-01

    The effect of bromide ion, organic carbon concentration (natural aquatic humic substances), pH, and solar irradiation on the formation of bromoform in ozonated groundwater has been studied. The studies were conducted on four unique samples of groundwater taken from different regions of the Biscayne Aquifer in southern Florida. All other conditions being equal, increases in bromide ion concentrations resulted in increases in CHBr/sub 3/ formation. In three of the four samples, CHBr/sub 3/ formation decreased as the pH level increased from 5 to 9. The fourth sample exhibited an opposite trend whereby the CHBr/sub 3/ concentration increased with increasing pH. Bromoform concentration increased with increased O/sub 3/ concentration over an ozone dosage range of 3.4 to 6.7 mg/L. Ozonated samples placed in sunlight immediately after ozone addition showed a decrease in the formation of CHBr/sub 3/ presumably due to the photodecomposition of HOBr/OBr.

  19. Impact of isoprene and HONO chemistry on ozone and OVOC formation in a semirural South Korean forest

    SciTech Connect

    Kim, Saewung; Kim, So-Young; Lee, Meehye; Shim, Heeyoun; Wolfe, Glenn; Guenther, Alex B.; He, Amy; Hong, Youdeog; Han, Jinseok

    2014-01-01

    Rapid urbanization and economic development in East Asia in past decades has led to photochemical air pollution problems such as excess photochemical ozone and aerosol formation. Asian megacities such as Seoul, Tokyo, Shanghai, Gangzhou, and Beijing are surrounded by densely forested areas and recent research has consistently demonstrated the importance of biogenic volatile organic compounds from vegetation in determining oxidation capacity in the suburban Asian megacity regions. Uncertainties in constraining tropospheric oxidation capacity, dominated by hydroxyl radical concentrations, undermine our ability to assess regional photochemical air pollution problems. We present an observational dataset of CO, NOX, SO2, ozone, HONO, and VOCs (anthropogenic and biogenic) from Taehwa Research Forest (TRF) near the Seoul Metropolitan Area (SMA) in early June 2012. The data show that TRF is influenced both by aged pollution and fresh BVOC emissions. With the dataset, we diagnose HOx (OH, HO2, and RO2) distributions calculated with the University of Washington Chemical Box Model (UWCM v 2.1). Uncertainty from unconstrained HONO sources and radical recycling processes highlighted in recent studies is examined using multiple model simulations with different model constraints. The results suggest that 1) different model simulation scenarios cause systematic differences in HOX distributions especially OH levels (up to 2.5 times) and 2) radical destruction (HO2+HO2 or HO2+RO2) could be more efficient than radical recycling (HO2+NO) especially in the afternoon. Implications of the uncertainties in radical chemistry are discussed with respect to ozone-VOC-NOX sensitivity and oxidation product formation rates. Overall, the VOC limited regime in ozone photochemistry is predicted but the degree of sensitivity can significantly vary depending on the model scenarios. The model results also suggest that RO2 levels are positively correlated with OVOCs production that is not routinely

  20. Photochemical grid model estimates of lateral boundary contributions to ozone and particulate matter across the continental United States

    NASA Astrophysics Data System (ADS)

    Baker, Kirk R.; Emery, Chris; Dolwick, Pat; Yarwood, Greg

    2015-12-01

    Multiple approaches to characterize lateral boundary contributions to photochemical model predicted ozone (O3) and particulate matter less than 2.5 microns in diameter (PM2.5) are available in the Comprehensive Air quality Model with extensions (CAMx). Here, three approaches are used for O3: (1) a comprehensive source apportionment scheme for chemical boundary conditions and emissions (OSAT), (2) chemically reactive tracers (RTRAC), and (3) chemically inert tracers. Two approaches are used for PM2.5: (1) particulate source apportionment (PSAT) and (2) chemically inert tracers. The inert tracer approach resulted in higher O3 lateral boundary contribution estimates because the method does not account for any O3 destruction reactions. OSAT and RTRAC estimate generally similar monthly average contributions during the warmer months although RTRAC estimates higher urban area contribution during the cold months because this RTRAC implementation did not treat O3 titration by NO. Accurate representation of lateral boundary O3 impacts must include appropriate accounting for O3 destruction reactions. OSAT and RTRAC were configured to estimate the contribution to modeled O3 from each of the four lateral faces of the model domain. RTRAC was configured to further stratify the western and northern boundaries by groups of vertical layers. The RTRAC approach showed that the largest O3 contributions to the continental U.S. are from the mid-troposphere, with less contribution from the upper troposphere/lower stratosphere. Inert tracers compared more closely to reactive tracers on average for PM2.5 compared to O3. This close agreement for PM2.5 indicates most of the lateral boundary contribution is from PM2.5 rather than precursor inflow. A strong relationship exists between model predicted PM2.5 boundary contribution and model overestimates of nitrate and organic carbon at IMPROVE monitor locations suggesting global model estimates of these species were overestimated at some places

  1. Formation Of Perchlorate By Ozonation Of Aqueous Oxy-chlorine Anions: An Insight To Natural Perchlorate Formation

    NASA Astrophysics Data System (ADS)

    Rao, B.; Jackson, A.; Kang, N.; Redder, A.

    2007-12-01

    Perchlorate (ClO4-) is a natural and anthropogenic contaminant of increasing concern. Natural perchlorate was first identified in Chilean nitrates from the Atacama dessert over 100 years ago. However, only in the last two years has the occurrence of natural perchlorate been seriously considered as a potential exposure source. Although there has been considerable research effort in understanding the occurrence, remediation, and impact of ClO4- in the environment, relatively little information is available regarding the mechanism(s) responsible for ClO4- formation. Perchlorate productions from ozone oxidation of chlorine and oxy- chlorine anions (Cl-, OCl-, ClO2-and ClO3-) were conducted in continuous flow reactors at constant ozone concentrations (approximately 6 mg L-1) and at varying concentrations of chlorine materials (ranging from 10 to 1000 mg L-1). Sub samples from both the main reaction flask and alkaline trapping flasks were taken over varying time intervals and the concentrations of oxy-chlorine anions including ClO4- were measured using various ion chromatographic methods whereas OCl- was determined iodometrically using the spectrophotometer. The experiment time ranged from 6 hrs to 7 days depending on the rate of decomposition of the reactants. Results indicate that ClO4- is readily formed during the ozonation of ClO2- and OCl- solutions (maximum conversion of 2.7 %) whereas the Cl- and ClO3- solutions produced relatively lower quantities of ClO4- ( maximum conversion of 0.02 %) . Further the presence of ClO2- in the initial OCl- solution is suspected to significantly contribute the total ClO4- generated augmenting the role of ClO2- in ClO4- formation as mentioned in recent study on the photochemical reactions of oxy-chlorine anions.

  2. Photochemical Formation of Fe(II) in the Aqueous Solutions of Fe(III)- Dicarboxylates

    NASA Astrophysics Data System (ADS)

    Okada, K.; Arakaki, T.

    2007-12-01

    Although there have been many studies reporting the photochemical formation of Fe(II) in various aqueous-phase such as rain, cloud waters, seawater and aerosols, the detailed formation mechanisms are not well understood. To better understand the mechanisms of Fe(II) formation, we attempted to determine the molar absorptivity and the quantum yield of Fe(II) photoformation for individual Fe(III)-dicarboxylate species. The concentrations of Fe(II) and total dissolved Fe were measured by a Ferrozine-HPLC method. The Visual MINTEQ computer program was used to calculate the equilibrium concentrations of chemical species in the solutions of Fe(III)-dicarboxylate complexes. The molar absorptivity and the product of the quantum yield and the molar absorptivity of Fe(III)- dicarboxylate complex can be analysed by UV-VIS spectrophotometer and photochemical experiments, and these experimental data were combined with the calculated equilibrium Fe(III) speciation to determine individual molar absorptivity and quantum yield of Fe(II) photoformation for a specific Fe(III)-dicarboxylate complex. Preliminary results, using an oxalate whose quantum yield has been previously reported, indicate that this approach gives lower quantum yield values in air saturated solutions than previously reported.

  3. Ozone and alkyl nitrate formation from the Deepwater Horizon oil spill atmospheric emissions

    NASA Astrophysics Data System (ADS)

    Neuman, J. A.; Aikin, K. C.; Atlas, E. L.; Blake, D. R.; Holloway, J. S.; Meinardi, S.; Nowak, J. B.; Parrish, D. D.; Peischl, J.; Perring, A. E.; Pollack, I. B.; Roberts, J. M.; Ryerson, T. B.; Trainer, M.

    2012-05-01

    Ozone (O3), alkyl nitrates (RONO2), and other photochemical products were formed in the atmosphere downwind from the Deepwater Horizon (DWH) oil spill by photochemical reactions of evaporating hydrocarbons with NOx (=NO + NO2) emissions from spill response activities. Reactive nitrogen species and volatile organic compounds (VOCs) were measured from an instrumented aircraft during daytime flights in the marine boundary layer downwind from the area of surfacing oil. A unique VOC mixture, where alkanes dominated the hydroxyl radical (OH) loss rate, was emitted into a clean marine environment, enabling a focused examination of O3 and RONO2 formation processes. In the atmospheric plume from DWH, the OH loss rate, an indicator of potential O3 formation, was large and dominated by alkanes with between 5 and 10 carbons per molecule (C5-C10). Observations showed that NOx was oxidized very rapidly with a 0.8 h lifetime, producing primarily C6-C10 RONO2 that accounted for 78% of the reactive nitrogen enhancements in the atmospheric plume 2.5 h downwind from DWH. Both observations and calculations of RONO2 and O3 production rates show that alkane oxidation dominated O3 formation chemistry in the plume. Rapid and nearly complete oxidation of NOx to RONO2 effectively terminated O3 production, with O3 formation yields of 6.0 ± 0.5 ppbv O3 per ppbv of NOx oxidized. VOC mixing ratios were in large excess of NOx, and additional NOx would have formed additional O3 in this plume. Analysis of measurements of VOCs, O3, and reactive nitrogen species and calculations of O3 and RONO2 production rates demonstrate that NOx-VOC chemistry in the DWH plume is explained by known mechanisms.

  4. Ozone formation and transport in southeastern United States: Overview of the SOS Nashville/Middle Tennessee Ozone Study

    NASA Astrophysics Data System (ADS)

    Meagher, James F.; Cowling, Ellis B.; Fehsenfeld, Fred C.; Parkhurst, William J.

    1998-09-01

    The Southern Oxidants Study (SOS) is a public-private partnership collectively engaged, since 1989, in a coordinated program of policy-relevant research to improve scientific and public understanding of tropospheric ozone pollution. In the summers of 1994 and 1995, SOS implemented the Nashville/Middle Tennessee Ozone Study. This effort, the second SOS urban intensive study, conducted a series of integrated, process-oriented airborne and surface measurement experiments to better understand the chemistry and meteorology associated with the production, transport, and impact of tropospheric ozone. Specific technical objectives addressed (1) the role of biogenic VOC and NOx emissions on local and regional ozone production, (2) the effect of urban-rural exchange/interchange on local and regional ozone production, (3) sub-grid-scale photochemical and meteorological processes, and (4) the provision of a high-quality chemical and meteorological data set to test and improve observation- and emission-based air quality forecast models. Some of the more significant findings of the 1994-1995 studies include the following: (1) Ozone production in Nashville was found to be close to the transition between NOx-sensitive and VOC-sensitive chemistry. (2) Ozone production efficiency (OPE) in power plant plumes, molecules of ozone formed per molecule of NOx emitted, was found to be inversely proportion to NOx emission rate, with the plants having the greatest NOx emissions exhibiting the lowest OPE. (3) During stagnant conditions, nighttime winds dominated pollutant transport and represent the major mechanism for transporting urban pollutants to rural areas. Ultimately, results provided by this research will allow improved assessment of existing ozone management strategies and provide better scientific tools for the development of future management strategies.

  5. Infrared matrix isolation study of the thermal and photochemical reactions of ozone with dimethylcadmium.

    PubMed

    McNally, Devin; Ault, Bruce S

    2012-03-01

    The matrix isolation technique has been combined with infrared spectroscopy and theoretical calculations to explore the reaction of (CH(3))(2)Cd with O(3) over a range of time scales and upon irradiation. During twin jet deposition, multiple novel product species were observed along with several stable "late" products. Following annealing of these matrices to 35 K, absorptions due to two novel product species increased in intensity. In addition, new bands appeared, indicating the formation of an additional product. Subsequent UV irradiation destroyed several of the initial products and produced a new photoproduct. On the basis of (18)O and (16,18)O spectroscopic data and theoretical calculations, the novel intermediates H(3)COCdCH(3), H(3)CCdCH(2)OH, H(3)COCdOOCH(3), and H(3)CCdCHO were identified. Merged jet deposition led to a number of stable "late" products, including H(2)CO, CH(3)OH, and C(2)H(6), identifications that were confirmed by (18)O substitution. Mechanistic inferences for this reaction are discussed. © 2012 American Chemical Society

  6. [Correlation Analysis Between Characteristics of VOCs and Ozone Formation Potential in Summer in Nanjing Urban District].

    PubMed

    Yang, Xiao-xiao; Tang, Li-li; Zhang, Yun-jiang; Mu, Ying-feng; Wang, Ming; Chen, Wen-tai; Zhou, Hong-cang; Hua, Yan; Jiang, Rong-xin

    2016-02-15

    Volatile organic compounds (VOCs) is an important precursor of photochemical ozone pollution (O3) in the atmosphere. Their concentration variation directly affects the characteristics of the ozone pollution. The concentration, speciation of VOCs, ozone and its precursors in Nanjing were analyzed and measured using online gas detection systems in August 2013. VOCs/NOx discriminant method was used to get the sensitive control factors of ozone. The results showed that the averaged volume fraction of VOCs was 52. 05 x 10(-9), and the largest one reached 200 x 10(-9) in Nanjing urban district. The order of volume fraction of each species VOCs was alkane > oxygen-containing VOCs > alkene > aromatics. The averaged concentration of ozone was 76.5 microg x m(-1) and the exceeding concentration of hourly standard was 5.9%. The change trends of ozone precursors VOCs and NOx were basically identical and Ozone showed the obvious negative correlation during the period of high concentrations of ozone. There were some differences in the concentrations of the same VOCs in different ozone concentration periods. The ozone generation in Nanjing urban district was sensitive to VOCs, and Nanjing belonged to VOCs control area in summer.

  7. Photochemical Pollution Modeling of Ozone at Metropolitan Area of Porto Alegre - RS/Brazil using WRF/Chem

    NASA Astrophysics Data System (ADS)

    Cuchiara, G. C.; Carvalho, J.

    2013-05-01

    One of the main problems related to air pollution in urban areas is caused by photochemical oxidants, particularly troposphere ozone (O3), which is considered a harmful substance. The O3 precursors (carbon monoxide CO, nitrogen oxides NOx and hydrocarbons HCs) are predominantly of anthropogenic origin in these areas, and vehicles are the main emission sources. Due to the increased urbanization and industrial development in recent decades, air pollutant emissions have increased likewise, mainly by mobile sources in the highly urbanized and developed areas, such as the Metropolitan Area of Porto Alegre-RS (MAPA). According to legal regulations implemented in Brazil in 2005, which aimed at increasing the fraction of biofuels in the national energy matrix, 2% biodiesel were supposed to be added to the fuel mixture within three years, and up to 5% after eight years of implementation of these regulations. Our work performs an analysis of surface concentrations for O3, NOx, CO, and HCs through numerical simulations with WRF/Chem (Weather Research and Forecasting model with Chemistry). The model is validated against observational data obtained from the local urban air quality network for the period from January 5 to 9, 2009 (96 hours). One part of the study focused on the comparison of simulated meteorological variables, to observational data from two stations in MAPA. The results showed that the model simulates well the diurnal evolution of pressure and temperature at the surface, but is much less accurate for wind speed. Another part included the evaluation of model results of WRF/Chem for O3 versus observed data at air quality stations Esteio and Porto Alegre. Comparisons between simulated and observed O3 revealed that the model simulates well the evolution of the observed values, but on many occasions the model did not reproduce well the maximum and minimum concentrations. Finally, a preliminary quantitative sensitivity study on the impact of biofuel on the

  8. The effect of ozone associated with summertime photochemical smog on the frequency of asthma visits to hospital emergency departments

    SciTech Connect

    Cody, R.P. ); Weisel, C.P.; Lioy, P.J. Environmental and Occupational Health Sciences Institute, Piscataway, NJ ); Birnbaum, G. )

    1992-08-01

    A retrospective study using ambient ozone, temperature, and other environmental variables and their effect on the frequency of hospital visits for asthma was conducted in New Jersey, an area that often exceeds the allowable national standard for ozone. Data on emergency department visits for asthma, bronchitis, and finger wounds (a nonrespiratory control) were analyzed for the period May through August for 1988 and 1989. Asthma visits were correlated with temperature while the correlation between asthma visits and ozone concentration was nonsignificant. However, when temperature was controlled for in a multiple regression analysis, a highly significant relationship between asthma visits and ozone concentration was identified. Between 13 and 15% of the variability of the asthma visits and ozone concentration was identified. Between 13 and 15% of the variability of the asthma visits was explained in the regression model by temperature and ambient ozone levels. This association, when compared to similar studies in Canada, shows the contribution of ozone to asthma admissions to be stronger in areas with higher ozone concentrations. Thus, among regions with periodic accumulations of ozone in the ambient atmosphere, an exposure-response relationship may be discernible. This supports the need to attain air quality standards for ozone to protect individuals in the general population from the adverse health effects caused by ambient ozone exposure. 21 refs., 1 fig., 6 tabs.

  9. Photochemical roles of rapid economic growth and potential abatement strategies on tropospheric ozone over South and East Asia in 2030

    NASA Astrophysics Data System (ADS)

    Chatani, S.; Amann, M.; Goel, A.; Hao, J.; Klimont, Z.; Kumar, A.; Mishra, A.; Sharma, S.; Wang, S. X.; Wang, Y. X.; Zhao, B.

    2014-04-01

    A regional air quality simulation framework including the Weather Research and Forecasting modelling system (WRF), the Community Multi-scale Air Quality modeling system (CMAQ), and precursor emissions to simulate tropospheric ozone over South and East Asia is introduced. Concentrations of tropospheric ozone and related species simulated by the framework are validated by comparing with observation data of surface monitorings, ozone zondes, and satellites obtained in 2010. The simulation demonstrates acceptable performance on tropospheric ozone over South and East Asia at regional scale. Future energy consumption, carbon dioxide (CO2), nitrogen oxides (NOx), and volatile organic compound (VOC) emissions in 2030 under three future scenarios are estimated. One of the scenarios assumes a business-as-usual (BAU) pathway, and other two scenarios consider implementation of additional energy and environmental strategies to reduce energy consumption, CO2, NOx, and VOC emissions in China and India. Future surface ozone under these three scenarios is predicted by the simulation. The simulation indicates future surface ozone significantly increases around India for a whole year and around north eastern China in summer. NOx is a main driver on significant seasonal increase of surface ozone, whereas VOC as well as increasing background ozone and methane is also an important factor on annual average of surface ozone in East Asia. Warmer weather around India is also preferable for significant increase of surface ozone. Additional energy and environmental strategies assumed in future scenarios are expected to be effective to reduce future surface ozone over South and East Asia.

  10. Photochemical formation of hydroxyl radical in red-soil-polluted seawater - effects of dissolved organic compounds

    NASA Astrophysics Data System (ADS)

    Uehara, M.; Arakaki, T.

    2006-12-01

    Development of pineapple farmlands and construction of recreational facilities caused runoff of red soil into the coastal ocean (locally termed as red soil pollution) in the north of Okinawa Island, Japan. Red soil is acidic and contains a few percent of iron oxide. We were interested in the formation of hydroxyl radical (·OH), the most potent oxidant in the environment, from the photo-Fenton reaction (reaction between Fe(II) and HOOH) in red-soil-polluted seawater. Various artificial seawater solutions were prepared by adding red soil, HOOH, and/or humic acid to clean seawater, and were used for photochemical experiments. Commercially available humic acid was used to represent natural organic compounds. All the solutions were filtered through 0.45 micron filter before conducting photochemical experiments. Comparisons among the solutions indicated that dissolved chemicals from the red-soil only slightly increased the OH radical photoformation. Photoformation rates of OH radicals of the HOOH + red soil solutions were similar to the calculated rates from direct photolysis of HOOH. Furthermore, addition of humic acid to the HOOH + red soil solutions did not significantly enhance the photo-Fenton reaction, suggesting that Fe(II), even if it had been formed, did not react with HOOH to form OH radicals at detectable level in seawater.

  11. Role of nitrite in the photochemical formation of radicals in the snow.

    PubMed

    Jacobi, Hans-Werner; Kleffmann, Jörg; Villena, Guillermo; Wiesen, Peter; King, Martin; France, James; Anastasio, Cort; Staebler, Ralf

    2014-01-01

    Photochemical reactions in snow can have an important impact on the composition of the atmosphere over snow-covered areas as well as on the composition of the snow itself. One of the major photochemical processes is the photolysis of nitrate leading to the formation of volatile nitrogen compounds. We report nitrite concentrations determined together with nitrate and hydrogen peroxide in surface snow collected at the coastal site of Barrow, Alaska. The results demonstrate that nitrite likely plays a significant role as a precursor for reactive hydroxyl radicals as well as volatile nitrogen oxides in the snow. Pollution events leading to high concentrations of nitrous acid in the atmosphere contributed to an observed increase in nitrite in the surface snow layer during nighttime. Observed daytime nitrite concentrations are much higher than values predicted from steady-state concentrations based on photolysis of nitrate and nitrite indicating that we do not fully understand the production of nitrite and nitrous acid in snow. The discrepancy between observed and expected nitrite concentrations is probably due to a combination of factors, including an incomplete understanding of the reactive environment and chemical processes in snow, and a lack of consideration of the vertical structure of snow.

  12. An analysis of the impacts of VOCs and NOx on the ozone formation in Guangzhou

    NASA Astrophysics Data System (ADS)

    Zou, Y.; Deng, X. J.; Wang, B. G.; Li, F.; Tan, H. B.; Deng, T.; Mai, B. R.; Liu, X. T.

    2014-07-01

    In this study, online monitoring instruments were used to monitor ozone, NOx and VOCs at the Guangzhou Panyu Atmospheric Composition Station (GPACS) of the China Meteorological Administration from June 2011 to May 2012, so as to obtain their characteristic seasonal and diurnal variations, as well as the impacts of NOx and VOCs on local ozone formation and Guangzhou ozone control strategies. The results show that during the observation period the seasonal variation of ozone concentration was lower in the spring and winter and higher in the summer and autumn, which is contrary that of NOx and VOCs. At around 09:00 LT in the summer, autumn and winter, both the ozone concentration and NO2/NO ratio begin to increase, and the NO2/NO ratio reached its maximum after a peak of ozone concentration, but this variation was not particularly evident in the spring. Aromatics and alkenes are the largest components for ozone formation potential, among which aromatic toluene, m-xylene, p-xylene and 1,3,5-trimethylbenzene are the most important components, with a total contribution of about 31.6% to ozone formation potential. Through the analysis on local ozone control by the VOC/NOX ratio, it was found that when the ozone concentration reached a peak in the summer and autumn in which high concentrations of ozone were prone to occur, ozone generation was NOx limited, thus NOx emissions must be controlled to regulate the occurrence of high-concentration ozone events. In the spring and winter, ozone generation was always VOCs controlled. Due to the relatively low ozone concentration, although NOx emissions could be controlled to increase ozone concentration, high-concentration ozone events would not occur. Therefore, for the control of ozone in Guangzhou, in addition to the control of VOCs emissions, more attention must be paid to reducing NOx emissions, so as to achieve the purpose of controlling high-concentration ozone.

  13. Estimating hydroxyl radical photochemical formation rates in natural waters during long-term laboratory irradiation experiments.

    PubMed

    Sun, Luni; Chen, Hongmei; Abdulla, Hussain A; Mopper, Kenneth

    2014-04-01

    In this study it was observed that, during long-term irradiations (>1 day) of natural waters, the methods for measuring hydroxyl radical (˙OH) formation rates based upon sequentially determined cumulative concentrations of photoproducts from probes significantly underestimate actual ˙OH formation rates. Performing a correction using the photodegradation rates of the probe products improves the ˙OH estimation for short term irradiations (<1 day), but not long term irradiations. Only the 'instantaneous' formation rates, which were obtained by adding probes to aliquots at each time point and irradiating these sub-samples for a short time (≤2 h), were found appropriate for accurately estimating ˙OH photochemical formation rates during long-term laboratory irradiation experiments. Our results also showed that in iron- and dissolved organic matter (DOM)-rich water samples, ˙OH appears to be mainly produced from the Fenton reaction initially, but subsequently from other sources possibly from DOM photoreactions. Pathways of ˙OH formation in long-term irradiations in relation to H2O2 and iron concentrations are discussed.

  14. Photochemical roles of rapid economic growth and potential abatement strategies on tropospheric ozone over South and East Asia in 2030

    NASA Astrophysics Data System (ADS)

    Chatani, S.; Amann, M.; Goel, A.; Hao, J.; Klimont, Z.; Kumar, A.; Mishra, A.; Sharma, S.; Wang, S. X.; Wang, Y. X.; Zhao, B.

    2014-09-01

    A regional air quality simulation framework including the Weather Research and Forecasting modeling system (WRF), the Community Multi-scale Air Quality modeling system (CMAQ), and precursor emissions to simulate tropospheric ozone over South and East Asia is introduced. Concentrations of tropospheric ozone and related species simulated by the framework are validated by comparing with observation data of surface monitoring, ozonesondes, and satellites obtained in 2010. The simulation demonstrates acceptable performance on tropospheric ozone over South and East Asia at regional scale. Future energy consumption, carbon dioxide (CO2), nitrogen oxides (NOx), and volatile organic compound (VOC) emissions in 2030 under three future scenarios are estimated. One of the scenarios assumes a business-as-usual (BAU) pathway, and other two scenarios consider implementation of additional energy and environmental strategies to reduce energy consumption, CO2, NOx, and VOC emissions in China and India. Future surface ozone under these three scenarios is predicted by the simulation. The simulation indicates future surface ozone significantly increases around India for a whole year and around northeastern China in summer. NOx is a main driver on significant seasonal increase of surface ozone, whereas VOC as well as increasing background ozone and methane is also an important factor on annual average of surface ozone in East Asia. Warmer weather around India is also preferable for significant increase of surface ozone. Additional energy and environmental strategies assumed in future scenarios are expected to be effective to reduce future surface ozone over South and East Asia.

  15. FORMATION OF MOLECULAR OXYGEN AND OZONE ON AMORPHOUS SILICATES

    SciTech Connect

    Jing Dapeng; He Jiao; Vidali, Gianfranco; Brucato, John Robert; Tozzetti, Lorenzo; De Sio, Antonio

    2012-09-01

    Oxygen in the interstellar medium is seen in the gas phase, in ices (incorporated in H{sub 2}O, CO, and CO{sub 2}), and in grains such as (Mg{sub x} Fe{sub 1-x} )SiO{sub 3} or (Mg{sub x} Fe{sub 1-x} ){sub 2}SiO{sub 4}, 0 < x < 1. In this investigation, we study the diffusion of oxygen atoms and the formation of oxygen molecules and ozone on the surface of an amorphous silicate film. We find that ozone is formed at low temperature (<30 K), and molecular oxygen forms when the diffusion of oxygen atoms becomes significant, at around 60 K. This experiment, besides being the first determination of the diffusion energy barrier (1785 {+-} 35 K) for oxygen atoms on a silicate surface, suggests bare silicates as a possible storage place for oxygen atoms in low-A{sub v} environments.

  16. Photochemical formation and chemistry of long-lived adamantylidene-quinone methides and 2-adamantyl cations.

    PubMed

    Basarić, Nikola; Zabcić, Ivana; Mlinarić-Majerski, Kata; Wan, Peter

    2010-01-01

    Hydroxymethylphenols strategically substituted with the 2-hydroxy-2-adamantyl moiety, AdPh 8-10, were synthesized, and their photochemical reactivity was investigated. On excitation to the singlet excited state, AdPh 8 undergoes intramolecular proton transfer coupled with a loss of H(2)O giving quinone methide 8QM. The presence of 8QM has been detected by laser flash photolysis (CH(3)CN-H(2)O 1:1, tau = 0.55 s) and UV-vis spectroscopy. Singlet excited states of AdPh 9 and 10 in the presence of H(2)O dehydrate giving 9QM and 10QM. Photochemically formed QMs are trapped by nucleophiles giving the addition products (e.g., Phi for methanolysis of 8 is 0.55). In addition, the zwitterionic 9QM undergoes an unexpected rearrangement involving transformation of the 2-phenyl-2-adamantyl cation into the 4-phenyl-2-adamantyl cation (Phi approximately 0.03). An analogous rearrangement was observed with methoxy derivatives 9a and 10a. Zwitterionic 9QM was characterized by LFP in 2,2,2-trifluoroethanol (tau = 1 mus). In TFE, in the ground state, AdPh 10 is in equilibrium with 10QM, which allowed for recording the (1)H and (13)C NMR spectra of the QM. Introduction of the adamantyl substituent into the o-hydroxymethylphenol moiety increased the quantum yield of the associated QM formation by up to 3-fold and significantly prolonged their lifetimes. Furthermore, adamantyl substituent made the study of the alkyl-substituted quinone methides easier by LFP by prolonging their lifetimes and increasing the quantum yields of formation.

  17. 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.

  18. EVALUATING THE PERFORMANCE OF REGIONAL-SCALE PHOTOCHEMICAL MODELING SYSTEMS: PART II--OZONE PREDICTIONS. (R825260)

    EPA Science Inventory

    In this paper, the concept of scale analysis is applied to evaluate ozone predictions from two regional-scale air quality models. To this end, seasonal time series of observations and predictions from the RAMS3b/UAM-V and MM5/MAQSIP (SMRAQ) modeling systems for ozone were spectra...

  19. Photochemical formation of hydroxyl radical from effluent organic matter: role of composition.

    PubMed

    Lee, Eunkyung; Glover, Caitlin M; Rosario-Ortiz, Fernando L

    2013-01-01

    The photochemical formation of hydroxyl radical (HO(•)) from effluent organic matter (EfOM) depends upon the chemical properties of this heterogeneous mixture. In this study, two EfOM samples collected from wastewater treatment plants (WWTP A and B) were fractionated by both hydrophobicity (bulk and non-humic) and apparent molecular weight (AMW). The apparent quantum yield for HO(•) formation (ΦHO(•)) and the maximum fluorescence quantum yield (ΦF) were subsequently measured for each subfraction. The formation rates of HO(•) (considering only the hydrogen-peroxide-independent pathways) for the bulk waters were 4.8 × 10(-10) and 9.6 × 10(-11) M s(-1) for WWTP A and B, respectively. For the AMW fractions, the values of ΦHO(•) increased as the AMW of the material decreased. For the WWTP A sample, the ΦHO(•) increased from 2.54 × 10(-4) (bulk water) to 6.29 × 10(-4) for the <1 kDa fraction, and for the WWTP B sample, the value of ΦHO(•) increased from 6.50 × 10(-5) for bulk water to 3.45 × 10(-4) for the <1 kDa fraction. In the case of fluorescence, the values of ΦF ranged from 2.37 × 10(-4) (bulk water) to 3.48 × 10(-4) (<1 kDa fraction) for WWTP A and 3.19 × 10(-4) (bulk water) to 5.75 × 10(-4) (<1 kDa fraction) for WWTP B. There was a linear correlation between ΦHO(•) and ΦF, suggesting that different photophysical processes occur in the chemical components of the fractions. Understanding the formation of HO(•) from EfOM is essential for understanding wastewater-impacted aquatic systems because these results influence the photochemical degradation and mineralization of trace organic contaminants.

  20. [Impact of catalytic ozonation with ferric hydroxide on HAAs formation potential of a filtered surface water].

    PubMed

    Zhang, Tao; Lu, Jin-Feng; Ma, Jun; Chen, Zhong-Lin; Shen, Su-Fang; Wang, Qun

    2006-08-01

    Formation potential of five haloacetic acids (HAA5FP) of a filtered surface water was studied after ozonation alone and catalytic ozonation with a ferric hydroxide (FeOOH). Factors studied were oxidation time, bromide, pH, bicarbonate alkalinity, and ozone dosages. The haloacetic acids detected were dichloroacetic acid (DCAA), trichloroacetic acid (TCAA), and dibromoacetic acid (DBAA) when bromide existed. The catalytic ozonation caused a reduction of HAA5FP of the non-bromide containing water for 9.5% - 18.3% compared to that of ozonation in 5-20 minutes. Incremental addition of bromide led to a much lower HAA5FP after catalytic ozonation than that after ozonation. HAA5FP of the water at neutral pH was higher than that at acidic and basic conditions. Catalytic ozonation showed a most advantageous potential in controlling HAA5FP over ozonation at neutral pH. The HAA5FP decreased as bicarbonate concentration increased, and the disparity between ozonation and catalytic ozonation was also reduced. The HAA5FP after catalytic ozonation was 11.2% to 28.0% lower than that after ozonation while the ratio of O3/TOC ranging from 0.45 to 1.43. The effect of catalytic ozonation on HAA5FP of the water is closely related to its enhanced generation of hydroxyl radicals in catalytic process.

  1. Source contributions of volatile organic compounds to ozone formation in southeast Texas

    NASA Astrophysics Data System (ADS)

    Ying, Qi; Krishnan, Anupama

    2010-09-01

    A source-oriented SAPRC-99 gas phase photochemical mechanism was incorporated into the Community Multiscale Air Quality (CMAQ) model to determine the contributions of volatile organic compounds (VOCs) to predicted net ozone (O3) formation rates during the Texas Air Quality Study (TexAQS) from 16 August to 7 September 2000. Contributions from biogenic sources, diesel vehicles, highway gasoline vehicles, off-highway gasoline vehicles, solvent utilization, petroleum industries, other industries and wildfires were determined. Peak column-averaged O3 formation rate due to industrial sources averaged over this episode was approximately 8.5 ppb hr-1. Contributions of gasoline vehicles and solvent utilization were large in urban areas to the west of the industrial region with highest column-averaged formation rates of 3.7 and 1.4 ppb hr-1, respectively. Large regional contributions of biogenic sources to O3 formation were predicted with highest O3 formation rate of 11.9 ppb hr-1 in downwind rural areas. Wildfires could contribute to large O3 formation but their influence was generally localized. Analysis of 2400 back-trajectories from areas with maximum daily 8-h O3 greater than 90 ppb showed that industrial sources were the largest anthropogenic sources of VOC that contributed to the these high O3 events, followed by gasoline vehicle sources. The median of relative contributions from biogenic and anthropogenic sources from this analysis was approximately 60% and 40%, respectively. Analysis of the back-trajectories where 1-h peak O3 concentrations were greater than 120 ppb showed that the median relative contributions due to anthropogenic sources were increased to over 60%. This suggests that high O3 events in the HGB region were driven by anthropogenic VOC emissions from industrial sources.

  2. Photochemical Hydrogen Doping Induced Embedded Two-Dimensional Metallic Channel Formation in InGaZnO at Room Temperature.

    PubMed

    Kim, Myeong-Ho; Lee, Young-Ahn; Kim, Jinseo; Park, Jucheol; Ahn, Seungbae; Jeon, Ki-Joon; Kim, Jeong Won; Choi, Duck-Kyun; Seo, Hyungtak

    2015-10-27

    The photochemical tunability of the charge-transport mechanism in metal-oxide semiconductors is of great interest since it may offer a facile but effective semiconductor-to-metal transition, which results from photochemically modified electronic structures for various oxide-based device applications. This might provide a feasible hydrogen (H)-radical doping to realize the effectively H-doped metal oxides, which has not been achieved by thermal and ion-implantation technique in a reliable and controllable way. In this study, we report a photochemical conversion of InGaZnO (IGZO) semiconductor to a transparent conductor via hydrogen doping to the local nanocrystallites formed at the IGZO/glass interface at room temperature. In contrast to thermal or ionic hydrogen doping, ultraviolet exposure of the IGZO surface promotes a photochemical reaction with H radical incorporation to surface metal-OH layer formation and bulk H-doping which acts as a tunable and stable highly doped n-type doping channel and turns IGZO to a transparent conductor. This results in the total conversion of carrier conduction property to the level of metallic conduction with sheet resistance of ∼16 Ω/□, room temperature Hall mobility of 11.8 cm(2) V(-1) sec(-1), the carrier concentration at ∼10(20) cm(-3) without any loss of optical transparency. We demonstrated successful applications of photochemically highly n-doped metal oxide via optical dose control to transparent conductor with excellent chemical and optical doping stability.

  3. Highly nonlinear ozone formation in the Houston region and implications for emission controls

    NASA Astrophysics Data System (ADS)

    Xiao, Xue; Cohan, Daniel S.; Byun, Daewon W.; Ngan, Fong

    2010-12-01

    Photochemical modeling with high-order sensitivity analysis is applied to simulate the nonlinear responses of ozone to NOx and VOC emissions from different source regions in the Houston-Galveston-Brazoria area and their interactions. First-order responses of daytime ozone to Houston NOx emissions are typically positive but are negative in the core region, indicating a NOx-inhibited chemical regime there. Houston anthropogenic VOC emissions exert a spatially smaller impact on ozone but are important to high ozone concentrations in the core region. Highest ozone concentrations in the Houston region typically occur where the impacts of the Houston Ship Channel NOx emissions coincide with those of NOx emitted from the rest of the Houston region. Daytime ozone is found to exhibit a more nonlinear responsiveness to precursor emissions in Houston than has been reported in other regions, including a strongly concave response to local NOx emissions and strong interactions between the impacts of NOx and VOC emissions changes. Due to this intense nonlinearity, moderate perturbations (10-30%) in either NOx or VOC emissions inventories could flip whether Houston ozone is modeled to be more responsive to VOC control or NOx control. Thus the accuracy of emission inventories could strongly influence predictions of ozone response to emission reductions.

  4. Aerosol formation yields from the reaction of catechol with ozone

    NASA Astrophysics Data System (ADS)

    Coeur-Tourneur, Cécile; Tomas, Alexandre; Guilloteau, Angélique; Henry, Françoise; Ledoux, Frédéric; Visez, Nicolas; Riffault, Véronique; Wenger, John C.; Bedjanian, Yuri

    The formation of secondary organic aerosol from the gas-phase reaction of catechol (1,2-dihydroxybenzene) with ozone has been studied in two smog chambers. Aerosol production was monitored using a scanning mobility particle sizer and loss of the precursor was determined by gas chromatography and infrared spectroscopy, whilst ozone concentrations were measured using a UV photometric analyzer. The overall organic aerosol yield ( Y) was determined as the ratio of the suspended aerosol mass corrected for wall losses ( Mo) to the total reacted catechol concentrations, assuming a particle density of 1.4 g cm -3. Analysis of the data clearly shows that Y is a strong function of Mo and that secondary organic aerosol formation can be expressed by a one-product gas-particle partitioning absorption model. The aerosol formation is affected by the initial catechol concentration, which leads to aerosol yields ranging from 17% to 86%. The results of this work are compared to similar studies reported in the literature.

  5. Impact of isoprene and HONO chemistry on ozone and OVOC formation in a semirural South Korean forest

    DOE PAGES

    Kim, S.; Kim, S. -Y.; Lee, M.; ...

    2015-04-29

    Rapid urbanization and economic development in East Asia in past decades has led to photochemical air pollution problems such as excess photochemical ozone and aerosol formation. Asian megacities such as Seoul, Tokyo, Shanghai, Guangzhou, and Beijing are surrounded by densely forested areas, and recent research has consistently demonstrated the importance of biogenic volatile organic compounds (VOCs) from vegetation in determining oxidation capacity in the suburban Asian megacity regions. Uncertainties in constraining tropospheric oxidation capacity, dominated by hydroxyl radical, undermine our ability to assess regional photochemical air pollution problems. We present an observational data set of CO, NOx, SO2, ozone, HONO,more » and VOCs (anthropogenic and biogenic) from Taehwa research forest (TRF) near the Seoul metropolitan area in early June 2012. The data show that TRF is influenced both by aged pollution and fresh biogenic volatile organic compound emissions. With the data set, we diagnose HOx (OH, HO2, and RO2) distributions calculated using the University of Washington chemical box model (UWCM v2.1) with near-explicit VOC oxidation mechanisms from MCM v3.2 (Master Chemical Mechanism). Uncertainty from unconstrained HONO sources and radical recycling processes highlighted in recent studies is examined using multiple model simulations with different model constraints. The results suggest that (1) different model simulation scenarios cause systematic differences in HOx distributions, especially OH levels (up to 2.5 times), and (2) radical destruction (HO2 + HO2 or HO2 + RO2) could be more efficient than radical recycling (RO2 + NO), especially in the afternoon. Implications of the uncertainties in radical chemistry are discussed with respect to ozone–VOC–NOx sensitivity and VOC oxidation product formation rates. Overall, the NOx limited regime is assessed except for the morning hours (8 a.m. to 12 p.m. local standard time), but the degree of sensitivity

  6. Impact of isoprene and HONO chemistry on ozone and OVOC formation in a semirural South Korean forest

    SciTech Connect

    Kim, S.; Kim, S. -Y.; Lee, M.; Shim, H.; Wolfe, G. M.; Guenther, A. B.; He, A.; Hong, Y.; Han, J.

    2015-04-29

    Rapid urbanization and economic development in East Asia in past decades has led to photochemical air pollution problems such as excess photochemical ozone and aerosol formation. Asian megacities such as Seoul, Tokyo, Shanghai, Guangzhou, and Beijing are surrounded by densely forested areas, and recent research has consistently demonstrated the importance of biogenic volatile organic compounds (VOCs) from vegetation in determining oxidation capacity in the suburban Asian megacity regions. Uncertainties in constraining tropospheric oxidation capacity, dominated by hydroxyl radical, undermine our ability to assess regional photochemical air pollution problems. We present an observational data set of CO, NOx, SO2, ozone, HONO, and VOCs (anthropogenic and biogenic) from Taehwa research forest (TRF) near the Seoul metropolitan area in early June 2012. The data show that TRF is influenced both by aged pollution and fresh biogenic volatile organic compound emissions. With the data set, we diagnose HOx (OH, HO2, and RO2) distributions calculated using the University of Washington chemical box model (UWCM v2.1) with near-explicit VOC oxidation mechanisms from MCM v3.2 (Master Chemical Mechanism). Uncertainty from unconstrained HONO sources and radical recycling processes highlighted in recent studies is examined using multiple model simulations with different model constraints. The results suggest that (1) different model simulation scenarios cause systematic differences in HOx distributions, especially OH levels (up to 2.5 times), and (2) radical destruction (HO2 + HO2 or HO2 + RO2) could be more efficient than radical recycling (RO2 + NO), especially in the afternoon. Implications of the uncertainties in radical chemistry are discussed with respect to ozone–VOC–NOx sensitivity and VOC oxidation product

  7. Laboratory photochemical processing of aqueous aerosols: formation and degradation of dicarboxylic acids, oxocarboxylic acids and α-dicarbonyls

    NASA Astrophysics Data System (ADS)

    Pavuluri, C. M.; Kawamura, K.; Mihalopoulos, N.; Swaminathan, T.

    2015-01-01

    To better understand the photochemical processing of dicarboxylic acids and related polar compounds, we conducted batch UV irradiation experiments on two types of aerosol samples collected from India, which represent anthropogenic (AA) and biogenic aerosols (BA), for time periods of 0.5 to 120 h. The irradiated samples were analyzed for molecular compositions of diacids, oxoacids and α-dicarbonyls. The results show that photochemical degradation of oxalic (C2) and malonic (C3) and other C8-C12 diacids overwhelmed their production in aqueous aerosols whereas succinic acid (C4) and C5-C7 diacids showed a significant increase (ca. 10 times) during the course of irradiation experiments. The photochemical formation of oxoacids and α-dicarbonyls overwhelmed their degradation during the early stages of experiment, except for ω-oxooctanoic acid (ωC8) that showed a similar pattern to that of C4. We also found a gradual decrease in the relative abundance of C2 to total diacids and an increase in the relative abundance of C4 during prolonged experiment. Based on the changes in concentrations and mass ratios of selected species with the irradiation time, we hypothesize that iron-catalyzed photolysis of C2 and C3 diacids dominates their concentrations in Fe-rich atmospheric waters, whereas photochemical formation of C4 diacid (via ωC8) is enhanced with photochemical processing of aqueous aerosols in the atmosphere. This study demonstrates that the ambient aerosols contain abundant precursors that produce diacids, oxoacids and α-dicarbonyls, although some species such as oxalic acid decompose extensively during an early stage of photochemical processing.

  8. Laboratory photochemical processing of aqueous aerosols: formation and degradation of dicarboxylic acids, oxocarboxylic acids and α-dicarbonyls

    NASA Astrophysics Data System (ADS)

    Pavuluri, C. M.; Kawamura, K.; Mihalopoulos, N.; Swaminathan, T.

    2015-07-01

    To better understand the photochemical processing of dicarboxylic acids and related polar compounds, we conducted batch UV irradiation experiments on two types of aerosol samples collected from India, which represent anthropogenic (AA) and biogenic (BA) aerosols, for time periods of 0.5 to 120 h. The irradiated samples were analyzed for molecular compositions of diacids, oxoacids and α-dicarbonyls. The results show that photochemical degradation of oxalic (C2), malonic (C3) and other C8-C12 diacids overwhelmed their production in aqueous aerosols, whereas succinic acid (C4) and C5-C7 diacids showed a significant increase (ca. 10 times) during the course of irradiation experiments. The photochemical formation of oxoacids and α-dicarbonyls overwhelmed their degradation during the early stages of experiment except for ω-oxooctanoic acid (ωC8), which showed a similar pattern to that of C4. We also found a gradual decrease in the relative abundance of C2 to total diacids and an increase in the relative abundance of C4 during prolonged experiment. Based on the changes in concentrations and mass ratios of selected species with the irradiation time, we hypothesize that iron-catalyzed photolysis of C2 and C3 diacids controls their concentrations in Fe-rich atmospheric waters, whereas photochemical formation of C4 diacid (via ωC8) is enhanced with photochemical processing of aqueous aerosols in the atmosphere. This study demonstrates that the ambient aerosols contain abundant precursors that produce diacids, oxoacids and α-dicarbonyls, although some species such as oxalic acid decompose extensively during an early stage of photochemical processing.

  9. Mass tracking for chemical analysis: the causes of ozone formation in southern Ontario during BAQS-Met 2007

    NASA Astrophysics Data System (ADS)

    Makar, P. A.; Zhang, J.; Gong, W.; Stroud, C.; Sills, D.; Hayden, K. L.; Brook, J.; Levy, I.; Mihele, C.; Moran, M. D.; Tarasick, D. W.; He, H.

    2010-06-01

    A three-level nested regional air pollution model has been used to study the processes leading to high ozone concentrations in the southern Great Lakes region of North America. The highest resolution simulations show that complex interactions between the lake breeze circulation and the synoptic flow lead to significant enhancements in the photochemical production and transport of ozone at the local scale. Significant improvements in model correlation with ozone observations are achieved in going to the highest spatial resolution. Mass tracking of individual model processes show that Lakes Erie and St. Clair frequently act as photochemical production regions, with average mid-day production rates of 6 to 8 ppbv per hour. Enhanced ozone levels are evident over these two lakes in 23-day-average surface ozone fields. Analysis of other model fields and aircraft measurements suggests that vertical recirculation enhances ozone levels over Lake St. Clair while strong subsidence enhances ozone over Lake Erie. The mass tracking of model transport shows that lake-breeze surface convergence zones combined with the synoptic flow can carry ozone and its precursors hundreds of kilometers from these source areas, in narrow, elongated features. Comparison with surface mesonet ozone observations confirm the presence, magnitude, and timing of these features, which create local ozone enhancements on the order of 20 ppbv above the regional ozone levels. High-resolution modelling is recommended in order to predict these local-scale features in operational air-quality forecasts.

  10. Direct measurements of the ozone formation potential from dairy cattle emissions using a transportable smog chamber

    NASA Astrophysics Data System (ADS)

    Howard, Cody J.; Yang, Wenli; Green, Peter G.; Mitloehner, Frank; Malkina, Irina L.; Flocchini, Robert G.; Kleeman, Michael J.

    Tropospheric ozone continues to be an air pollution problem in the United States, particularly in California, Texas, and across the eastern seaboard. The obvious sources of ozone precursors have been largely controlled over the past several decades, leading to the critical examination of secondary sources. In particular, California has new air quality rules addressing agricultural sources of ozone precursors, including dairy farms. Some recent estimates predict that dairy cattle are second only to on-road vehicles as a leading source of ozone precursor emissions in California's San Joaquin Valley. The objective of this work was to directly measure the ozone formation potential from dairy housing. A transportable "smog" chamber was constructed and validated using organic gases known to be present in dairy emissions. The ozone formation potential of emissions from eight non-lactating dairy cows and their fresh waste was then directly evaluated in the field at a completely enclosed cow corral on the campus of the University of California, Davis. The results demonstrate that the majority of the ozone formation is explained by ethanol (EtOH) in the emissions from the dairy cows, not by acetone as previously thought. Ozone formation potential is generally small, with <20 ppb of ozone produced under typical conditions when EtOH concentrations were ˜200 ppb and NO x concentrations were ˜50 ppb. The results match our current understanding of atmospheric ozone formation potential, ruling out the possibility of unknown organic compounds in dairy emissions with significant ozone formation potential. Simulations carried out with a modified form of the Caltech Atmospheric Chemistry Mechanism verify that actual ozone formation from dairy emissions is much lower than what would be predicted using the current regulatory profiles. Based on these results, the ozone formation potential of emissions from dairy cattle in California seems to be lower than previously estimated.

  11. Differences in ozone photochemical characteristics between the megacity Nanjing and its suburban surroundings, Yangtze River Delta, China.

    PubMed

    An, Junlin; Zou, Jianan; Wang, Junxiu; Lin, Xu; Zhu, Bin

    2015-12-01

    Rapid economic growth has led to a significant increase in ozone (O3) precursor emissions in many regions of China. Improved understanding of O3 formation in response to different precursor emissions is imperative to address the highly nonlinear O3 problem and to provide a solid scientific basis for efficient O3 abatement in these regions. A comparative study was conducted in summer using a set of observational data at urban and suburban sites in Nanjing. The results showed that high O3 concentrations were frequently encountered at both sites. The probability distributions of O3 in both sites show a fair resemblance to each other, suggesting strong regional mixing over the polluted Nanjing. A distinction between the characteristics of O3 precursors has been found at different sites. During the observation period, O3 concentrations varied monthly, reaching a minimum in June and peaking in August. The daily maximum O3 concentration was found to exceed 80 ppb for 27 days at residential area (RA), whereas it only exceeded 80 ppb for 22 days at industrial area (IA), 16 days at traffic area (TA), and 14 days at commercial area (CA). This pattern suggests a higher continuous ozone exposure risk at RA. The daily maximum O3 concentrations at different sites were 135.1 ppb (IA), 134.1 ppb (RA), 129.2 ppb (TA), and 110.6 ppb (CA), respectively. The daily maximum O3 concentration occurred at 16:00 in IA, at 17:00 in TA and CA, and at 18:00 in RA. Nitrogen dioxide (NO2) and carbon monoxide (CO) showed similar double-peak diurnal cycles. NO2 showed maximum values in June and minimum values in July. CO showed a similar diurnal variation to NO2. This effect may be explained by their common sources and the similar chemical losses. During the day, O3 tended to rapidly increase during the morning, reaching a maximum value of 9-11 ppb h(-1). The differences in O3 and NO2 between workdays and weekends were small. The CO levels were higher on weekdays than on weekends in urban areas and

  12. Photochemical aerosol formation in planetary atmospheres: A comparison between Pluto and Titan

    NASA Astrophysics Data System (ADS)

    Lavvas, Panayotis; Strobel, Darrell F.; Lellouch, Emmanuel; Gurwell, Mark A.; Cheng, Andrew F.; Summers, Michael; Gladstone, Randy

    2016-10-01

    The New Horizons mission observations have revealed us that Pluto's atmosphere is rich in photochemical hazes that extend to high altitudes above its surface [1], apparently similar to those observed in Titan's atmosphere [2].We use detailed models combining photochemistry and microphysics in order to simulate the aerosol formation and growth in Pluto's atmosphere, as performed for Titan's atmosphere [3]. Here we discuss the possible mechanisms leading to the formation of haze particles in Pluto's atmosphere, and we evaluate the contribution of different growth processes (e.g. coagulation vs. condensation) to the resulting particle properties.Moreover we investigate the role of these particles in the radiative balance of Pluto's atmosphere and we compare the resulting particle properties, with those retrieved for Titan's upper atmosphere based on Cassini observations [4]. We discuss the similarities and difference between Pluto's and Titan's aerosols.[1] Gladstone et al., 2016, Science, 351, 6271[2] West et al., 2015, Titan's Haze, in Titan, Interior, Surface, Atmosphere and Space environment, Cambridge University Press[3] Lavvas et al., 2013, PNAS, pnas.1217059110[4] Lavvas et al., 2015, DPS47, id.205.08

  13. Temperature dependence of the photochemical formation of hydroxyl radical from dissolved organic matter.

    PubMed

    McKay, Garrett; Rosario-Ortiz, Fernando L

    2015-04-07

    The temperature dependence of the photochemical production of the hydroxyl radical (•OH) from dissolved organic matter (DOM) was investigated by measuring the apparent temperature dependence of the quantum yield (Φa) for this process. Temperature dependent Φa values were analyzed using the Arrhenius equation. Apparent activation energies obtained for DOM isolates purchased from the International Humic Substances Society ranged from 16 to 34 kJ mol(-1). Addition of 40 units mL(-1) catalase, used to hinder the hydrogen peroxide (H2O2)-dependent pathway to •OH, did not impact the observed activation energy. However, an increase in activation energy was observed in lower molecular weight DOM obtained by size fractionation. We also measured the temperature dependence of p-benzoquionone photolysis as a model compound for DOM and observed no temperature dependence (slope p = 0.41) for the formation of phenol from oxidation of benzene (the •OH probe used), but a value of about 10 kJ mol(-1) for p-benzoquinone loss, which is consistent with formation of a quinone-water exciplex. These data provide insight into DOM photochemistry as well as provide parameters useful for modeling steady state •OH concentrations in natural systems.

  14. [Control of THMs formation potential of filtered surface water with catalytic ozonation by ferric hydroxide].

    PubMed

    Lu, Jin-feng; Zhang, Tao; Ma, Jun; Chen, Zhong-lin; Jiang, Jin

    2006-05-01

    Catalytic ozonation of a filtered surface water with ferric hydroxide (FeOOH) was compared with ozonation alone for trihalomathane formation potential (THMFP). Factors studied included bromide, pH, alkalinity, ratio of O3/TOC, reaction time, and dosage of FeOOH. THMFP of the water after catalytic ozonation was 30.5% lower than that after ozonation. High bromide concentration resulted in the predominance of brominated THMFP, at which condition the brominated THMFP after catalytic ozonation was 45%-65.5% of that after ozonation. The catalytic ozonation showed a significant advantage over ozonation in controlling THMFP of the water at the conditions applied in this experiment, i.e., at pH of 6.33-9.43, O3/TOC of 0.65-2.05, and reaction time of 2-20 min. High concentration of alkalinity decreased THMFP of the water after ozonation and catalytic ozonation. It also weakened the advantage of catalytic ozonation. There existed an optimal dosage of FeOOH in respect of controlling THMFP. The lower THMFP of the water after catalytic ozonation is caused by its higher TOC removal than ozonation, and the possible enhanced oxidation of some of the THM precursors by hydroxyl radicals generated in this process.

  15. 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.

  16. Oxidant supply and aqueous photochemical SOA formation in cloud droplets and aqueous aerosol

    NASA Astrophysics Data System (ADS)

    Turpin, B. J.; Ervens, B.; Lim, Y. B.

    2012-12-01

    Many recent laboratory, field and model studies point to significant contributions to the total secondary organic aerosol (SOA) budget from aqueous phase reactions in cloud droplets and aqueous aerosol particles. Laboratory studies of the photochemical oxidation of glyoxal and methylglyoxal in the aqueous phase show a strong dependence on the initial concentration of dissolved organics, with preferential formation of large molecules (dimers, oligomers) at the high concentrations found in ambient deliquesced aerosol particles. In such experimental studies OH radicals are produced in the aqueous phase (via hydrogen peroxide photolysis) and OH radical is assumed to be the major oxidant. An explicit aqueous photooxidation mechanism has been validated, in part, based on the observed temporal evolution of organic intermediates and products in these experiments. In this work, this mechanism was incorporated into multiphase process models (box, cloud parcel) in order to further explore aqueous SOA formation in dilute cloud droplets and concentrated aerosol particles. We found that the predicted SOA mass in both aqueous phases can be comparable despite the much lower liquid water content in aerosols, where oligomer formation is favored. Direct uptake from the gas phase was the largest source of OH radicals in the aqueous phase. In-situ production through the Fenton reaction (Fe), hydrogen peroxide and nitrate photolysis were minor sources. Since phase transfer is slower than the OH(aq) consumption by organics, modeled OH(aq) concentrations were smaller by 1-2 orders of magnitude than predicted based on thermodynamic equilibrium. Our model studies suggest that, unless there are substantial additional sources of OH radical in the aqueous phase, aqueous SOA formation will be oxidant limited. Since the phase transfer rate is a function of the drop (or particle) surface area, aqueous SOA formation may occur preferentially at or near the drop/particle surface (e.g., be surface

  17. Photochemically assisted fast abiotic oxidation of manganese and formation of δ-MnO 2 nanosheets in nitrate solution

    SciTech Connect

    Jung, Haesung; Chadha, Tandeep S.; Kim, Doyoon; Biswas, Pratim; Jun, Young-Shin

    2017-01-01

    This study introduces a new and previously unconsidered fast abiotic formation of Mn(IV) oxides. We report photochemically assisted fast abiotic oxidation of Mn2+ (aq) to Mn(IV) (s) by superoxide radicals generated from nitrate photolysis. This photochemical pathway generates randomly stacked layered birnessite (δ-MnO2) nanosheets.

  18. Megacity impacts on regional ozone formation: observations and WRF-Chem modeling for the MIRAGE-Shanghai field campaign

    NASA Astrophysics Data System (ADS)

    Tie, X.; Geng, F.; Guenther, A.; Cao, J.; Greenberg, J.; Zhang, R.; Apel, E.; Li, G.; Weinheimer, A.; Chen, J.; Cai, C.

    2013-01-01

    The MIRAGE-Shanghai experiment was designed to characterize the factors controlling regional air pollution near a Chinese Megacity (Shanghai) and was conducted during September 2009. This paper provides an overview of the measurements conducted for this study. In addition to the measurements, a regional chemical/dynamical model (version 3 of Weather Research and Forecasting Chemical model - WRF-Chemv3) is applied for this study. The model results are intensively compared with the measurements to evaluate the model capability for calculating air pollutants in the Shanghai region, especially the chemical species related to ozone formation. The results show that the model is able to calculate the general distributions (the level and the variability) of air pollutants in the Shanghai region, and the difference between the model calculation and the measurement are mostly smaller than 30%, except the calculations of HONO at PD (Pudong) and CO at DT (Dongtan). The main scientific focus is the study of ozone chemical formation not only in the urban area, but also on a regional scale of the surrounding area of Shanghai. The results show that during the experiment period, the ozone photochemical formation was strongly under the VOC-limited condition in the urban area of Shanghai. Moreover, the VOC-limited condition occurred not only in the city, but also in the larger regional area. There was a continuous enhancement of ozone concentrations in the downwind of the megacity of Shanghai, resulting in a significant enhancement of ozone concentrations in a very large regional area in the surrounding region of Shanghai. The sensitivity study of the model suggests that there is a threshold value for switching from VOC-limited condition to NOx-limited condition. The threshold value is strongly dependent on the emission ratio of NOx/VOCs. When the ratio is about 0.4, the Shanghai region is under a strong VOC-limited condition over the regional scale. In contrast, when the ratio is

  19. Megacity impacts on regional ozone formation: observations and WRF-Chem modeling for the MIRAGE-Shanghai field campaign

    NASA Astrophysics Data System (ADS)

    Tie, X.; Geng, F.; Guenther, A.; Cao, J.; Greenberg, J.; Zhang, R.; Apel, E.; Li, G.; Weinheimer, A.; Chen, J.; Cai, C.

    2013-06-01

    The MIRAGE-Shanghai experiment was designed to characterize the factors controlling regional air pollution near a Chinese megacity (Shanghai) and was conducted during September 2009. This paper provides information on the measurements conducted for this study. In order to have some deep analysis of the measurements, a regional chemical/dynamical model (version 3 of Weather Research and Forecasting Chemical model - WRF-Chemv3) is applied for this study. The model results are intensively compared with the measurements to evaluate the model capability for calculating air pollutants in the Shanghai region, especially the chemical species related to ozone formation. The results show that the model is able to calculate the general distributions (the level and the variability) of air pollutants in the Shanghai region, and the differences between the model calculation and the measurement are mostly smaller than 30%, except the calculations of HONO (nitrous acid) at PD (Pudong) and CO (carbon monoxide) at DT (Dongtan). The main scientific focus is the study of ozone chemical formation not only in the urban area, but also on a regional scale of the surrounding area of Shanghai. The results show that during the experiment period, the ozone photochemical formation was strongly under the VOC (volatile organic compound)-limited condition in the urban area of Shanghai. Moreover, the VOC-limited condition occurred not only in the city, but also in the larger regional area. There was a continuous enhancement of ozone concentrations in the downwind of the megacity of Shanghai, resulting in a significant enhancement of ozone concentrations in a very large regional area in the surrounding region of Shanghai. The sensitivity study of the model suggests that there is a threshold value for switching from VOC-limited condition to NOx (nitric oxide and nitrogen dioxide)-limited condition. The threshold value is strongly dependent on the emission ratio of NOx / VOCs. When the ratio is about

  20. Formation of oxidation byproducts from ozonation of wastewater.

    PubMed

    Wert, Eric C; Rosario-Ortiz, Fernando L; Drury, Doug D; Snyder, Shane A

    2007-04-01

    Disinfection byproduct (DBP) formation in tertiary wastewater was examined after ozonation (O(3)) and advanced oxidation with O(3) and hydrogen peroxide (O(3)/H(2)O(2)). O(3) and O(3)/H(2)O(2) were applied at multiple dosages to investigate DBP formation during coliform disinfection and trace contaminant oxidation. Results showed O(3) provided superior disinfection of fecal and total coliforms compared to O(3)/H(2)O(2). Color, UV absorbance, and SUVA were reduced by O(3) and O(3)/H(2)O(2), offering wastewater utilities a few potential surrogates to monitor disinfection or trace contaminant oxidation. At equivalent O(3) dosages, O(3)/H(2)O(2) produced greater concentrations of assimilable organic carbon (5-52%), aldehydes (31-47%), and carboxylic acids (12-43%) compared to O(3) alone, indicating that organic DBP formation is largely dependent upon hydroxyl radical exposure. Bromate formation occurred when O(3) dosages exceeded the O(3) demand of the wastewater. Bench-scale tests with free chlorine showed O(3) is capable of reducing total organic halide (TOX) formation potential by at least 20%. In summary, O(3) provided superior disinfection compared to O(3)/H(2)O(2) while minimizing DBP concentrations. These are important considerations for water reuse, aquifer storage and recovery, and advanced wastewater treatment applications.

  1. Ozone

    MedlinePlus

    ... reactive form of oxygen. In the upper atmosphere, ozone forms a protective layer that shields us from the sun’s ultraviolet rays. At ground level, ozone is a harmful air pollutant and a primary ...

  2. Photochemical smog effects in mixed conifer forests along a natural gradient of ozone and nitrogen deposition in the San Bernardino Mountains.

    PubMed

    Arbaugh, Michael; Bytnerowicz, Andrzej; Grulke, Nancy; Fenn, Mark; Poth, Mark; Temple, Patrick; Miller, Paul

    2003-06-01

    Toxic effects of photochemical smog on ponderosa and Jeffrey pines in the San Bernardino Mountains were discovered in the 1950s. It was revealed that ozone is the main cause of foliar injury manifested as chlorotic mottle and premature needle senescence. Various morphological, physiological and biochemical alterations in the affected plants have been reported over a period of about 40 years of multidisciplinary research. Recently, the focus of research has shifted from studying the effects of ozone to multiple pollutant effects. Recent studies have indicated that the combination of ozone and nitrogen may alter biomass allocation in pines towards that of deciduous trees, accelerate litter accumulation, and increase carbon sequestration rates in heavily polluted forests. Further study of the effects of multiple pollutants, and their long-term consequences on the mixed conifer ecosystem, cannot be adequately done using the original San Bernardino Mountains Air Pollution Gradient network. To correct deficiencies in the design, the new site network is being configured for long-term studies on multiple air pollutant concentrations and deposition, physiological and biochemical changes in trees, growth and composition of over-story species, biogeochemical cycling including carbon cycling and sequestration, water quality, and biodiversity of forest ecosystems. Eleven sites have been re-established. A comparison of 1974 stand composition with data from 2000 stand composition indicate that significant changes in species composition have occurred at some sites with less change at other sites. Moist, high-pollution sites have experienced the greatest amount of forest change, while dryer low-pollution sites have experienced the least amount of stand change. In general, ponderosa pine had the lowest basal area increases and the highest mortality across the San Bernardino Mountains.

  3. Ozone

    MedlinePlus

    Ozone is a gas. It can be good or bad, depending on where it is. "Good" ozone occurs naturally about 10 to 30 miles above ... the sun's ultraviolet rays. Part of the good ozone layer is gone. Man-made chemicals have destroyed ...

  4. Atmospheric Ozone Formation and Observation Effects on Waterless Rocky Exoplanets around M Dwarfs

    NASA Astrophysics Data System (ADS)

    Mai, Chuhong; Tian, Feng

    2015-11-01

    It is recently proposed that up to two thousand bars of O2 atmospheres could buildup on rocky planets near M dwarfs as the result of stellar luminosity evolution and runaway water loss (Luger and Barnes, 2015). Here we use a one-dimensional photochemical model to study ozone distributions in these hypothetical O2-rich atmospheres. Our study showed that ozone layers in denser O2 atmospheres locate at higher altitudes than that in the Earth’s atmospheres. A higher ozone layer should generate stronger O3 absorption feature, potentially different from that of our Earth. We also present the enhancement of transmission spectral features which could be useful to identify such dense O2-rich atmospheres by future exoplanet characterization missions and facilities such as JWST.

  5. Mass tracking for chemical analysis: the causes of ozone formation in southern Ontario during BAQS-Met 2007

    NASA Astrophysics Data System (ADS)

    Makar, P. A.; Zhang, J.; Gong, W.; Stroud, C.; Sills, D.; Hayden, K. L.; Brook, J.; Levy, I.; Mihele, C.; Moran, M. D.; Tarasick, D. W.; He, H.; Plummer, D.

    2010-11-01

    A three-level nested regional air pollution model has been used to study the processes leading to high ozone concentrations in the southern Great Lakes region of North America. The highest resolution simulations show that complex interactions between the lake-breeze circulation and the synoptic flow lead to significant enhancements in the photochemical production and transport of ozone at the local scale. Mass tracking of individual model processes show that Lakes Erie and St. Clair frequently act as photochemical ozone production regions, with average mid-day production rates of up to 3 ppbv per hour. Enhanced ozone levels are evident over these two lakes in 23-day-average surface ozone fields. Analysis of other model fields and aircraft measurements suggests that vertical circulation enhances ozone levels at altitudes up to 1500 m over Lake St. Clair, whereas subsidence enhances ozone over Lake Erie in a shallow layer only 250 m deep. Mass tracking of model transport shows that lake-breeze surface convergence zones combined with the synoptic flow can then carry ozone and its precursors hundreds of kilometers from these source areas, in narrow, elongated features. Comparison with surface mesonet ozone observations confirm the presence, magnitude, and timing of these features, which can create local ozone enhancements on the order of 30 ppbv above the regional ozone levels. Sensitivity analyses of model-predicted ozone and HOx concentrations show that most of the region is VOC-limited, and that the secondary oxidation pathways of aromatic hydrocarbons have a key role in setting the region's ozone and HOx levels.

  6. Ozone interactions with human hair: Ozone uptake rates and product formation

    NASA Astrophysics Data System (ADS)

    Pandrangi, Lakshmi S.; Morrison, Glenn C.

    In this study, the cumulative ozone uptake, the ozone reaction probability and product yields of volatile aldehydes and ketones were quantified for human scalp hair. Hair was chosen because ozone reacts readily with skin oils and the personal-care products that coat hair. Due to their proximity to the breathing zone, these reactions can influence personal exposure to ozone and its volatile reaction products. Hair samples were collected before and after washing and/or application of personal hair-care products. Samples were exposed to ozone for 24 h in a tubular Teflon reactor; ozone consumption rates and product emission rates were quantified. The mean values of integrated ozone uptake, initial and final follicle reaction probability values for eight washed and unwashed samples were, respectively, 5.1±4.4 μmol O 3 g -1, (13±8)×10 -5, and (1.0±1.3)×10 -5. Unwashed hair taken close to the scalp exhibited the highest integrated ozone uptake and reaction probability, indicating that scalp oils are responsible for much of the ozone reactivity. Otherwise there was no significant difference between washed and unwashed hair. Compounds (geranyl acetone, 6-methyl-5-hepten-2-one, and decanal) associated with ozone reacting with sebum were observed as secondary products more frequently from unwashed hair than for washed hair and the summed yield of aldehydes ranged from 0.00 to 0.86. Based on reaction probabilities, cumulative ozone uptake and typical sebum generation rates, ozone flux to skin and hair is anticipated to be nearly transport limited, reducing personal exposure to ozone and increasing exposure to reaction products.

  7. Characteristics of polar stratospheric clouds during the formation of the Antarctic ozone hole

    NASA Technical Reports Server (NTRS)

    Hamill, Patrick; Toon, O. B.; Turco, R. P.

    1986-01-01

    Measured properties of Antarctic polar stratospheric clouds are described, and the possible relationship between the clouds and the formation of the ozone hole is considered. It is shown that the ozone hole develops and the clouds dissipate in the same place and at the same time. There may be a causal relationship between cloud particle evaporation and ozone depletion. A heterogeneous mechanism involving chemical reactions in the cloud droplets is suggested.

  8. N-Nitrosodimethylamine formation from ozonation of chlorpheniramine: Influencing factors and transformation mechanism.

    PubMed

    Lv, Juan; Wang, Lin; Song, Yun; Li, Yongmei

    2015-12-15

    As a disinfection byproduct, the detection of N-nitrosodimethylamine (NDMA) in aquatic environments across the globe has caused widespread concern due to its potential carcinogenicity. In this study, the possibility of NDMA formation from chlorpheniramine ozonation was investigated. The influencing factors including the initial chlorpheniramine concentration, ozone dose, pH, and water matrix were quantified. Furthermore, the mechanisms for chlorpheniramine transformation and NDMA formation were explored. Our results demonstrate that ozonation is effective in removing chlorpheniramine. Generation of dimethylamine (DMA) and NDMA was observed during chlorpheniramine ozonation. Higher initial chlorpheniramine concentration and ozone dose resulted in higher production of NDMA. Acidic conditions (pH≤5) did not facilitate the production of NDMA. Ozone molecules played a dominant role in chlorpheniramine degradation, and influenced DMA release and NDMA formation. DMA and NDMA generations as well as their degradations were mainly attributed to hydroxyl radicals (·OH) produced by ozone decomposition. Water matrix properties such as HCO3(-) and humic acid affected DMA and NDMA generation due to ·OH competition. The degradation intermediates of chlorpheniramine were identified, among which only the intermediates with a DMA group were attributable to NDMA formation. A possible pathway for NDMA formation from chlorpheniramine ozonation is proposed.

  9. [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.

  10. An influence of hypothetical products of dimethylamine ozonation on N-nitrosodimethylamine formation.

    PubMed

    Andrzejewski, P; Fijolek, L; Nawrocki, J

    2012-08-30

    The paper concerns formation of N-nitrosodimethylamine (NDMA) upon ozonation of dimethylamine (DMA) aqueous solutions. According to current hypothesis ozonated DMA is oxidized to N-dimethylhydroxylamine (DMHA), then to N-methylhydroxylamine (MHA) and finally to hydroxylamine (HA). HA subsequently reacts with the remain part of DMA to form unsymmetrical dimethylhydrazine (UDMH). Finally UDMH undergoes oxidation with ozone to form NDMA. HA is thought to be an important by-product that increases the NDMA formation. We decided to verify the hypothesis by an ozonation of DMA aqueous solutions in the presence of DMHA, MHA and HA. We have clearly proved that ozonation of DMA in the presence of DMHA and/or MHA does not increase NDMA formation. These results do not exclude the possibility of HA formation during DMA ozonation, but unambiguously show that even if HA is formed during this reaction, it does not have any impact on NDMA formation. In authors opinion the formation of MHA and HA is however doubtful since both compounds seem to be rather products of reduction than oxidation. Therefore HA-DMA reaction cannot be responsible for the formation of NDMA when DMA aqueous solution is ozonized. Copyright © 2012 Elsevier B.V. All rights reserved.

  11. Medical ozone therapy decreases postoperative uterine adhesion formation in rats.

    PubMed

    Uysal, Bulent; Demirbag, Suzi; Poyrazoglu, Yavuz; Cayci, Tuncer; Yesildaglar, Narter; Guven, Ahmet; Sürer, Ilhami; Korkmaz, Ahmet

    2012-11-01

    Various studies have been performed to find out novel treatment strategies to prevent postoperative adhesion formation. Ozone therapy (OT) is shown to reduce inflammation in several pathological conditions. Therefore, we aimed to evaluate the efficacy of OT in a rat model of experimental uterine adhesion (EUA). Thirty female Wistar rats (200-250 g) were divided into three groups: sham, EUA and EUA+OT. EUA and EUA+OT groups were subjected to the postoperative adhesion procedure by bipolar coagulation on the uterine horns and corresponding pelvic sidewall parietal peritoneum. EUA+OT group received 0.7 mg/kg daily single dose for 3 days of ozone/oxygen mixture intraperitoneally after adhesion induction. All animals were killed on the 7th day and uterine adhesions were scored. Uterine tissues and peritoneal washing fluid were harvested for all analyses. Uterine malondialdehyde levels in the EUA group were significantly higher compared to the other groups. However, in the EUA group, uterine superoxide dismutase and glutathione peroxidase activities were lower than in other groups. Peritoneal fluid TNF-α levels were found to be significantly different for all groups (p < 0.001). Macroscopic total adhesion score was significantly higher in the EUA group compared to the other groups (p < 0.001). But, total score in the EUA+OT group was lower than in the EUA group (p = 0.006). Medical OT prevents postoperative uterine adhesions by modulating TNF-α levels and oxidative/antioxidative status in an experimental uterine adhesion model.

  12. Effect of magnetic ion exchange and ozonation on disinfection by-product formation.

    PubMed

    Kingsbury, Ryan S; Singer, Philip C

    2013-03-01

    The purpose of this research was to investigate the performance of treatment with magnetic ion exchange (MIEX) resin followed by ozonation in achieving disinfection goals while controlling bromate and chlorinated disinfection by-product (DBP) formation. Three water samples were collected from raw water supplies impacted by the San Francisco Bay Delta to represent the varying levels of bromide and total organic carbon (TOC) that occur throughout the year. A fourth water was prepared by spiking bromide into a portion of one of the samples. Samples of each water were pre-treated with alum or virgin MIEX resin, and the raw and treated waters were subsequently ozonated under semi-batch conditions to assess the impact of treatment on ozone demand, ozone exposure for disinfection ("CT"), and bromate formation. Finally, aliquots of raw, coagulated, resin-treated, and ozonated waters were chlorinated in order to measure trihalomethane formation potential (THMFP). In the waters studied, MIEX resin removed 41-68% of raw water TOC, compared to 12-44% for alum. MIEX resin also reduced the bromide concentration by 20-50%. The removal of TOC by alum and MIEX resin significantly reduced the ozone demand of all waters studied, resulting in higher dissolved ozone concentrations and CT values for a given amount of ozone transferred into solution. For a given level of disinfection (CT), the amount of bromate produced by ozonation of MIEX-treated waters was similar to or slightly less than that of raw water and significantly less than that of alum-treated water. MIEX resin removed 39-85% of THMFP compared to 16-56% removal by alum. Ozonation reduced THMFP by 35-45% in all cases. This work indicates that in bromide-rich waters in which ozone disinfection is used, MIEX resin is a more appropriate treatment than alum for the removal of organic carbon, as it achieves superior TOC and THM precursor removal and decreases the production of bromate from ozone.

  13. 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) ...

  14. 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) ...

  15. Characteristics of volatile organic compounds and their role in ground-level ozone formation in the Beijing-Tianjin-Hebei region, China

    NASA Astrophysics Data System (ADS)

    Li, Lingyu; Xie, Shaodong; Zeng, Limin; Wu, Rongrong; Li, Jing

    2015-07-01

    To better understand the chemical speciation of volatile organic compounds (VOCs) and their role in ground-level ozone formation in the Beijing-Tianjin-Hebei region, China, measurements of 56 non-methane hydrocarbons (NMHCs) and 12 carbonyls were conducted at three sites in summer. Alkanes were the largest group of NMHCs (>50%), followed by alkenes and aromatics. Acetone was the most abundant carbonyl species (>50%). The OH loss rates (LOH) of VOCs were calculated to estimate their chemical reactivities. Alkenes played a predominant role in VOC reactivity, among which ethene and propene were the largest contributors. Isoprene contributed 11.61-38.00% of the total reactivity of measured VOCs. Alkenes and aromatics were the largest contributors (47.65-61.53% totally) to the total Ozone Formation Potential (OFP) of measured VOCs based on the observed mixing ratio. Isoprene was the most reactive species, but originated mainly from biogenic emissions. Ethene, m/p-xylene, toluene, propene, o-xylene, and 1-butene were considered to play significant roles in ground-level ozone formation in this region. The OFPs of total measured NMHCs increased by 10.20-22.05% when they were calculated based on the initial mixing ratio. Photochemical losses of hydrocarbons and the secondary formation of carbonyls in this region were also determined. Vehicle exhaust emissions contributed substantially to ambient VOCs.

  16. Effect of chemical kinetics uncertainties on calculated constituents in a tropospheric photochemical model

    NASA Technical Reports Server (NTRS)

    Thompson, Anne M.; Stewart, Richard W.

    1991-01-01

    Random photochemical reaction rates are employed in a 1D photochemical model to examine uncertainties in tropospheric concentrations and thereby determine critical kinetic processes and significant correlations. Monte Carlo computations are used to simulate different chemical environments and their related imprecisions. The most critical processes are the primary photodissociation of O3 (which initiates ozone destruction) and NO2 (which initiates ozone formation), and the OH/methane reaction is significant. Several correlations and anticorrelations between species are discussed, and the ozone/transient OH correlation is examined in detail. One important result of the modeling is that estimates of global OH are generally about 25 percent uncertain, limiting the precision of photochemical models. Techniques for reducing the imprecision are discussed which emphasize the use of species and radical species measurements.

  17. Secondary organic aerosol formation initiated from reactions between ozone and surface-sorbed squalene

    NASA Astrophysics Data System (ADS)

    Wang, Chunyi; Waring, Michael S.

    2014-02-01

    Previous research has shown that ozone reactions on surface-sorbed D-limonene can promote gas phase secondary organic aerosol (SOA) formation indoors. In this work, we conducted 13 steady state chamber experiments to measure the SOA formation entirely initiated by ozone reactions with squalene sorbed to glass, at chamber ozone of 57-500 ppb for two relative humidity (RH) conditions of 21% and 51%, in the absence of seed particles. Squalene is a nonvolatile compound that is a component of human skin oil and prevalent on indoor surfaces and in settled dust due to desquamation. The size distributions, mass and number secondary emission rates (SER), aerosol mass fractions (AMF), and aerosol number fractions (ANF) of formed SOA were quantified. The surface AMF and ANF are defined as the change in SOA mass or number formed, respectively, per ozone mass consumed by ozone-squalene reactions. All experiments but one exhibited nucleation and mass formation. Mass formation was relatively small in magnitude and increased with ozone, most notably for the RH = 51% experiments. The surface AMF was a function of the chamber aerosol concentration, and a multi-product model was fit using the 'volatility basis set' framework. Number formation was relatively strong at low ozone and low RH conditions. Though we cannot extrapolate our results because experiments were conducted at high air exchange rates, we speculate that this process may enhance particle number more than mass concentrations indoors.

  18. Technique for monitoring ozone precursor hydrocarbons in air at photochemical assessment monitoring stations: Sorbent preconcentration, closed-cycle cooler cryofocusing, and GC-FID analysis

    NASA Astrophysics Data System (ADS)

    Oliver, Karen D.; Adams, Jeffrey R.; Hunter Daughtrey, E.; McClenny, William A.; Yoong, Matthias J.; Pardee, Michael A.

    An automated gas chromatograph (autoGC) system that may be used to collect and analyze both polar and nonpolar volatile organic compounds in ambient air has been evaluated. This system combines the use of dual multiadsorbent traps for sampling 57 min h -1 at ambient temperature, a dry helium purge to remove residual water from the sorbents, thermal desorption of analytes onto a Stirling-cooled trap for refocusing, and GC-flame ionization detection (FID). Method detection limits (MDLs), linearity, cleanliness, precision, and accuracy of the autoGC were determined for a set of 57 ozone precursor hydrocarbons. For most of the compounds tested, MDLs were less than 0.40 ppbv, the FID response was linear over the 5-40-ppbv range, and the trap-to-trap precision was ± 10%. This autoGC was found to be a reliable system that would be suitable for use in field sites such as the Photochemical Assessment Monitoring Stations network, which is being implemented in the United States of America.

  19. Source apportionment of biogenic contributions to ozone formation over the United States

    NASA Astrophysics Data System (ADS)

    Zhang, Rui; Cohan, Alexander; Pour Biazar, Arastoo; Cohan, Daniel S.

    2017-09-01

    Vegetation is the leading emitter of volatile organic compounds (VOC), a key ingredient for ozone formation. The contribution of biogenic VOC (BVOC) emissions to regional ozone formation needs better quantification so that air quality regulators can effectively design emission control strategies. One of the key uncertainties for modeling BVOC emissions comes from the estimation of photosynthetically active radiation (PAR) reaching canopy. Satellite insolation retrieval data provide an alternative to prognostic meteorological models for representing the spatial and temporal variations of PAR. In this study, biogenic emission estimates generated with the MEGAN and BEIS biogenic emissions models using satellite or prognostic PAR are used to examine the contribution of BVOC to ozone in the United States. The Comprehensive Air Quality Model with Extensions (CAMx) is applied with Ozone Source Apportionment Technology (OSAT) and brute force zero-out sensitivity runs to quantify the biogenic contributions to ozone formation during May through September 2011. The satellite PAR retrievals are on average lower than modeled PAR and exhibit better agreement with SCAN and SURFRAD network measurements. Using satellite retrievals instead of modeled PAR reduces BEIS and MEGAN estimates of isoprene by an average of 3%-4% and 9%-12%, respectively. The simulations still overestimate observed ground-level isoprene concentrations by a factor of 1.1 for BEIS and 2.6 for MEGAN. The spatial pattern of biogenic ozone contribution diagnosed from OSAT differs from the brute force zero-out sensitivity results, with the former more smoothly distributed and the latter exhibiting peak impacts near metropolitan regions with intense anthropogenic NOx emissions. OSAT tends to apportion less ozone to biogenics as BVOC emissions increase, since that shifts marginal ozone formation toward more NOx-limited conditions. By contrast, zero-out source apportionment of ozone to biogenics increases with BVOC

  20. Regional impacts of oil and gas development on ozone formation in the western United States.

    PubMed

    Rodriguez, Marco A; Barna, Michael G; Moore, Tom

    2009-09-01

    The Intermountain West is currently experiencing increased growth in oil and gas production, which has the potential to affect the visibility and air quality of various Class I areas in the region. The following work presents an analysis of these impacts using the Comprehensive Air Quality Model with extensions (CAMx). CAMx is a state-of-the-science, "one-atmosphere" Eulerian photochemical dispersion model that has been widely used in the assessment of gaseous and particulate air pollution (ozone, fine [PM2.5], and coarse [PM10] particulate matter). Meteorology and emissions inventories developed by the Western Regional Air Partnership Regional Modeling Center for regional haze analysis and planning are used to establish an ozone baseline simulation for the year 2002. The predicted range of values for ozone in the national parks and other Class I areas in the western United States is then evaluated with available observations from the Clean Air Status and Trends Network (CASTNET). This evaluation demonstrates the model's suitability for subsequent planning, sensitivity, and emissions control strategy modeling. Once the ozone baseline simulation has been established, an analysis of the model results is performed to investigate the regional impacts of oil and gas development on the ozone concentrations that affect the air quality of Class I areas. Results indicate that the maximum 8-hr ozone enhancement from oil and gas (9.6 parts per billion [ppb]) could affect southwestern Colorado and northwestern New Mexico. Class I areas in this region that are likely to be impacted by increased ozone include Mesa Verde National Park and Weminuche Wilderness Area in Colorado and San Pedro Parks Wilderness Area, Bandelier Wilderness Area, Pecos Wilderness Area, and Wheeler Peak Wilderness Area in New Mexico.

  1. Wavelength and temperature-dependent apparent quantum yields for photochemical formation of hydrogen peroxide in seawater.

    PubMed

    Kieber, David J; Miller, Gary W; Neale, Patrick J; Mopper, Kenneth

    2014-04-01

    Wavelength and temperature-dependent apparent quantum yields (AQYs) were determined for the photochemical production of hydrogen peroxide using seawater obtained from coastal and oligotrophic stations in Antarctica, the Pacific Ocean at Station ALOHA, the Gulf of Mexico, and at several sites along the East Coast of the United States. For all samples, AQYs decreased exponentially with increasing wavelength at 25 °C, ranging from 4.6 × 10(-4) to 10.4 × 10(-4) at 290 nm to 0.17 × 10(-4) to 0.97 × 10(-4) at 400 nm. AQYs for different seawater samples were remarkably similar irrespective of expected differences in the composition and concentrations of metals and dissolved organic matter (DOM) and in prior light exposure histories; wavelength-dependent AQYs for individual seawater samples differed by less than a factor of two relative to respective mean AQYs. Temperature-dependent AQYs increased between 0 and 35 °C on average by a factor of 1.8 per 10 °C, consistent with a thermal reaction (e.g., superoxide dismutation) controlling H2O2 photochemical production rates in seawater. Taken together, these results suggest that the observed poleward decrease in H₂O₂ photochemical production rates is mainly due to corresponding poleward decreases in irradiance and temperature and not spatial variations in the composition and concentrations of DOM or metals. Hydrogen peroxide photoproduction AQYs and production rates were not constant and not independent of the photon exposure as has been implicitly assumed in many published studies. Therefore, care should be taken when comparing and interpreting published H₂O₂ AQY or photochemical production rate results. Modeled depth-integrated H₂O₂ photochemical production rates were in excellent agreement with measured rates obtained from in situ free-floating drifter experiments conducted during a Gulf of Maine cruise, with differences (ca. 10%) well within measurement and modeling uncertainties. Results from this study

  2. Formation of free radicals in the photochemical modification of antifrictional plastic compositions

    SciTech Connect

    Klimov, E.S.; Vakar, A.A.; Sokolov, V.P.; Okhlobystin, O.Yu.

    1987-09-20

    Using ESR spectroscopy the authors investigated the photolysis and radical composition of a plastic lubricant composed of polyethylene, perfluoroalkylpolyester 240, oleic acid, mineral oil, and benzophenone. The spectra are comprehensively analyzed. Hyperfine structure and spin trapping are given for the polyalkyl radicals. The photochemical modification of the lubricant leading to these radicals, and their reaction with oxygen, are determined to be responsible for the enhanced adhesion of the plasticizers to the polymer.

  3. Photochemical formation of hydrogen peroxide in surface and ground waters exposed to sunlight

    SciTech Connect

    Cooper, W.J.; Zika, R.G.

    1983-05-13

    A rapid increase in the concentration of hydrogen peroxide was observed when samples of natural surface and ground water from various locations in the United States were exposed to sunlight. The hydrogen peroxide is photochemically generated from organic constitutents present in the water; humic materials are believed to be the primary agent producing the peroxide. Studies with superoxide dismutase suggest that the superoxide anion is the precursor of the peroxide.

  4. Secondary organic aerosol formation from ozone reactions with single terpenoids and terpenoid mixtures

    NASA Astrophysics Data System (ADS)

    Waring, Michael S.; Wells, J. Raymond; Siegel, Jeffrey A.

    2011-08-01

    Ozone reacts with indoor-emitted terpenoids to form secondary organic aerosol (SOA). Most SOA research has focused on ozone reactions with single terpenoids or with consumer products, and this paper reports the results from an investigation of SOA formation from ozone reactions with both single terpenoids and mixtures of D-limonene, α-pinene, and α-terpineol. Transient experiments were conducted at low (25 ppb) and high (100 ppb) initial concentrations of ozone. The three terpenoids were tested singly and in combinations in a manner that controlled for their different reaction rates with ozone. The SOA formation was assessed by examining the evolution in time of the resulting number size-distributions and estimates of the mass concentrations. The results suggest that at higher ozone and terpenoid concentrations, SOA number formation follows a linear trend as a function of the initial rate of reaction. This finding was valid for both single terpenoids and mixtures. Generally speaking, higher ozone and terpenoid concentrations also led to larger geometric mean diameters and smaller geometric standard deviations of fitted lognormal distributions of the formed SOA. By assuming a density, mass concentrations were also assessed and did not follow as consistent of a trend. At low ozone concentration conditions, reactions with only D-limonene yielded the largest number concentrations of any experiment, even more than experiments with mixtures containing D-limonene and much higher overall terpenoid concentrations. This finding was not seen for high ozone concentrations. These experiments demonstrate quantifiable trends for SOA forming reactions of ozone and mixtures, and this work provides a framework for expanding these results to more complex mixtures and consumer products.

  5. Ozonation of piperidine, piperazine and morpholine: Kinetics, stoichiometry, product formation and mechanistic considerations.

    PubMed

    Tekle-Röttering, Agnes; Jewell, Kevin S; Reisz, Erika; Lutze, Holger V; Ternes, Thomas A; Schmidt, Winfried; Schmidt, Torsten C

    2016-01-01

    Piperidine, piperazine and morpholine as archetypes for secondary heterocyclic amines, a structural unit that is often present in pharmaceuticals (e.g., ritalin, cetirizine, timolol, ciprofloxacin) were investigated in their reaction with ozone. In principle the investigated compounds can be degraded with ozone in a reasonable time, based on their high reaction rate constants with respect to ozone (1.9 × 10(4)-2.4 × 10(5) M(-1) s(-1)). However, transformation is insufficient (13-16%), most likely due to a chain reaction, which decomposes ozone. This conclusion is based on OH scavenging experiments, leading to increased compound transformation (18-27%). The investigated target compounds are similar in their kinetic and stoichiometric characteristics. However, the mechanistic considerations based on product formation indicate various reaction pathways. Piperidine reacts with ozone via a nonradical addition reaction to N-hydroxypiperidine (yield: 92% with and 94% without scavenging, with respect to compound transformation). However, piperazine degradation with ozone does not lead to N-hydroxypiperazine. In the morpholine/ozone reaction, N-hydroxymorpholine was identified. Additional oxidation pathways in all cases involved the formation of OH with high yields. One important pathway of piperazine and morpholine by ozonation could be the formation of C-centered radicals after ozone or OH radical attack. Subsequently, O2 addition forms unstable peroxyl radicals, which in one pathway loose superoxide radicals by generating a carbon-centered cation. Subsequent hydrolysis of the carbon-centered cation leads to formaldehyde, whereby ozonation of the N-hydroxy products can proceed in the same way and in addition give rise to hydroxylamine. A second pathway of the short-lived peroxyl radicals could be a dimerization to form short-lived tetraoxides, which cleave by forming hydrogen peroxide. All three products have been found.

  6. Photochemical Formation of Fe(II) and Peroxides in Coastal Seawater Collected around Okinawa Island, Japan - Impact of Red Soil Pollution

    NASA Astrophysics Data System (ADS)

    Okada, K.; Nakajima, H.; Higuchi, T.; Fujimura, H.; Arakaki, T.; Taira, H.

    2003-12-01

    In a study to elucidate the impacts of red soil pollution on the oxidizing power of seawater, photochemical formation of Fe(II) and peroxides was studied in seawaters collected around Okinawa Island, Japan. The northern part of Okinawa Island suffers from red soil pollution which is caused mainly by land development such as pineapple farming and the construction of recreational facilities. We studied photochemical formation of peroxides and Fe(II) in the same seawater samples because the reaction between HOOH and Fe(II) forms hydroxyl radical (OH radical), the most potent environmental oxidant. Photochemical formation of Fe(II) was fast and reached steady-state in 30 minutes of simulated sunlight illumination and the steady-state Fe(II) concentrations were about 80% of total iron concentrations. Photochemical formation of peroxides was relatively slow and formation kinetics varied, depending on the initial peroxide concentrations. Because photochemical formation of peroxides was faster and total iron concentrations in the red soil polluted seawater were higher, red soil polluted seawater is expected to have greater oxidizing power than seawater that is not polluted with red soil.

  7. EXPERIMENTAL EVIDENCE FOR WATER FORMATION VIA OZONE HYDROGENATION ON DUST GRAINS AT 10 K

    SciTech Connect

    Mokrane, H.; Chaabouni, H.; Accolla, M.; Congiu, E.; Dulieu, F.; Chehrouri, M.; Lemaire, J. L.

    2009-11-10

    The formation of water molecules from the reaction between ozone (O{sub 3}) and D-atoms is studied experimentally for the first time. Ozone is deposited on non-porous amorphous solid water ice (H{sub 2}O), and D-atoms are then sent onto the sample held at 10 K. HDO molecules are detected during the desorption of the whole substrate where isotope mixing takes place, indicating that water synthesis has occurred. The efficiency of water formation via hydrogenation of ozone is of the same order of magnitude as that found for reactions involving O-atoms or O{sub 2} molecules and exhibits no apparent activation barrier. These experiments validate the assumption made by models using ozone as one of the precursors of water formation via solid-state chemistry on interstellar dust grains.

  8. Role of the propagation reactions on the hydroxyl radical formation in ozonation and peroxone (ozone/hydrogen peroxide) processes.

    PubMed

    Liu, Yongze; Jiang, Jin; Ma, Jun; Yang, Yi; Luo, Congwei; Huangfu, Xiaoliu; Guo, Zhongkai

    2015-01-01

    To better predict the elimination of highly ozone-refractory organic micro-pollutants from wastewater in ozonation and peroxone (O₃/H₂O₂) processes, it is important to understand the OH• formation therein. Nevertheless, the contribution of the propagation reactions (in brief, OH• + DOM (Dissolved Organic Matter) + O₂ → O₂•⁻, O₃ + O₂•⁻ → O₃•⁻ → OH•) to the OH• yields (Ф) in these two processes has not received great attention so far. In this study, >25% of O₃ was estimated to be consumed via the propagation reactions in ozonation of wastewater effluents. The competition method (taking the OH• exposure and scavenging capacity of water matrix into account) was recommended to determine the Ф values, and thus the relatively higher values (i.e., 33–58% vs. 6–24%) in ozonation were obtained as compared with the "tert-Butanol (tBuOH) assay" (with excess tBuOH to scavenge OH• producing stoichiometric formaldehyde), where the contribution of the propagation reactions was otherwise neglected when excess tBuOH completely scavenged OH. In peroxone of wastewater effluents, the rate constant of O₃ consumption increased significantly with the increase of H₂O₂ concentration ([H₂O₂]:[O₃] = 0.1–0.35). However, compared to ozonation alone, the improvement of the Ф values was negligible over a wide range of [H₂O₂]:[O₃] = 0.1–2.0. This discrepancy was mainly ascribed to the fact that substantial O₃ consumption via the propagation reactions resulted in comparable Ф values in peroxone vs. ozonation processes.

  9. The relationship between total ozone content and the baric formations

    NASA Astrophysics Data System (ADS)

    Glushchenko, Iu. V.

    1991-06-01

    Results are presented on the distribution of ozone in the altitudinal pressure fields, which were obtained during the 1979-1980 time period by means of airborne measurements above the European USSR and Central Asia between the latitudes of 39 and 55 deg N. It is shown that the relative distribution of ozone among the pressure crests, pressure troughs, and frontal zones depends mainly on the dynamics of the atmosphere.

  10. Sensitivty of ozone production to organic nitrate formation in Sacramento and Los Angeles

    NASA Astrophysics Data System (ADS)

    Browne, E. C.; Cohen, R. C.

    2010-12-01

    Total alkyl and multifunctional nitrates (ΣANs) are formed by a minor channel of the NO + RO2 reaction and thus represent a termination step of ozone production. ΣANs formation becomes most significant in the cross-over regime between NOx saturated (VOC limited) and NOx limited ozone production. In models that fail to account for changing rates of ΣANs formation, the NOx and VOC levels are considered independent parameters: to lower ozone production all that is needed is to decrease the limiting parameter. It has been recently shown that this view on ozone production may lead to counterproductive air quality control strategies (Farmer et al., 2010 submitted). Using both an analytical model and measurements from Mexico City, Farmer et al. demonstrated that ΣANs formation effectively couples VOCs and NOx. Analytical models show that VOC reduction strategies that result in a decrease in ΣANs yield will result in increased ozone production for NOx less than 3 ppb. We expand upon the work of Farmer et al. by investigating the sensitivity of ozone production to ΣANs formation using a regional three dimensional chemical transport model, WRF-CHEM. The standard chemistry treats all ΣANs species as a single model species with a given lifetime and NOx recycling efficiency. We implement a revised ΣANs representation that treats monofunctional, multifunctional saturated, multifunctional unsaturated, aromatic, isoprene, and monoterpene nitrates as unique model species with appropriate lifetimes and NOx recycling efficiencies. We investigate how this improved ΣANs representation affects ozone, and we compare these results to ground and airborne measurements in the Sacramento and Los Angeles areas. Additionally, we investigate the sensitivity of ozone formation to ΣANs formation rate, lifetime, and NOx recycling efficiency.

  11. N-nitrosodimethylamine (NDMA) formation during ozonation of dimethylamine-containing waters.

    PubMed

    Andrzejewski, Przemysław; Kasprzyk-Hordern, Barbara; Nawrocki, Jacek

    2008-02-01

    Ozonation of aqueous solutions of dimethylamine (DMA) leads to the formation of nitrosodimethylamine (NDMA). The yield of reaction is low (below 0.4% in relation to DMA) and increases with increasing pH. Contact time, ozone/DMA ratio and radical scavengers are other variables controlling the yield of reaction. Data from the literature and observed ozonation by-products suggest that nitrosation of DMA might be responsible for nitrosamine generation. NDMA can be recognized as a by-product of ozonation of DMA in water, which is formed in a specific, but reasonable, range of ozone/DMA ratios. The reaction may have potential importance for water treatment technology assuming reasonable micrograms per liter of DMA concentrations in raw waters.

  12. 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.

  13. Reduction of soil carbon formation by tropospheric ozone under increased carbon dioxide levels.

    PubMed

    Loya, Wendy M; Pregitzer, Kurt S; Karberg, Noah J; King, John S; Giardina, Christian P

    2003-10-16

    In the Northern Hemisphere, ozone levels in the troposphere have increased by 35 per cent over the past century, with detrimental impacts on forest and agricultural productivity, even when forest productivity has been stimulated by increased carbon dioxide levels. In addition to reducing productivity, increased tropospheric ozone levels could alter terrestrial carbon cycling by lowering the quantity and quality of carbon inputs to soils. However, the influence of elevated ozone levels on soil carbon formation and decomposition are unknown. Here we examine the effects of elevated ozone levels on the formation rates of total and decay-resistant acid-insoluble soil carbon under conditions of elevated carbon dioxide levels in experimental aspen (Populus tremuloides) stands and mixed aspen-birch (Betula papyrifera) stands. With ambient concentrations of ozone and carbon dioxide both raised by 50 per cent, we find that the formation rates of total and acid-insoluble soil carbon are reduced by 50 per cent relative to the amounts entering the soil when the forests were exposed to increased carbon dioxide alone. Our results suggest that, in a world with elevated atmospheric carbon dioxide concentrations, global-scale reductions in plant productivity due to elevated ozone levels will also lower soil carbon formation rates significantly.

  14. Control of disinfection by-product formation using ozone-based advanced oxidation processes.

    PubMed

    Chen, Kuan-Chung; Wang, Yu-Hsiang

    2012-01-01

    The effects of ozone dosage, water temperature and catalyst addition in an ozonation-fluidized bed reactor (O3/FBR) on treated water quality and on the control of chlorinated and ozonated disinfection by-products (DBPs) were investigated. A biofiltration column was used to evaluate its removal efficiency on biodegradable organic matter and to reduce DBP formation. The Dong-Gang River, polluted by agricultural and domestic wastewater in Pingtung, Taiwan, was used as the water source. The treated water quality in terms of dissolved organic carbon (DOC), biodegradable DOC, ultraviolet absorbance at 254 nm (UV254) and specific UV absorbance (SUVA) improved with increasing ozone and catalyst dosages. Catalytic ozonation was more effective than ozonation alone at reducing the formation of DBPs at a given dosage. Experimental results show that water temperature had little effect on the treated water quality with the O3/FBR system used in this study (p > 0.05). The combination of O3/FBR and the biofiltration process effectively decreased the amount ofDBP precursors. The concentration of total trihalomethanes (TTHMs) was less than the maximum contaminant level (MCL) requirement, which is 80 microg/L, for all treated waters and the concentration of five haloacetic acids (HAA5) fell below 60 microg/L with an ozone dosage higher than 2.5 mg/L.

  15. Effects of ozonation on disinfection byproduct formation and speciation during subsequent chlorination.

    PubMed

    Mao, Yuqin; Wang, Xiaomao; Yang, Hongwei; Wang, Haoyu; Xie, Yuefeng F

    2014-12-01

    Ozone has been widely used for drinking water treatment recently. This study was conducted to investigate the effect of dosing ozone on the formation potentials and speciation of disinfection by-products (DBPs, brominated DBPs in particular) during subsequent chlorination. Trihalomethanes (THMs), trihaloacetic acids (THAAs), dihaloacetic acids (DHAAs), dihaloacetonitriles (DHANs), chloral hydrate (CH)and trichloronitromethane (TCNM) were included. The results showed that the yields of THMs, THAAs and DHAAs reached the maxima at 1.83, 0.65 and 0.56 μM, respectively, corresponding to an ozone dose approximately at 2 mg L(-1). The formation potentials of CH and TCNM increased, while that of DHAN decreased, with the increase of ozone dose up to 6 mg L(-1). The bromide incorporation factor values of THMs, THAAs, DHAAs and DHANs increased from 0.62, 0.37, 0.45 and 0.39 at O3=0 mg L(-1) to 0.89, 0.65, 0.62 and 0.89 at O3=6 mg L(-1), respectively. It indicated that the use of ozone as a primary disinfectant may cause a shift to more brominated DBPs during subsequent chlorination, and the shift may be more evident with increased ozone dose. The total percentage of brominated DBPs (as bromide) reached the maximum value of 55% at 2 mg L(-1) ozone dose.

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

    SciTech Connect

    Shukairy, H.M.; Summers, R.S. ); Miltner, R.J. . Drinking Water Research Div.)

    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 may 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.

  17. Effect of the conditions of structure formation on the physicochemical properties of ozonated shungites

    NASA Astrophysics Data System (ADS)

    Emel'Yanova, G. I.; Gorlenko, L. E.; Rozhkova, N. N.; Rumyantseva, M. N.; Lunin, V. V.

    2010-08-01

    It was investigated the influence of ozone on the physicochemical properties of shungites (type 1) (75-98% C) from Nigozero and Chebolaksha deposits (Karelia) formed by hydrothermal (Nigozero) and high-temperature (Chebolaksha) processes. Ozonation was found to affect the specific surface and the total pore volume of shungites considerably. The pore size distribution pattern depends on the volume morphology (texture) of the sample. An increase in the temperature and pressure during the structure formation of shungite (Chebolaksha) led to a shift of the maximum on the distribution pattern towards the formation of mesopores. The size distribution of pores with the dominant contents of micro- and submesopores for both shungites correlated with the basic structural nanoelements of shungite carbon. The peculiarities of the ozonation of shungite nanocarbon found previously (the non-steady state vibrational kinetics of ozonation and the absence of carbon(II) oxide among the reaction products) were confirmed.

  18. Impacts of thermal circulations induced by urbanization on ozone formation in the Pearl River Delta region, China

    NASA Astrophysics Data System (ADS)

    Li, Mengmeng; Song, Yu; Mao, Zhichun; Liu, Mingxu; Huang, Xin

    2016-02-01

    Thermal circulations induced by urbanization could exert important effects on regional ozone (O3) formation through regulating the chemical transformations and transport of O3 and its precursors. In this study, the Weather Research and Forecasting/Chemistry (WRF/Chem) model combined with remote sensing are used to investigate the impacts of urbanization-induced circulations on O3 formation in the Pearl River Delta (PRD) region, China. The urban heat island (UHI) effect in PRD significantly enhances turbulent mixing and modifies local circulations, i.e., initiates the UHI circulation and strengthens the sea breeze, which in turn cause a detectable decrease of daytime O3 concentration (-1.3 ppb) and an increase of O3 (+5.2 ppb) around the nocturnal rush-hours. The suppressed O3 titration destruction due to NOx dilution into the deeper urban boundary layer (200-400 m) is the main reason for elevated nocturnal O3 levels. In the daytime, however, the upward transport of O3 precursors weakens near-surface O3 photochemical production and conversely enhances upper-level O3 generation. Furthermore, the surface UHI convergence flow and intensified sea breeze act to effectively trap O3 at the suburban and coastal regions.

  19. Ozone consumption and volatile byproduct formation from surface reactions with aircraft cabin materials and clothing fabrics

    NASA Astrophysics Data System (ADS)

    Coleman, Beverly K.; Destaillats, Hugo; Hodgson, Alfred T.; Nazaroff, William W.

    We measured ozone consumption and byproduct formation on materials commonly found in aircraft cabins at flight-relevant conditions. Two series of small-chamber experiments were conducted, with most runs at low relative humidity (10%) and high air-exchange rate (˜20 h -1). New and used cabin materials (seat fabric, carpet, and plastic) and laundered and worn clothing fabrics (cotton, polyester, and wool) were studied. We measured ozone deposition to many material samples, and we measured ozone uptake and primary and secondary emissions of volatile organic compounds (VOCs) from a subset of samples. Deposition velocities ranged from 0.06 to 0.54 cm s -1. Emissions of VOCs were higher with ozone than without ozone in every case. The most commonly detected secondary emissions were C 1 through C 10 saturated aldehydes and the squalene oxidation products 6-methyl-5-hepten-2-one and acetone. For the compounds measured, summed VOC emission rates in the presence of 55-128 ppb (residual level) ozone ranged from 1.0 to 8.9 μmol h -1 m -2. Total byproduct yield ranged from 0.07 to 0.24 moles of product volatilized per mole of ozone consumed. Results were used to estimate the relative contribution of different materials to ozone deposition and byproduct emissions in a typical aircraft cabin. The dominant contributor to both was clothing fabrics, followed by seat fabric. Results indicate that ozone reactions with surfaces substantially reduce the ozone concentration in the cabin but also generate volatile byproducts of potential concern for the health and comfort of passengers and crew.

  20. 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

  1. Evidence for the formation of CCN by photochemical processes in Mexico City

    NASA Astrophysics Data System (ADS)

    Baumgardner, D.; Raga, G. B.; Muhlia, A.

    Cloud condensation nuclei (CCN) concentrations in Mexico City have a diurnal cycle that is similar to those of condensation nuclei (CN) and PM 2.5 but CCN, on average, lags the changes in CN and PM 2.5 by almost an hour. The nature of these patterns is related to the onset of emissions from vehicular traffic in the morning followed by the photochemical production of secondary organics that condense on the primary particles. The rates at which particles grow and the detection thresholds of the instruments that measure them impose the apparent lag in CCN trends. A size-resolved aerosol model simulates the observed trend when instrument thresholds and boundary layer growth are taken into account. The measurements made in the year 2000 show no discernible decrease in maximum daily CCN concentrations when compared to similar measurements made in 1984, despite the efforts of local authorities to decrease pollution levels in Mexico City.

  2. Sensitivity analysis of ozone formation and transport for a Central California air pollution episode

    SciTech Connect

    Jin, Ling; Tonse, Shaheen; Cohan, Daniel S.; Mao, Xiaoling; Harley, Robert A.; Brown, Nancy J.

    2009-05-15

    CMAQ-HDDM is used to determine spatial and temporal variations in ozone limiting reagents and local vs upwind source contributions for an air pollution episode in Central California. 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 five-day ozone episode (29th July-3rd Aug, 2000). Despite considerable spatial variations, nitrogen oxides (NO{sub x}) emission reductions are overall more effective than volatile organic compound (VOC) control for attaining the 8-hr ozone standard in this region for this episode, in contrast to the VOC control that works better for attaining the prior 1-hr ozone standard. Inter-basin source contributions of NO{sub 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{sub x} and AVOC, and the rate coefficient of the OH + NO{sub 2} termination reaction, have the greatest effect on first-order ozone responses to changes in NO{sub x} emissions. Uncertainties in biogenic VOC emissions only have a modest effect because they are generally not collocated with anthropogenic sources in this region.

  3. Modeling ozone formation from industrial emission events in Houston, Texas

    NASA Astrophysics Data System (ADS)

    Vizuete, William; Kim, Byeong-Uk; Jeffries, Harvey; Kimura, Yosuke; Allen, David T.; Kioumourtzoglou, Marianthi-Anna; Biton, Leiran; Henderson, Barron

    It is now generally accepted that industrial emission events are occurring from chemical processing facilities in Houston, Texas with daily frequencies and significant temporal variability. These events have been reported to last from hours to days, and a large fraction are made up of four highly reactive volatile organic compounds (HRVOCs): ethene, propene, butenes, and 1,3-butadiene. The Texas Commission on Environmental Quality (TCEQ) has targeted industrial sources of HRVOCs by imposing annual and hourly limits and creating a market-based HRVOC emissions cap and trade (HECT) program. The HECT program uses the Maximum Incremental Reactivity (MIR) scale to calculate the magnitude needed to trade between HRVOCs. The work reported here used the TCEQ regulatory model to evaluate the HECT program's use of the MIR scale by simulating a series of hypothetical but observational-based industrial emission events for different VOC species. The magnitude of each release was adjusted based on the MIR scale under the assumption that this would give the same increase in ozone. The regulatory model, however, predicted that o-xylene caused the largest increase in ozone. In every simulation, ozone production was directly related to the amount of hydroxyl radicals produced from the photolysis of formaldehyde and other aldehydes. The sensitivity of ozone production to these hydroxyl radical sources appeared regardless of whether the industrial emission event plume encountered high sources of NO x. The MIR scale was developed for an average urban atmosphere and its failure in equating ozone reactivity here may be due to the extreme levels of NO x and VOC seen in event emissions in Houston.

  4. Photochemical process on chloromethyl formate and vinyl formate in low-temperature matrices: infrared spectra and ab initio calculations on chloromethanol and vinyl alcohol

    SciTech Connect

    Kunttu, H.; Dahlqvist, M.; Murto, J.; Raesaenen, M.

    1988-03-24

    The UV decomposition of chloromethyl formate and vinyl formate has been studied in low-temperature noble gas matrices at wavelengths between 200 and 260 nm. Two distinct channels in cage photolysis were observed: (i) ClH/sub 2/COCHO ..-->.. ClH/sub 2/COH + CO; H/sub 2/CCHOCHO ..-->.. H/sub 2/CCHOH + CO. (ii) ClH/sub 2/COCHO ..-->.. H/sub 2/CO + HCl + CO; H/sub 2/CCHOCHO ..-->.. CH/sub 3/CHO + CO. There is a well-established wavelength dependence influencing the product ratios in these photochemical processes. Decomposition due to irradiation at wavelengths near 250 nm prefers channel i, where the formic acid esters decompose to the corresponding alcoholic species, chloromethanol (a new compound), and vinyl alcohol. On the other hand, at shorter wavelengths, channel ii dominates. Neither chloromethanol nor vinyl alcohol were observed to decompose at wavelengths above 200 nm. The photoprocesses of vinyl formate were also studied in NO-doped Ar matrices as well as in solid Xe in order to get information concerning the mechanisms of photochemical decomposition of formic acid esters. The assignment of the vibrational spectra is based on ab inito calculations performed at the Hartree-Fock 6-31G** level for chloromethanol and at the MP2/6-31G** level for vinyl alcohol. A detailed vibrational analysis is given for chloromethanol, chloromethanol-O-d, and vinyl alcohol.

  5. Studies in photochemical smog chemistry. 1. Atmospheric chemistry of toulene. 2. Analysis of chemical reaction mechanisms for photochemical smog

    SciTech Connect

    Leone, J.A.

    1985-01-01

    This study focuses on two related topics in the gas phase organic chemistry of importance in urban air pollution. An experimental effort aimed at developing a new explicit reaction mechanism for the atmospheric photooxidation of toluene is described. This mechanism is tested using experimental data from both indoor and outdoor smog chamber facilities. The predictions of the new reaction mechanism are found to be in good agreement with both sets of experimental data. Additional simulations performed with the new mechanism are used to investigate various mechanistic paths. A theoretical analysis of lumped chemical reaction mechanisms for photochemical smog is presented. Included is a description of a new counter species analysis technique which can be used to analyze any complex chemical reaction mechanism. When applied to mechanisms for photochemical smog, this analysis is shown capable of providing answers to previously inaccessible questions such as the relative contributions of individual organics to photochemical ozone formation.

  6. 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.

  7. Effects of ozone and ozone/peroxide pretreatments on disinfection byproduct formation during subsequent chlorination and chloramination.

    PubMed

    Yang, Xin; Peng, Jinfeng; Chen, Baiyang; Guo, Wanhong; Liang, Yongmei; Liu, Wei; Liu, Lu

    2012-11-15

    Ozone (O3) and ozone/hydrogen peroxide (O3/H2O2) can be used in water treatment facilities to remove many organic micropollutants with taste, odor, and color implications. The effects of O3 and O3/H2O2 on the formation of disinfection byproducts (DBPs) in subsequent chlorination and chloramination processes, however, are not well determined. In this study, we compared the yields of a series of regulated and emerging DBPs during sequenced O3-Cl2, O3/H2O2-Cl2, O3-NH2Cl, and O3/H2O2-NH2Cl oxidation of 11 samples, each with different hydrophobicity, bromide concentration, soluble microbial products, and humic substances. For most water, pretreatment with O3 and O3/H2O2 increased the formation of chloral hydrate (CH), trichloronitromethane (TCNM) and haloketones (HKs) but lowered the yields of haloacetonitriles (HANs) during chlorination processes. Compared with O3 alone, O3/H2O2 in combination generated more CH and HKs during chlorination, and their extents of formation appeared to depend on the O3 doses. In terms of chloramination, both O3 and O3/H2O2 reduced THM, HAA, and HAN formation significantly without increasing CH, TCNM, or HKs. These results suggest that O3 or O3/H2O2 pretreatments may provide some benefits for the chloramination process in controlling regulated and emerging DBPs in waters without high bromide content.

  8. A composite study on the structure and formation of ozone miniholes and minihighs over central Europe

    NASA Astrophysics Data System (ADS)

    Koch, G.; Wernli, H.; Schwierz, C.; Staehelin, J.; Peter, T.

    2005-06-01

    Two different mechanisms have been proposed to be important for the formation of extreme total ozone events in mid-latitudes, so-called miniholes: (A) far-range meridional transport of air masses from regions with different climatological ozone mixing ratios, and (B) (local) adiabatic vertical displacement of isentropes. Here, the relative importance of these two mechanisms is studied using two different ozone profile reconstruction techniques for all miniholes and minihighs (events with anomalously high ozone) during the time period 1980-1989 over Switzerland. Composites for the two types of events of their vertical potential vorticity (PV) reveal a vertical dipole structure of PV anomalies in the lower and middle stratosphere. They, in agreement with the profile reconstructions, highlight the importance of fast far-range transport (mechanism A). Dynamically consistent with this PV structure is a relatively weak vertical displacement of isentropes between the PV dipole, that provides an additional but less important contribution (mechanism B).

  9. Impact of a magnetic ion exchange resin on ozone demand and bromate formation during drinking water treatment.

    PubMed

    Johnson, Clayton J; Singer, Philip C

    2004-10-01

    The objective of this research was to examine the impact of a magnetic ion exchange resin (MIEX) on ozone demand and bromate formation in two different ozonated waters at bench scale. The first raw water had a high bromide ion concentration, a high ozone demand, and was highly colored. Based on experimental findings from the first water, the second water was selected as a model water in which more controlled experiments were performed. The waters were treated with the MIEX resin using jar test procedures to find the optimal MIEX dosage based upon the removal of ultraviolet (UV)-absorbing substances, dissolved organic carbon (DOC), and bromide. The optimal resin dosage was chosen for bulk MIEX treatment and subsequent ozonation in a semi-batch reactor. The ozone demand and formation of bromate were analyzed as a function of ozone dosage and dissolved ozone concentration for the MIEX pre-treated water, and compared to the results obtained by ozonating the water without MIEX pre-treatment. The results indicate that pre-treatment of the water with the MIEX resin significantly reduces total organic carbon, DOC, UV absorbance, color, and to some extent, bromide. MIEX pre-treatment of the water prior to ozonation substantially lowered the ozone demand and formation of bromate during subsequent ozonation.

  10. Kinetics and mechanisms of nitrate and ammonium formation during ozonation of dissolved organic nitrogen.

    PubMed

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

    2017-01-01

    Dissolved organic nitrogen (DON) is an emerging concern in oxidative water treatment because it exerts oxidant demand and may form nitrogenous oxidation/disinfection by-products. In this study, we investigated the reactions of ozone with DON with a special emphasis on the formation of nitrate (NO3(-)) and ammonium (NH4(+)). In batch ozonation experiments, the formation of NO3(-) and NH4(+) was investigated for natural organic matter standards, surface water, and wastewater effluent samples. A good correlation was found between NO3(-) formation and the O3 exposure (R(2) > 0.82) during ozonation of both model DON solutions and real water samples. To determine the main precursor of NO3(-), solutions composed of tannic acid and model compounds with amine functional groups were ozonated. The NO3(-) yield during ozonation was significantly higher for glycine than for trimethylamine and dimethylamine. Experiments with glycine also showed that NO3(-) was formed via an intermediate with a second-order rate constant of 7.7 ± 0.1 M(-1)s(-1) while NH4(+) was formed by an electron-transfer mechanism with O3 as confirmed from a hydroxyl radical (OH) yield of 24.7 ± 1.9%. The NH4(+) concentrations, however, were lower than the OH yield (0.03 mol NH4(+)/mol OH) suggesting other OH-producing reactions that compete with NH4(+) formation. This study concludes that NO3(-) formation during ozonation of DON is induced by an oxygen-transfer to nitrogen forming hydroxylamine and oxime, while NH4(+) formation is induced by electron-transfer reactions involving C-centered radicals and imine intermediates. Copyright © 2016 Elsevier Ltd. All rights reserved.

  11. Stratosphere-Troposphere Interactions in Positive Local Ozone Anomalies Formation Case Studies

    NASA Astrophysics Data System (ADS)

    Shlender, Tsimafei; Bahdziun, Anatol; Krasouski, Alexander; Barodka, Siarhei

    2013-04-01

    One of the characteristic phenomena in Northern Hemisphere ozone layer dynamics in recent decades is the increasing number of observed negative (positive) local ozone anomalies, defined as local areas with very low (very high) total ozone column. Ozone anomalies formation and development is a complicated process involving both the stratosphere and the troposphere. The importance of negative local anomalies study is due to significant biological impact of the associated low total ozone values; accordingly, negative anomalies were a subject of intense research. On the other hand, positive anomalies have received less attention. However, from the climate and weather research point of view, study of both categories of anomalies is of great interest. For example, it has been shown that total ozone content field over polar regions can serve as a predictor of future atmospheric circulation in mid-latitudes [1]. It has been argued [2] that sizeable ozone anomalies correspond to a certain stratification of the atmosphere, and that negative and positive anomalies are characterized by opposite "dipole structures": combinations of independent circulation processes in the troposphere and the stratosphere. The present study focuses on the influence of tropospheric processes on stratospheric ozone dynamics and the associated ozone anomalies development. On the basis of WRF-ARW modelling system, adapted for our study, we analyze the relationship between pressure formations in the troposphere and the stratosphere and their impact on stratospheric ozone distribution, using GFS meteorological data for WRF input data and TOMS data for ozone maps. We conclude that: - Higher total ozone values are observed in the rear part of the cyclone and the front part of the anticyclone, confirming the "dipole structure" hypothesis. - Projections of the anomalies on the 50 hPa and 15 hPa isobaric surfaces are situated in the transient zone between warm air and cold air regions. - The "dipole

  12. Ozone

    SciTech Connect

    Not Available

    1988-06-01

    The author discusses the debate over whether concern about a hole in the ozone layer in Antarctic is real or science fiction. There is a growing consensus that efforts must be taken to protect the ozone layer. The issue now is not whether chlorofluorocarbons (CFCs) should be controlled and regulated but how much and how soon. The United States has urged that the production of dangerous CFCs, and any other chemicals that affect the ozone layer, be restricted immediately to current levels and that their use be reduced 95 percent over the next decade. The American position was too strong for many European nations and the Japanese. Negotiations at an international conference on the matter broke down. The breakdown is due in part to a more acute concern for environmental matters in the United States than exists in many countries. Meanwhile CFCs are linked to another environmental problem that equally threatens the world - the Greenhouse Effect. The earth is in a natural warming period, but man could be causing it to become even warmer. The Greenhouse Effect could have a catastrophic impact on mankind, although nothing has been proven yet.

  13. Documentation of ozone as the primary phytotoxic agent in photochemical oxidant smog. Final report, 23 February 1987-23 May 1988

    SciTech Connect

    Olszyk, D.M.

    1988-05-01

    The study evaluated whether equivalent ozone concentrations in ambient oxidant smog and added ozone in filtered air produce the same physiological, growth, yield, and injury effects in plants. Three treatments of alfalfa cultivars were used in open-top field chambers: charcoal-filtered air (CF); non-filtered air (NF); and filtered air plus ozone added to equal the ozone concentration in the ambient air according to the same temporal pattern. The O/sup 3/ treatment resulted in significantly greater leaf injury, chlorophyll concentrations, and a distinct trend toward a large reduction in dry weight compared with the NF treatment. The results indicate that use of dry air to generate ozone may overestimate losses due to ambient ozone. Conversely, use of oxygen to generate ozone may underestimate losses due to ambient oxidants as other detrimental oxidants such as nitric acid vapor are not present as they would be in ambient air.

  14. Triclosan removal from surface water by ozonation - Kinetics and by-products formation.

    PubMed

    Orhon, Kemal B; Orhon, Aybala Koc; Dilek, Filiz B; Yetis, Ulku

    2017-09-11

    Removal of triclosan from surface water by ozonation was investigated. The results showed that complete elimination of triclosan from a surface water bearing 1-5 mg/L triclosan via continuous ozonation at 5 mg/L, require an ozonation time of 20-30 min depending on pH. Triclosan oxidation followed pseudo-first order kinetics with an apparent reaction rate constant varying from 0.214 min(-1) to 0.964 min(-1) depending on pH, initial triclosan concentration and water composition. Although the effect of pH was complex due to possible existence of different moieties, higher TCS removal efficiencies were obvious at weak-base conditions. Experiments performed to identify degradation by-products showed the formation of four by-products, namely, 2,4-dichlorophenol, 4-chlorocatechol and two unidentified compounds. Additionally, 2,4-dichloroanisole was detected when a methyl moieties exist in water. By-products were found to be eliminated upon further ozonation. The required exposure time varied from 20 to 30 min depending on pH of water. The ozone demand exerted for the complete oxidation of triclosan and its by-products was calculated as 13.04 mg ozone per mg of triclosan. A triclosan degradation pathway, which was found to be highly pH dependent, was proposed. Copyright © 2017. Published by Elsevier Ltd.

  15. 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

  16. 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 ...

  17. 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 ...

  18. Aerosol Formation In The Presence of Iodine and Ozone, Atmospheric Implications Based On Laboratory and Modelling Results

    NASA Astrophysics Data System (ADS)

    McFiggans, G.; Plane, J.; Joseph, M.; Casey, J.; Coe, H.; Williams, P.

    The magnitude of the radiative forcing by aerosol depends on the number reaching optically active size (the direct effect) and the number that will activate into cloud droplets (the indirect effect). Aerosol number will depend on coagulation and depo- sitional loss processes in addition to the generation of nucleation mode particles to repopulate the ambient aerosol distribution. Great uncertainties surround the formation mechanisms of such atmospheric ultrafine particles, the dominant mechanisms changing with location and prevailing conditions (see e.g. Coe et al., 2000 &refs therein). It has been suggested that coastal ultrafine particle bursts measured under a wide variety of conditions (e.g. O Dowd et al., 1999) are related to iodocarbon compounds (Hoffmann et al., 2001) released by macroalgae in intertidal beds exposed during low tide (Carpenter et al., 1999). Since the particle bursts are only observed during daytime, it has been postulated that they are formed as a result of iodine photochemistry, probably involving higher iodine oxides. It has been known for some time that thick smokes are formed in laboratory kinetics exper- iments where iodine has been studied in the presence of ozone (Cox &Coker, 1983). The purpose of this study is to investigate whether the mechanism responsible for the laboratory phenomenon is a candidate for the formation of particles in the atmosphere. This study presents data from flow reactor experiments in which diiodomethane was photolysed in the presence of ozone under a variety of conditions. The formation of ultrafine particles and the subsequent evolution of the distribution was measured by a SMPS system. Such distributions were collected as a function of reactant concentra- tion, light intensity, relative humidity and a variety of other conditions and the results were found to be consistent and highly repeatable. A photochemical model has been developed to investigate the laboratory system. An existing gas phase model (Mc

  19. Investigations into the chemistry, toxicology, mode of action and photochemical formation of some delayed toxic sulfur-containing organophosphorus triesters

    SciTech Connect

    Chukwudebe, A.C.

    1987-01-01

    Examination of a limited series of O,S,S-trialkyl phosphorodithionates revealed that very minor changes in the alkyl substituents resulted in wide changes in toxicity. However, alkaline hydrolysis rate constants did not vary significantly with changes in alkyl substituents. O,S,S-trimethyl phosphorodithioate was several fold more reactive, and more toxic to the rat, than its corresponding phosphorothioate analogue, O,O,S-trimethyl phosphorothioate. The toxicological feasibility of sulfoxidation was examined further by the peracide oxidation of O-ethyl-S-/sup 13/C-methyl ethyl-phosphonothiate (I) using /sup 13/C-NMR as the monitoring tool. Several lines of evidence pointed to the formation of the sulfoxide of I. The photochemical formation of the delayed toxicants from methyl parathion, fenthion, methidathion, azinphosmethyl, malathion, temephos, chlorpyrifos-methyl, chlorpyrifos-ethyl and diazinon in measurable amounts, suggested that they might be of some toxicological significance in the environment. This photoalteration had a strong link with the numerical closeness between the spectral emissivity of the light sources and the UV lambda max of the irradiated phosphorothioate insecticide as well as the magnitude of the latter's a/sub M/ values. The levels of the delayed toxicants produced following irradiations are not expect to pose acute toxic hazards to field workers dealing routinely with agricultural chemicals.

  20. Winter ozone formation and VOC incremental reactivities in the Upper Green River Basin of Wyoming

    NASA Astrophysics Data System (ADS)

    Carter, William P. L.; Seinfeld, John H.

    2012-04-01

    The Upper Green River Basin (UGRB) in Wyoming experiences ozone episodes in the winter when the air is relatively stagnant and the ground is covered by snow. A modeling study was carried out to assess relative contributions of oxides of nitrogen (NOx) and individual volatile organic compounds (VOCs), and nitrous acid (HONO) in winter ozone formation episodes in this region. The conditions of two ozone episodes, one in February 2008 and one in March 2011, were represented using a simplified box model with all pollutants present initially, but with the detailed SAPRC-07 chemical mechanism adapted for the temperature and radiation conditions arising from the high surface albedo of the snow that was present. Sensitivity calculations were conducted to assess effects of varying HONO inputs, ambient VOC speciation, and changing treatments of temperature and lighting conditions. The locations modeled were found to be quite different in VOC speciation and sensitivities to VOC and NOx emissions, with one site modeled for the 2008 episode being highly NOx-sensitive and insensitive to VOCs and HONO, and the other 2008 site and both 2011 sites being very sensitive to changes in VOC and HONO inputs. Incremental reactivity scales calculated for VOC-sensitive conditions in the UGRB predict far lower relative contributions of alkanes to ozone formation than in the traditional urban-based MIR scale and that the major contributors to ozone formation were the alkenes and the aromatics, despite their relatively small mass contributions. The reactivity scales are affected by the variable ambient VOC speciation and uncertainties in ambient HONO levels. These box model calculations are useful for indicating general sensitivities and reactivity characteristics of these winter UGRB episodes, but fully three-dimensional models will be required to assess ozone abatement strategies in the UGRB.

  1. [Studies of ozone formation potentials for benzene and ethylbenzene using a smog chamber and model simulation].

    PubMed

    Jia, Long; Xu, Yong-Fu

    2014-02-01

    Ozone formation potentials from irradiations of benzene-NO(x) and ethylbenzene-NO(x) systems under the conditions of different VOC/NO(x) ratios and RH were investigated using a characterized chamber and model simulation. The repeatability of the smog chamber experiment shows that for two sets of ethylbenzene-NO(x) irradiations with similar initial concentrations and reaction conditions, such as temperature, relative humidity and relative light intensity, the largest difference in O3 between two experiments is only 4% during the whole experimental run. On the basis of smog chamber experiments, ozone formation of photo-oxidation of benzene and ethylbenzene was simulated in terms of the master chemical mechanism (MCM). The peak ozone values for benzene and ethylbenzene simulated by MCM are higher than the chamber data, and the difference between the MCM-simulated results and chamber data increases with increasing RH. Under the conditions of sunlight irradiations, with benzene and ethylbenzene concentrations being in the range of (10-50) x 10(-9) and NO(x) concentrations in the range of (10-100) x 10(-9), the 6 h ozone contributions of benzene and ethylbenzene were obtained to be (3.1-33) x 10(-9) and (2.6-122) x 10(-9), whereas the peak O3 contributions of benzene and ethylbenzene were (3.5-54) x 10(-9) and (3.8-164) x 10(-9), respectively. The MCM-simulated maximum incremental reactivity (MIR) values for benzene and ethylbenzene were 0.25/C and 0.97/C (per carbon), respectively. The maximum ozone reactivity (MOR) values for these two species were obtained to be 0.73/C and 1.03/C, respectively. The MOR value of benzene from MCM is much higher than that obtained by carter from SAPRC, indicating that SAPRC may underestimate the ozone formation potential of benzene.

  2. A Reevaluation of the Ozone Budget with HALOE UARS Data: No Evidence for the Ozone Deficit.

    PubMed

    Crutzen, P J; Grooß, J U; Brühl, C; Müller, R; Russell, J M

    1995-05-05

    Recently, additional ozone production mechanisms have been proposed to resolve the ozone deficit problem, which arises from greater ozone destruction than production in several photochemical models of the upper stratosphere and lower mesosphere. A detailed ozone model budget analysis was performed with simultaneous observations of O(3), HCl, H(2)O, CH(4), NO, and NO(2) from the Halogen Occultation Experiment (HALOE) on the Upper Atmosphere Research Satellite (UARS) under conditions with the strongest photochemical control of ozone. The results indicate that an ozone deficit may not exist. On the contrary, the use of currently recommended photochemical parameters leads to insufficient ozone destruction in the model.

  3. Urban Climate, Ozone Formation, and Public Health: Should Heat be Regulated as a Traditional Air Pollutant?

    NASA Astrophysics Data System (ADS)

    Stone, B.

    2003-12-01

    The return of record breaking heat waves to North American and European cities in 2003 highlights the growing need for urban planners to develop heat mitigation strategies for large metropolitan regions. Long associated with public health through its effects on human heat stress and heat related mortality, rising urban temperatures also hold important implications for regional air quality. This presentation will outline the results of a study focused on the relationship between regional temperatures and annual tropospheric ozone exceedances in the fifty largest (by population) metropolitan regions in the United States. With the aid of data from the EPA's National Emissions Inventory and NASA's Earth Observing System Data and Information System, this study examines trends in metropolitan emissions of nitrogen oxides, volatile organic compounds, mean regional temperatures, and annual ozone exceedances in U.S. metropolitan regions for the years 1990 through 1999. The intent of this work is to better establish connections between recent trends urban climate and ozone formation and to explore policy approaches to mitigating urban temperatures through physical planning. The results of this research indicate that annual violations of the national ozone standard during the decade of the 1990s were more closely associated with regional temperatures than with the emissions of regulated ozone precursors from mobile and stationary sources. Based on the results of this analysis, I argue that the air quality management strategies outlined in the Clean Air Act may be proving insufficient to control ozone formation due to ongoing and unanticipated changes in global and regional climate. I further argue that the emergence of urban heat as a significant threat to human health demands a strategic response from the fields of urban planning and public health. The presentation will conclude with a discussion of the linkages between urban form and ambient heat and will outline a set of

  4. Reducing bromate formation with H(+)-form high silica zeolites during ozonation of bromide-containing water: Effectiveness and mechanisms.

    PubMed

    Zhang, Tao; Hou, Pin; Qiang, Zhimin; Lu, Xiaowei; Wang, Qunhui

    2011-01-01

    This paper investigated the effect of H(+)-form high silica ZSM-5 (HZSM-5) zeolites on bromate formation. HZSM-5 zeolites with different Si/Al molar ratios (i.e., 25-300) were tested taking ozonation alone as control. The zeolites were more effective in reducing bromate formation for the filtered surface water than CeO₂, a former reported oxide that can reduce bromate formation at slightly acidic pH. The reduction efficiencies were not closely related to their Si/Al ratios. The HZSM-5 (Si/Al=300) selected for detailed studies effectively reduced bromate formation by 58% for the filtered water, and also enhanced the removal of dissolved organic carbon (DOC) during ozonation. The efficiency of the HZSM-5 in reducing bromate formation increased with ozone dose (0.38-1.16 mg O₃ mg⁻¹ DOC) and pH (6.6-9.3). The HZSM-5 adsorbed OBr⁻ (one of the critical intermediates in bromate formation) quickly with an adsorption capacity of 54 mg g⁻¹, but had no adsorption for ozone, Br⁻, HOBr and BrO₃⁻. It also significantly inhibited the formation of trace H₂O₂ which was generated from ozone decomposition and had been considered promoting bromate formation at low concentrations during ozonation. The reduction of bromate formation in O₃/HZSM-5 is possibly ascribed to the selective OBr⁻ adsorption in combination with the inhibited H₂O₂ formation. Copyright © 2010 Elsevier Ltd. All rights reserved.

  5. Photochemical Formation of Aerosol in Planetary Atmospheres: Photon and Water Mediated Chemistry of SO_2

    NASA Astrophysics Data System (ADS)

    Kroll, Jay A.; Donaldson, D. J.; Vaida, Veronica

    2016-06-01

    Sulfur compounds have been observed in a number of planetary atmospheres throughout our solar system. Our current understanding of sulfur chemistry explains much of what we observe in Earth's atmosphere. However, several discrepancies between modeling and observations of the Venusian atmosphere show there are still problems in our fundamental understanding of sulfur chemistry. This is of particular concern due to the important role sulfur compounds play in the formation of aerosols, which have a direct impact on planetary climates, including Earth's. We investigate the role of water complexes in the hydration of sulfur oxides and dehydration of sulfur acids and will present spectroscopic studies to document such effects. I will present recent work investigating mixtures of SO_2 and water that generate large quantities of aerosol when irradiated with solar UV light, even in the absence of traditional OH chemistry. I will discuss a proposed mechanism for the formation of sulfurous acid (H_2SO_3) and present recent experimental work that supports this proposed mechanism. Additionally, the implications that photon-induced hydration of SO_2 has for aerosol formation in the atmosphere of earth as well as other planetary atmospheres will be discussed.

  6. Contribution of regional-scale fire events to ozone and PM2.5 air quality estimated by photochemical modeling approaches

    NASA Astrophysics Data System (ADS)

    Baker, K. R.; Woody, M. C.; Tonnesen, G. S.; Hutzell, W.; Pye, H. O. T.; Beaver, M. R.; Pouliot, G.; Pierce, T.

    2016-09-01

    Two specific fires from 2011 are tracked for local to regional scale contribution to ozone (O3) and fine particulate matter (PM2.5) using a freely available regulatory modeling system that includes the BlueSky wildland fire emissions tool, Spare Matrix Operator Kernel Emissions (SMOKE) model, Weather and Research Forecasting (WRF) meteorological model, and Community Multiscale Air Quality (CMAQ) photochemical grid model. The modeling system was applied to track the contribution from a wildfire (Wallow) and prescribed fire (Flint Hills) using both source sensitivity and source apportionment approaches. The model estimated fire contribution to primary and secondary pollutants are comparable using source sensitivity (brute-force zero out) and source apportionment (Integrated Source Apportionment Method) approaches. Model estimated O3 enhancement relative to CO is similar to values reported in literature indicating the modeling system captures the range of O3 inhibition possible near fires and O3 production both near the fire and downwind. O3 and peroxyacetyl nitrate (PAN) are formed in the fire plume and transported downwind along with highly reactive VOC species such as formaldehyde and acetaldehyde that are both emitted by the fire and rapidly produced in the fire plume by VOC oxidation reactions. PAN and aldehydes contribute to continued downwind O3 production. The transport and thermal decomposition of PAN to nitrogen oxides (NOX) enables O3 production in areas limited by NOX availability and the photolysis of aldehydes to produce free radicals (HOX) causes increased O3 production in NOX rich areas. The modeling system tends to overestimate hourly surface O3 at routine rural monitors in close proximity to the fires when the model predicts elevated fire impacts on O3 and Hazard Mapping System (HMS) data indicates possible fire impact. A sensitivity simulation in which solar radiation and photolysis rates were more aggressively attenuated by aerosol in the plume

  7. 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.

  8. Impact of biogenic emissions on ozone formation in the Mediterranean area - a BEMA modelling study

    NASA Astrophysics Data System (ADS)

    Thunis, P.; Cuvelier, C.

    The aim of this modelling study is to understand and quantify the influence of biogenic volatile organic compound (BVOC) emissions on the formation of tropospheric ozone in the Burriana area (north of Valencia) on the east coast of Spain. The mesoscale modelling system used consists of the meteorology/transport module TVM and the chemical reaction mechanism RACM. The results of the model simulations are validated and compared with the data collected during the biogenic emissions in the mediterranean area (BEMA) field campaign that took place in June 1997. Anthropogenic and biogenic emission inventories have been constructed with an hourly resolution. Averaged (over the land area and over 24 h) emission fluxes for AVOC, anthropogenic NO x, BVOC and biogenic NO x are given by 16.0, 9.9, 6.2, and 0.7 kg km -2 day -1, respectively. The impact of biogenic emissions is investigated on peak ozone values by performing simulations with and without biogenic emissions, while keeping anthropogenic emissions constant. The impact on ozone formation is also studied in combination with some anthropogenic emissions reduction strategies, i.e. when anthropogenic VOC emissions and/or NO x emissions are reduced. A factor separation technique is applied to isolate the impact due to biogenic emissions from the overall impact due to biogenic and anthropogenic emissions together. The results indicate that the maximum impact of biogenic emissions on ozone formation represents at the most 10 ppb, while maximum ozone values are of the order of 100 ppb. At different locations the maximum impact is reached at different times of the day depending on the arrival time of the sea breeze. It is also shown that this impact does not coincide in time with the maximum simulated ozone concentrations that are reached over the day. By performing different emission reduction scenarios, BVOC impacts are found to be sensitive mainly to NO x, and not to AVOC. Finally, it is shown that amongst the various BVOCs

  9. Comparison of N-nitrosodimethylamine formation mechanisms from dimethylamine during chloramination and ozonation: A computational study.

    PubMed

    Liu, Yong Dong; Zhong, Rugang

    2017-01-05

    N-nitrosodimethylamine (NDMA) as a disinfection by-product has recently become the focus of considerable research interest due to its unusually high carcinogenicity. In this study, the formation mechanisms of NDMA from dimethylamine (DMA) during chloramination and ozonation were investigated by using the quantum chemical G4 method. The reactivity of haloamines and hydroxylamine reacting with DMA was found in the order: NHCl2∼NHBrCl (Br-leaving)>NHBr2>NH2Cl∼NH2Br>NH2OH. This offers a theoretical support for the experimentally proposed mechanism that dimethylamine reacts with NHCl2 rather than NH2Cl to form chlorinated unsymmetrical dimethylhydrazine intermediate and the existence of bromochloramine in the presence of bromide during chloramination, and explains the observation that NDMA yield during ozonation is much lower than that during chloramination. Importantly, an N,N-dimethylaminonitrene was found to be a significant intermediate to form NDMA in oxidation reactions by molecular oxygen and ozone. Additionally, results suggest that the amines containing the second nitrogen source directly connecting or close to the N-(CH3)2 moiety are potential significant NDMA precursors upon ozonation. The findings of this study are helpful for expanding the knowledge of NDMA formation mechanism, and predicting potential NDMA precursors during disinfection. Copyright © 2016 Elsevier B.V. All rights reserved.

  10. Photochemical reactions of divalent mercury with thioglycolic acid: formation of mercuric sulfide particles.

    PubMed

    Si, Lin; Ariya, Parisa A

    2015-01-01

    Mercury (Hg) is a key toxic global pollutant. Studies in aquatic environment have suggested that thiols could be important for mercury speciation. Thioglycolic acid has been detected in various natural water systems and used as a model compound to study the complicated interaction between mercury and polyfunctional dissolved organic matter (DOM). We herein presented the first evidence for mercury particle formation during kinetic and product studies on the photochemistry of divalent mercury (Hg(2+)) with thioglycolic acid at near environmental conditions. Mercuric sulfide (HgS) particles formed upon photolysis were identified by high-resolution transmission electron microscopy coupled with energy dispersive spectrometry and select area electron diffraction. Kinetic data were obtained using UV-visible spectrophotometry and cold vapour atomic fluorescent spectrometry. The apparent first-order reaction rate constant under our experimental conditions was calculated to be (2.3±0.4)×10(-5) s(-1) at T=296±2 K and pH 4.0. It was found that (89±3)% of the reactants undergo photoreduction to generate elemental mercury (Hg(0)). The effects of ionic strengths, pH and potassium ion were also investigated. The formation of HgS particles pointed to the possible involvement of heterogeneous processes. Our kinetic results indicated the importance of weak binding sites on DOM to Hg in photoreduction of Hg(2+) to Hg(0). The potential implications of our data on environmental mercury transformation were discussed.

  11. Protein cross-linking and oligomerization through dityrosine formation upon exposure to ozone

    NASA Astrophysics Data System (ADS)

    Liu, Fobang; Kampf, Christopher; Reinmuth-Selzle, Kathrin; Berkemeier, Thomas; Shiraiwa, Manabu; Pöschl, Ulrich

    2015-04-01

    Air pollution is a potential factor for the increasing prevalence of allergic diseases. Airborne allergenic proteins can be directly exposed to air pollution promoting post-translational modifications, which can enhance the allergenic potential of proteins. The formation of dimers or oligomers of allergenic proteins has been reported to result in an enhanced allergenicity. However, the oligomerization process for proteins at atmospherically relevant concentration of O3 is still largely unknown. In this study, the kinetics and reaction mechanism of protein oligomerization upon ozone exposure were studied at atmospherically relevant ozone concentrations and relative humidity (RH) in coated-wall flow tube experiments. Bovine Serum Albumin (BSA) was used as a model protein. Protein ozone exposure was studied for different protein phase-states, i.e. amorphous solid (45% RH experiments), semi-solid (96% RH experiments) and liquid (bulk solution experiments) to account for the differences of phase in atmospheric particulates, e.g., aerosol particles and cloud droplets. Product analysis was performed using a size exclusion chromatography-high performance liquid chromatography-diode array detector (SEC-HPLC-DAD). We demonstrate that protein cross-linking upon ozone exposure can be attributed to the formation of covalent intermolecular dityrosine species by gel electrophoretic and fluorescence spectroscopic methods. The exposure experiments indicate that in addition to ozone concentration, the oligomerization process was depending on the phase-state of protein. In liquid-phase experiments, dimer formation was significantly enhanced, thus indicating a potential relevance of in-cloud processes for protein oligomerization. The reactive turnover is higher at 96% RH compared to 45% RH, indicating a higher bulk diffusion coefficient at high RH, which is explicitly resolved by kinetic modeling. Further, the reactive turnover showed a strong correlation to particle surface

  12. 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.

  13. Organic Aerosol Formation in the Humid, Photochemically-Active Southeastern US: SOAS Experiments and Simulations

    NASA Astrophysics Data System (ADS)

    Sareen, N.; Lim, Y. B.; Carlton, A. G.; Turpin, B. J.

    2013-12-01

    Aqueous multiphase chemistry in the atmosphere can lead to rapid transformation of organic compounds, forming highly oxidized low volatility organic aerosol and, in some cases, light absorbing (brown) carbon. Because liquid water is globally abundant, this chemistry could substantially impact climate, air quality, health, and the environment. Gas-phase precursors released from biogenic and anthropogenic sources are oxidized and fragmented forming water-soluble gases that can undergo reactions in the aqueous phase (in clouds, fogs, and wet aerosols) leading to the formation of secondary organic aerosol (SOAAQ). Recent studies have highlighted the role of certain precursors like glyoxal, methylglyoxal, glycolaldehyde, acetic acid, acetone, and epoxides in the formation of SOAAQ. The goal of this work is to identify other precursors that are atmospherically important. In this study, ambient mixtures of water-soluble gases were scrubbed from the atmosphere at Brent, Alabama during the Southern Oxidant and Aerosol Study (SOAS). Four mist chambers in parallel collected ambient gases in a DI water medium at 20-25 LPM with a 4 hr collection time. Total organic carbon (TOC) values in daily composited samples were 64-180 μM. Aqueous OH radical oxidation experiments were conducted with these mixtures in a newly designed cuvette chamber to understand the formation of SOA through gas followed by aqueous chemistry. OH radicals (3.5E-2 μM [OH] s-1) were formed in-situ in the chamber, continuously by H2O2 photolysis. Precursors and products of these aqueous OH experiments were characterized using ion chromatography (IC), electrospray ionization mass spectrometry (ESI-MS), and IC-ESI-MS. ESI-MS results from a June 12th, 2013 sample showed precursors to be primarily odd, positive mode ions, indicative of the presence of non-nitrogen containing alcohols, aldehydes, organic peroxides, or epoxides. Products were seen in the negative mode and included organic acid ions like pyruvate

  14. Evidence for photochemical formation of H[sub 2]O[sub 2] and oxidation of SO[sub 2] in authentic fog water

    SciTech Connect

    Yuegang Zuo, Hoigne, J. )

    1993-04-02

    When samples of rain and fog water were exposed to ultraviolet and visible light, reactive transients such as hydrogen peroxide were formed and dissolved organic matter and sulfur dioxide were depleated. These results, in conjunction with those from previous studies, imply that dissolved organic compounds and transition metals such as iron ions are involved in the photochemical formation of hydrogen peroxide and other photooxidants in atmospheric waters.

  15. Photochemical Formation of Hydroxyl Radical, Hydrogen Peroxide and Fe(II) in the Sea Surface Microlayer (SML) Collected in Okinawa, Japan

    NASA Astrophysics Data System (ADS)

    Higaonna, Y.; Tachibana, C.; Kasaba, T.; Ishikawa, R.; Arakaki, T.

    2014-12-01

    The sea surface microlayer (SML) covers upper 1 to 1000 μm deep boundary layer of the ocean, where important biogeochemical processes take place. Photo-chemical reactions are activated by sunlight, so it is assumed that more photo-chemical reactions occur in SML than underlying bulk seawater (bulk). We initiated a study to understand chemical changes occurring in the SML by studying photochemical formation of oxidants such as hydrogen peroxide and hydroxyl radical (OH), both of which react with various organic substances and determine their lifetimes. Since OH can be formed by reaction between hydrogen peroxide and Fe(II), Fe(II) photoformation was also studied. We collected SML samples using a widely-used glass plate method and bulk samples by using a polyethylene bottles near the coast of Okinawa Island, Japan. Results showed that dissolved organic carbon (DOC) concentrations in the SML were about twice those of bulk seawater samples. Hydrogen peroxide formation in the SML samples was ca. 2.8 times faster than the bulk seawater samples. On the other hand, Fe(II) and OH photoformation kinetics was similar for both SML and bulk samples. Although it was predicted that more OH could be formed from reaction between hydrogen peroxide and Fe(II), OH formation kinetics was similar in both SML and bulk, suggesting that either Fe(II) did not react with hydrogen peroxide or reaction is very slow, possibly by forming a complex with organic compounds in the SML and bulk.

  16. Effect of trichlorofluoromethane and molecular chlorine on ozone formation by simulated solar radiation

    NASA Technical Reports Server (NTRS)

    Bittker, D. A.; Wong, E. L.

    1977-01-01

    Mixtures of air with either Cl2 or CFCl3 were photolyzed in a reaction chamber by simulated solar radiation. Ozone formation was temporarily inhibited by Cl2 and permanently inhibited by CFCl3. A chemical mechanism including gas phase and wall reactions is proposed to explain these results. The CFCl3 is assumed to be adsorbed on the chamber walls and to poison the sites for Cl destruction.

  17. Theoretical analysis of isotope effects on ozone formation in oxygen photochemistry

    NASA Technical Reports Server (NTRS)

    Kaye, J. A.

    1986-01-01

    In situ measurements of stratospheric ozone and laboratory studies of ozone production in electric discharge through oxygen have shown previously that ozone containing heavy isotopes of oxygen (O-17, O-18) may be formed preferentially. In order to assess the relevance of thee latter experiment to the stratospheric measurements, detailed understanding of the effect of isotopic substitution on the O3 formation reaction O + O2 + M yields O3 + M and on the O atom exchange reaction O + O2 + O yields O2 + O is necessary. In this work, an estimate of the effect of isotopic substitution on the recombination rate is made by us of approximate dynamical theories and statistical mechanics. The results indicate the possibility of isotope effects on the O + O2 recombination rate of the order of several percent at stratospheric temperatures. In general, recombination reactions involving heavy (mass 49, 50) O3 formation are found to be slower than the reaction leading to normal (mass 48) O3 formation. The calculated isotope effects are sufficiently small that the uncertainties in the model input and the approximations in the dynamical theories will probably make the quantitative nature of these results subject to considerable uncertainty. This isotope effect should not be observable in the atmosphere given the precision of the current measurements but may be crucial in the understanding of the laboratory experiments, where observed enhancements are only of the order of several percent. Possible reasons for this discrepancy between the observed enhancement and predicted depletion are presented.

  18. Effects of 10% biofuel substitution on ground level ozone formation in Bangkok, Thailand

    NASA Astrophysics Data System (ADS)

    Milt, Austin; Milano, Aaron; Garivait, Savitri; Kamens, Richard

    2009-12-01

    The Thai Government's search for alternatives to imported petroleum led to the consideration of mandating 10% biofuel blends (biodiesel and gasohol) by 2012. Concerns over the effects of biofuel combustion on ground level ozone formation in relation to their conventional counterparts need addressing. Ozone formation in Bangkok is explored using a trajectory box model. The model is compared against O 3, NO, and NO 2 time concentration data from air monitoring stations operated by the Thai Pollution Control Department. Four high ozone days in 2006 were selected for modeling. Both the traditional trajectory approach and a citywide average approach were used. The model performs well with both approaches but slightly better with the citywide average. Highly uncertain and missing data are derived within realistic bounds using a genetic algorithm optimization. It was found that 10% biofuel substitution will lead to as much as a 16 ppb peak O 3 increase on these four days compared to a 48 ppb increase due to the predicted vehicle fleet size increase between 2006 and 2012. The approach also suggests that when detailed meteorological data is not available to run three dimensional airshed models, and if the air is stagnant or predominately remains over an urban area during the day, that a simple low cost trajectory analysis of O 3 formation may be applicable.

  19. Formation of carbonyl groups on cellulose during ozone treatment of pulp: consequences for pulp bleaching.

    PubMed

    Pouyet, Frédéric; Chirat, Christine; Potthast, Antje; Lachenal, Dominique

    2014-08-30

    The formation of carbonyl groups during the ozone treatment (Z) of eucalyptus (Eucalyptus grandis and Eucalyptus urophylla hybrid) kraft pulps and their behaviors during subsequent alkaline stages were investigated by the CCOA method with carbazole-9-carboxylic acid [2-(2-aminooxethoxy)-ethoxy] amide (CCOA) as the carbonyl-selective fluorescence label. Several pulp samples with or without lignin and hexenuronic acids (hexA) were used to elucidate the effects of these components when present in unbleached kraft pulp. Both hexA and lignin increased the formation of carbonyl groups on cellulose and hemicellulose during ozonation. It was concluded that radicals are likely formed when ozone reacts with either lignin or hexA. These carbonyl groups were involved in cellulose depolymerization during subsequent alkaline extraction stages with sodium hydroxide (E) and alkaline hydrogen peroxide (P, in ZEP or ZP). Their numbers decreased after E but increased during P when H2O2 was not stabilized enough. Several ways to minimize the occurrence of carbonyl group formation are suggested. Copyright © 2014. Published by Elsevier Ltd.

  20. Theoretical analysis of isotope effects on ozone formation in oxygen photochemistry

    NASA Technical Reports Server (NTRS)

    Kaye, J. A.

    1986-01-01

    In situ measurements of stratospheric ozone and laboratory studies of ozone production in electric discharge through oxygen have shown previously that ozone containing heavy isotopes of oxygen (O-17, O-18) may be formed preferentially. In order to assess the relevance of thee latter experiment to the stratospheric measurements, detailed understanding of the effect of isotopic substitution on the O3 formation reaction O + O2 + M yields O3 + M and on the O atom exchange reaction O + O2 + O yields O2 + O is necessary. In this work, an estimate of the effect of isotopic substitution on the recombination rate is made by us of approximate dynamical theories and statistical mechanics. The results indicate the possibility of isotope effects on the O + O2 recombination rate of the order of several percent at stratospheric temperatures. In general, recombination reactions involving heavy (mass 49, 50) O3 formation are found to be slower than the reaction leading to normal (mass 48) O3 formation. The calculated isotope effects are sufficiently small that the uncertainties in the model input and the approximations in the dynamical theories will probably make the quantitative nature of these results subject to considerable uncertainty. This isotope effect should not be observable in the atmosphere given the precision of the current measurements but may be crucial in the understanding of the laboratory experiments, where observed enhancements are only of the order of several percent. Possible reasons for this discrepancy between the observed enhancement and predicted depletion are presented.

  1. Formation and Destruction of Ozone in Ices Relevant to Planetary and Satellite Surfaces

    NASA Technical Reports Server (NTRS)

    Moore, Marla H.; Huson, Reggie L.; Sivaraman, Bhala; Mason, Nigel

    2008-01-01

    Ozone, O3, has been observed on the surfaces of Ganymede and the Saturnian satellites Dione and Rhea. It is generally accepted that in each case the O3 is formed by the magnetospheric irradiation of oxygen, O2, within water-rich icy surfaces. Carbon dioxide ice, which has been detected on a number of planetary-satellite surfaces, is another possible source of O3 after irradiation. Laboratory work to date has focused on O3 formation from irradiated O2 at 10 K using < 1O eV and 5 keV electrons and 100 keV protons. The temperature-dependent formation of O3 in solid O2 from 11 to 30 K using 5 keV electrons also has been examined. The objectives of the present laboratory study are (1) to compare O3 formation in O2 and CO2 ices using MeV proton and 10 keV electron bombardment at different temperatures, and (2) to examine ozone's thermal stability in different icy matrices (O2, CO2, H2O) during warming. Our results will aid in the understanding of these possible abiotic ozone sources, which is necessary when assessing O3 as a potential biomarker.

  2. Chlorinated and nitrogenous disinfection by-product formation from ozonation and post-chlorination of natural organic matter surrogates.

    PubMed

    Bond, Tom; Templeton, Michael R; Rifai, Omar; Ali, Hussain; Graham, Nigel J D

    2014-09-01

    Ozonation before chlorination is associated with enhanced formation of chloropicrin, a halonitromethane disinfection by-product (DBP), during drinking water treatment. In order to elucidate reasons for this, five natural organic matter (NOM) surrogates were treated using both chlorination and ozonation-chlorination under controlled laboratory conditions. Selected surrogates comprised two phenolic compounds, two free amino acids and one dipeptide; these were resorcinol, 3-aminophenol, L-aspartic acid, β-alanine and ala-ala, respectively. Quantified DBPs included chloropicrin, chloroform, dichloroacetonitrile and trichloroacetonitrile. Relative to chlorination alone, increases in the formation of chloropicrin from ozonation-chlorination varied from 138% for 3-aminophenol to 3740% for ala-ala for the four amine surrogates. This indicates that ozone is more effective than chlorine in mediating a rate-limiting oxidation step in chloropicrin formation, most plausibly involving conversion of an amine group to a nitro group. While both hydrophilic and hydrophobic surrogates acted as chloropicrin precursors, ala-ala was the most reactive precursor following ozonation-chlorination. Since peptides are far commoner in drinking water sources than free amino acids, further research into chemical oxidation of these species by ozone and chlorine is recommended. In contrast, oxidation with ozone prior to chlorination reduced chloroform formation moderately for the two phenolic compounds.

  3. Unveiling formation mechanism of carcinogenic N-nitrosodimethylamine in ozonation of dimethylamine: a density functional theoretical investigation.

    PubMed

    Zhang, Siyu; Yu, Gang; Chen, Jingwen; Wang, Bin; Huang, Jun; Deng, Shubo

    2014-08-30

    Recent studies found that ozonation of organic pollutants with dimethylamino groups produces N-nitrosodimethylamine (NDMA) that is highly carcinogenic to humans. However, the formation mechanism of NDMA remains inexplicit, and previously proposed mechanisms are inconsistent with experimental observations. In this study, the formation mechanism of NDMA in ozonation was explored by density functional theory (DFT) calculations, with dimethylamine (DMA) as a model compound. By calculating Gibbs energies and energy barriers, formation of NDMA in ozonation of DMA was observed to proceed through a hydroxylamine mechanism. The calculation results show that hydroxylamine is generated through DMA reacting with hydroxyl radicals (HO•) formed from hydrolysis of ozone. DMA reacting with hydroxylamine can produce unsymmetrical dimethylhydrazine (UDMH), a well-known NDMA precursor. Transformation of UDMH to NDMA is mainly induced by ozone or HO• rather than dissolved oxygen proposed previously. The reaction of DMA and hydroxylamine is pH dependent, with energy barriers increasing from neutral pH to the second pKa of hydroxylamine and then decreasing. This is in accordance with the experimentally observed pH dependence of NDMA yield in ozonation, indicating that the hydroxylamine mechanism is responsible for the NDMA formation in ozonation. Copyright © 2014 Elsevier B.V. All rights reserved.

  4. Evaluation of the Community Multiscale Air Quality Model for Simulating Winter Ozone Formation in the Uinta Basin with Intensive Oil and Gas Production

    NASA Astrophysics Data System (ADS)

    Matichuk, R.; Tonnesen, G.; Luecken, D.; Roselle, S. J.; Napelenok, S. L.; Baker, K. R.; Gilliam, R. C.; Misenis, C.; Murphy, B.; Schwede, D. B.

    2015-12-01

    The western United States is an important source of domestic energy resources. One of the primary environmental impacts associated with oil and natural gas production is related to air emission releases of a number of air pollutants. Some of these pollutants are important precursors to the formation of ground-level ozone. To better understand ozone impacts and other air quality issues, photochemical air quality models are used to simulate the changes in pollutant concentrations in the atmosphere on local, regional, and national spatial scales. These models are important for air quality management because they assist in identifying source contributions to air quality problems and designing effective strategies to reduce harmful air pollutants. The success of predicting oil and natural gas air quality impacts depends on the accuracy of the input information, including emissions inventories, meteorological information, and boundary conditions. The treatment of chemical and physical processes within these models is equally important. However, given the limited amount of data collected for oil and natural gas production emissions in the past and the complex terrain and meteorological conditions in western states, the ability of these models to accurately predict pollution concentrations from these sources is uncertain. Therefore, this presentation will focus on understanding the Community Multiscale Air Quality (CMAQ) model's ability to predict air quality impacts associated with oil and natural gas production and its sensitivity to input uncertainties. The results will focus on winter ozone issues in the Uinta Basin, Utah and identify the factors contributing to model performance issues. The results of this study will help support future air quality model development, policy and regulatory decisions for the oil and gas sector.

  5. Use of satellite data to study tropospheric ozone in the tropics

    NASA Technical Reports Server (NTRS)

    Fishman, Jack; Minnis, Patrick; Reichle, Henry G., Jr.

    1986-01-01

    Three independent examples are discussed which suggest that photochemical ozone production in the troposphere can be observed in the tropics from an analysis of total ozone data. The first finding shows that the seasonal cycle of total columnar ozone is dominated by the seasonal cycle of tropospheric ozone, even though tropospheric ozone accounts for only 5-15 percent of the total ozone. Second, a case study is presented which shows that enhanced total ozone observed over the Amazon Basin can be associated with the presence of biomass burning. In situ measurements have confirmed that biomass burning does result in the production of photochemically generated ozone, analogous to the formation of 'smog' near industrialized areas. Third, an analysis of the distribution of carbon monoxide obtained from a Space Shuttle platform is strongly correlated with the concurrent distribution of total ozone between 5 deg S and 10 deg N. Because all of the sources of carbon monoxide are located in the troposphere, this finding likewise suggests that the gradients of total ozone at low latitudes must also reflect processes occurring in the troposphere.

  6. Spatiotemporal variation of ozone precursors and ozone formation in Hong Kong: Grid field measurement and modelling study.

    PubMed

    Lyu, X P; Liu, M; Guo, H; Ling, Z H; Wang, Y; Louie, P K K; Luk, C W Y

    2016-11-01

    Grid field measurements of volatile organic compounds (VOCs) covering the entire territory of Hong Kong were simultaneously carried out twice daily on 27 September 2013 and 24 September 2014, respectively, to advance our understanding on the spatiotemporal variations of VOCs and ozone (O3) formation, the factors controlling O3 formation and the efficacy of a control measure in Hong Kong. From before to after the control measure on liquefied petroleum gas (LPG) fueled vehicles, the VOCs originated from LPG vehicle exhaust deceased from 41.3±1.2μg/m(3) (49.7±1.5%) to 32.8±1.4μg/m(3) (38.8±1.7%) (p<0.05). In contrast, the contribution to VOCs made by gasoline and diesel vehicle exhaust and solvent usage increased (p<0.05). VOCs and nitric oxide (NO) in LPG source experienced the highest reductions at the roadside sites, while the variations were not significant at the urban and new town sites (p>0.05). For O3 production, LPG vehicle exhaust generally made a negative contribution (-0.17±0.06 ppbv) at the roadside sites, however it turned to a slightly positive contribution (0.004±0.038 ppbv) after the control measure. At the urban sites, although the reductions of VOCs and NO were minor (p>0.05), O3 produced by LPG vehicle significantly reduced from 4.19±1.92 ppbv to 0.95±0.38 ppbv (p<0.05). Meanwhile, O3 produced by LPG at the new town sites remained stable. The analysis of O3-precursor relationships revealed that alkenes and aromatics were the main species limiting roadside O3 formation, while aromatics were the most predominant controlling factor at urban and new town sites. In contrast, isoprene and sometimes NOx limited the O3 formation in rural environment.

  7. Effects of ozonation pretreatment on natural organic matter and wastewater derived organic matter - Possible implications on the formation of ozonation by-products.

    PubMed

    Papageorgiou, Alexandros; Stylianou, Stylianos K; Kaffes, Pavlos; Zouboulis, Anastasios I; Voutsa, Dimitra

    2017-03-01

    The aim of this study was to investigate possible implications of natural and wastewater derived organic matter in river water that is subsequently used following treatment for drinking purposes. River water was subjected to lab-scale ozonation experiments under different ozone doses (0.1, 0.4, 0.8, 1.0 and 2.0 mgO3/mgC) and contact times (1, 3, 5, 8 and 10 min). Mixtures of river water with humic acids or wastewaters (sewage wastewater and secondary effluents) at different proportions were also ozonated. Dissolved organic carbon and biodegradable dissolved organic carbon concentrations as well as spectroscopic characteristics (UV absorbance and fluorescence intensities) of different types of dissolved organic matter and possible changes due to the ozonation treatment are presented. River water, humic substances and wastewater exhibited distinct spectroscopic characteristics that could serve for pollution source tracing. Wastewater impacted surface water results in higher formation of carbonyl compounds. However, the formation yield (μg/mgC) of wastewaters was lower than that of surface water possibly due to different composition of wastewater derived organic matter and the presence of scavengers, which may limit the oxidative efficiency of ozone. Copyright © 2016 Elsevier Ltd. All rights reserved.

  8. Aircraft observations above London city during a day and a night: ozone and alkyl nitrate formation

    NASA Astrophysics Data System (ADS)

    Aruffo, Eleonora; Di Carlo, Piero; Dari Salisburgo, Cesare; Biancofiore, Fabio; Giammaria, Franco; Busilacchio, Marcella; Lee, James; Moller, Sarah; Bauguitte, Stephane; O'Sullivan, Debbie; Morgan, Will; Ouyang, Bin; Kennedy, Oliver; Jones, Rod; Forster, Grant; Reeves, Claire; Vaughan, Stewart; Heard, Dwayne

    2013-04-01

    Measurements of NO2, ΣPNs, ΣANs and HNO3 have been done using a TD-LIF instrument, installed on board the FAAM BAe-146 research aircraft, during the RONOCO (ROle of Nighttime chemistry in controlling the Oxidising Capacity) campaign. We analyse in detail the chemical mechanisms that have been established during two flights (B536 and B548) characterized by a similar track (flying above the M25 highway around London) and carried out during a day (B548) and a night (B536). In the daytime flight, the chemical species around London present a net spatial distribution defining two distinct areas: the East London region (up-wind) with an older and less polluted (lowest concentrations of NOx) air masses and the West London region (down-wind) with fresh emissions and more polluted (highest concentrations of NOx with peaks of about 30 ppb). In correspondence of these peaks strong ozone tritation phenomena due to the high NOx levels are verified with a corresponding increase of the ΣANs concentrations. In order to verify the impact of the high concentrations of alkyl nitrate (with maximum values of about 3 ppb) on the tropospheric ozone budget, the production and loss of ozone and ΣANs has been studied. The slopes between the production of ozone and alkyl nitrates confirm that around London the ΣANs formation on one side and the relative ozone loss on the other side represent significant processes. Moreover, the loss of the O3 during the nocturnal flight (B536) is less evident that during the B548 flight.

  9. Photochemical grid model implementation and application of ...

    EPA Pesticide Factsheets

    For the purposes of developing optimal emissions control strategies, efficient approaches are needed to identify the major sources or groups of sources that contribute to elevated ozone (O3) concentrations. Source-based apportionment techniques implemented in photochemical grid models track sources through the physical and chemical processes important to the formation and transport of air pollutants. Photochemical model source apportionment has been used to track source impacts of specific sources, groups of sources (sectors), sources in specific geographic areas, and stratospheric and lateral boundary inflow on O3. The implementation and application of a source apportionment technique for O3 and its precursors, nitrogen oxides (NOx) and volatile organic compounds (VOCs), for the Community Multiscale Air Quality (CMAQ) model are described here. The Integrated Source Apportionment Method (ISAM) O3 approach is a hybrid of source apportionment and source sensitivity in that O3 production is attributed to precursor sources based on O3 formation regime (e.g., for a NOx-sensitive regime, O3 is apportioned to participating NOx emissions). This implementation is illustrated by tracking multiple emissions source sectors and lateral boundary inflow. NOx, VOC, and O3 attribution to tracked sectors in the application are consistent with spatial and temporal patterns of precursor emissions. The O3 ISAM implementation is further evaluated through comparisons of apportioned am

  10. Application of OMI Observations to a Space-Based Indicator of NOx and VOC Controls on Surface Ozone Formation

    NASA Technical Reports Server (NTRS)

    Duncan, Bryan N.; Yoshida, Yasuko; Olson, Jennifer R.; Sillman, Sanford; Martin, Randall V.; Lamsal, Lok; Hu, Yongtao; Pickering, Kenneth E.; Retscher, Christian; Allen, Dale J.; Crawford, James H.

    2010-01-01

    We investigated variations in the relative sensitivity of surface ozone formation in summer to precursor species concentrations of volatile organic compounds (VOCs) and nitrogen oxides (NOx) as inferred from the ratio of the tropospheric columns of formaldehyde to nitrogen dioxide (the "Ratio") from the Aura Ozone Monitoring Instrument (OMI). Our modeling study suggests that ozone formation decreases with reductions in VOCs at Ratios less than 1 and NOx at Ratios greater than 2; both NOx and VOC reductions may decrease ozone formation for Ratios between 1 and 2. Using this criteria. the OMI data indicate that ozone formation became: 1. more sensitive to NOx over most of the United States from 2005 to 2007 because of the substantial decrease in NOx emissions, primarily from stationary sources, and the concomitant decrease in the tropospheric column of NO2. and 2. more sensitive to NOx with increasing temperature, in part because emissions of highly reactive, biogenic isoprene increase with temperature, thus increasing the total VOC reactivity. In cities with relatively low isoprene emissions (e.g .. Chicago). the data clearly indicate that ozone formation became more sensitive to NOx from 2005 to 2007. In cities with relatively high isoprene emissions (e.g ., Atlanta), we found that the increase in the Ratio due to decreasing NOx emissions was not obvious as this signal was convolved with variations in the Ratio associated with the temperature dependence of isoprene emissions and, consequently, the formaldehyde concentration.

  11. Emission characteristics of VOCs emitted from consumer and commercial products and their ozone formation potential.

    PubMed

    Dinh, Trieu-Vuong; Kim, Su-Yeon; Son, Youn-Suk; Choi, In-Young; Park, Seong-Ryong; Sunwoo, Young; Kim, Jo-Chun

    2015-06-01

    The characteristics of volatile organic compounds (VOCs) emitted from several consumer and commercial products (body wash, dishwashing detergent, air freshener, windshield washer fluid, lubricant, hair spray, and insecticide) were studied and compared. The spray products were found to emit the highest amount of VOCs (~96 wt%). In contrast, the body wash products showed the lowest VOC contents (~1.6 wt%). In the spray products, 21.6-96.4 % of the VOCs were propane, iso-butane, and n-butane, which are the components of liquefied petroleum gas. Monoterpene (C10H16) was the dominant component of the VOCs in the non-spray products (e.g., body wash, 53-88 %). In particular, methanol was present with the highest amount of VOCs in windshield washer fluid products. In terms of the number of carbon, the windshield washer fluids, lubricants, insecticides, and hair sprays comprised >95 % of the VOCs in the range C2-C5. The VOCs in the range C6-C10 were predominantly found in the body wash products. The dishwashing detergents and air fresheners contained diverse VOCs from C2 to C11. Besides comprising hazardous VOCs, VOCs from consumer products were also ozone precursors. The ozone formation potential of the consumer and commercial spray products was estimated to be higher than those of liquid and gel materials. In particular, the hair sprays showed the highest ozone formation potential.

  12. Direct measurements of the ozone formation potential from livestock and poultry waste emissions.

    PubMed

    Howard, Cody J; Kumar, Anuj; Mitloehner, Frank; Stackhouse, Kimberly; Green, Peter G; Flocchini, Robert G; Kleeman, Michael J

    2010-04-01

    The global pattern of expanding urban centers and increasing agricultural intensity is leading to more frequent interactions between air pollution emissions from urban and agricultural sources. The confluence of these emissions that traditionally have been separated by hundreds of kilometers is creating new air quality challenges in numerous regions across the United States. An area of particular interest is California's San Joaquin Valley (SJV), which has an agricultural output higher than many countries, a rapidly expanding human population, and ozone concentrations that are already higher than many dense urban areas. New regulations in the SJV restrict emissions of reactive organic gases (ROGs) from animal sources in an attempt to meet Federal and State ozone standards designed to protect human health. The objective of this work is to directly measure the ozone formation potential (OFP) of agricultural animal plus waste sources in representative urban and rural atmospheres using a transportable "smog" chamber. Four animal types were examined: beef cattle, dairy cattle, swine, and poultry. Emissions from each animal plus waste type were captured in a 1 m(3) Teflon bag, mixed with representative background NO(x) and ROG concentrations, and then exposed to UV radiation so that ozone formation could be quantified. The emitted ROG composition was also measured so that the theoretical incremental reactivity could be calculated for a variety of atmospheres and directly compared with the measured OFP under the experimental conditions. The results demonstrate that OFP associated with waste ROG emissions from swine (0.39 +/- 0.04 g-O(3) per g-ROG), beef cattle (0.51 +/- 0.10 g-O(3) per g-ROG), and dairy cattle (0.42 +/- 0.07 g-O(3) per g-ROG) are lower than OFP associated with ROG emissions from gasoline powered light-duty vehicles (LDV) (0.69 +/- 0.05 g-O(3) per g-ROG). The OFP of ROG emitted from poultry waste (1.35 +/- 0.73 g-O(3) per g-ROG) is approximately double the

  13. 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

  14. Formation potentials of typical disinfection byproducts and changes of genotoxicity for chlorinated tertiary effluent pretreated by ozone.

    PubMed

    Cao, Nan; Miao, Tingting; Li, Kuixiao; Zhang, Yu; Yang, Min

    2009-01-01

    The effects of ozonation on the formation potential of typical disinfection byproducts (DBPs) and the changes of genotoxicity during post chlorination of tertiary effluent from a sewage treatment plant were investigated. Ozonation enhanced the yields of all detected chlorine DBPs except CHCl3. At a chlorine dose of 5 mg/L, the three brominated THMs and five HAAs increased, while chloroform decreased with the increase of ozone dose from 0 to 10 mg/L (ozone dose in consumption base). At a chlorine dose of 10 mg/L, the two mixed bromochloro species THMs and two dominant HAAs (DCAA and TCAA) increased firstly and then decreased with the increase of ozone dose, with the turning point approximately occurring at an ozone dose of 5 mg/L. The genotoxicity detected using umu test, on the other hand, was removed from 7 microg 4-NQO/L to a negligible level by ozonation under an ozone dose of 5 mg/L. Chlorination could further remove the genotoxicity to some extent. It was found that SUVA (UV absorbance divided by DOC concentration) might be used as an indicative parameter for monitoring the removal of genotoxicity during the oxidation.

  15. Contribution of regional-scale fire events to ozone and PM2.5 air quality estimated by photochemical modeling approaches

    EPA Science Inventory

    Two specific fires from 2011 are tracked for local to regional scale contribution to ozone (O3) and fine particulate matter (PM2.5) using a freely available regulatory modeling system that includes the BlueSky wildland fire emissions tool, Spare Matrix Operator Kernel Emissions (...

  16. Contribution of regional-scale fire events to ozone and PM2.5 air quality estimated by photochemical modeling approaches

    EPA Science Inventory

    Two specific fires from 2011 are tracked for local to regional scale contribution to ozone (O3) and fine particulate matter (PM2.5) using a freely available regulatory modeling system that includes the BlueSky wildland fire emissions tool, Spare Matrix Operator Kernel Emissions (...

  17. Hydroxyl radical formation during ozonation of multiwalled carbon nanotubes: performance optimization and demonstration of a reactive CNT filter.

    PubMed

    Oulton, Rebekah; Haase, Jason P; Kaalberg, Sara; Redmond, Connor T; Nalbandian, Michael J; Cwiertny, David M

    2015-03-17

    We explored factors influencing hydroxyl radical (•OH) formation during ozonation of multiwalled carbon nanotubes (MWCNTs) and assessed this system's viability as a next-generation advanced oxidation process (AOP). Using standard reactivity metrics for ozone-based AOPs (RCT values), MWCNTs promoted •OH formation during ozonation to levels exceeding ozone (both alone and with activated carbon) and equivalent to ozone with hydrogen peroxide. MWCNTs oxidized with nitric acid exhibited vastly greater rates of ozone consumption and •OH formation relative to as-received MWCNTs. While some of this enhancement reflects their greater suspension stability, a strong correlation between RCT values and surface oxygen concentrations from X-ray photoelectron spectroscopy suggests that surface sites generated during MWCNT oxidation promote •OH exposure. Removal of several ozone-recalcitrant species [para-chlorobenzoic acid (p-CBA), atrazine, DEET, and ibuprofen] was not significantly inhibited in the presence of radical scavengers (humic acid, carbonate), in complex aquatic matrices (Iowa River water) and after 12 h of continuous exposure of MWCNTs to concentrated ozone solutions. As a proof-of-concept, oxidized MWCNTs deposited on a ceramic membrane chemically oxidized p-CBA in a flow through system, with removal increasing with influent ozone concentration and mass of deposited MWCNTs (in mg/cm2). This hybrid membrane platform, which integrates adsorption, oxidation, and filtration via an immobilized MWCNT layer, may serve as the basis for future novel nanomaterial-enabled technologies, although long-term performance trials under representative treatment scenarios remain necessary.

  18. AOPs with ozone and UV radiation in drinking water: contaminants removal and effects on disinfection byproducts formation.

    PubMed

    Collivignarelli, C; Sorlini, S

    2004-01-01

    In this study, the advanced oxidation with ozone and UV radiation (with two low pressure UV lamps, at 254 and 185 nm wavelength) were experimented on a surface water in order to study the removal of two odorous compounds (geosmin and 2-methylisoborneol) and a pesticide (metolachlor), the influence on organic compounds (UV absorbance and THM precursors) and bromate formation. Different batch tests were performed with ozone concentration up to 10 mg/L, UV dose up to 14,000 J/m2 and a maximum contact time of 10 minutes. The main results show that metolachlor can be efficiently removed with ozone alone while for geosmin and MIB a complete removal can be obtained with the advanced oxidation of ozone (with concentration of 1.5-3 mg/L and contact time of 2-3 minutes) with UV radiation (with doses of 5,000-6,000 J/m2). As concerns the influence on the organic precursors, all the experimented processes show a medium removal of about 20-40% for UV absorbance and 15-30% for THMFP (trihalomethanes formation potential). As concerns bromate formation, the advanced oxidation of ozone/UV 254 nm shows a bromate formation that is about 40% lower with respect to conventional oxidation with ozone.

  19. 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.

  20. 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.

  1. The Sensitivity of U.S. Surface Ozone Formation to NOx, and VOCs as Viewed from Space

    NASA Technical Reports Server (NTRS)

    Duncan, Bryan N.; Yoshida, Yasuko; Sillman, Sanford; Retscher, Christian; Pickering, Kenneth E.; Martin, Randall V.; Celarier, Edward A.

    2009-01-01

    We investigated variations in the sensitivity of surface ozone formation in summer to precursor species concentrations of volatile organic compounds (VOCs) and nitrogen oxides (NO(x)) as inferred from the ratio of tropospheric columns of formaldehyde and nitrogen dioxide from the Aura Ozone Monitoring Instrument (OMI). The data indicate that ozone formation became: 1. more sensitive to NO(x) over most of the U.S, from 2005 to 2007 because of substantial decreases in NO(x) emissions primarily from stationary sources, and 2. more sensitive to NO(x) with increasing temperature, in part because emissions of highly reactive, biogenic isoprene increase with temperature, thus increasing the total VOC reactivity. Based on our interpretation of the data, current strategies implemented to reduce unhealthy levels of surface ozone should focus more on reducing NO(x) emissions, except in some downtown areas which have historically benefited from reductions in VOC emissions.

  2. Formation of water-soluble dicarboxylic acids, oxoacids and a-dicarbonyls by ozone oxidation of isoprene

    NASA Astrophysics Data System (ADS)

    Kawamura, K.; Tachibana, E.; Sakamoto, Y.; Hirokawa, J.

    2014-12-01

    Water-soluble dicarboxylic acids such as oxalic acid (C2) are the dominant organic compound class in atmospheric aerosols. They can act as cloud condensation nuclei and affect on the Earth climate. Diacids can be primary emitted from fossil fuel combustion and biomass burning and secondarily produced by photochemical oxidations of biogenic and anthropogenic hydrocarbons. However, their sources and formation processes are still not well understood. Recently model and observation studies suggested the importance of isoprene as a precursor of oxalic acid. Isoprene is the most abundant BVOC emitted from terrestrial plants and can serve as important precursors of diacids. We conducted a laboratory oxidation of isoprene (2.0 ppm) with ozone (4.3 ppm) in a Teflon bag for 10 to 480 min. The formed particles were collected with quartz fiber filters and analyzed for diacids, oxoacids and a-dicarbonyls employing water extraction and butyl ester derivatization and using GC and GC/MS techniques. Here, we report the analytical results to better understand the formation process of diacids and related compounds from isoprene. We detected homologous series of saturated diacids (C2-C6), unsaturated diacids (maleic and methylmaleic acids), w-oxocarboxylic acids (C2-C9), pyruvic acid, glyoxal and methylglyoxal. We found that oxalic acid (3000-9700 ngm-3) is the most abundant diacid followed by succinic (C4) or malonic (C3) acid. Their concentrations increased with reaction time showing a maximum in 4 hours. Interestingly, C3/C4 ratios increased with time. The second most abundant species after oxalic acid was generally methylglyoxal (3600-9600 ngm-3), except for the 30 min. sample where methylglyoxal was more abundant than oxalic acid. Glyoxylic acid (wC2) was found as the most abundant oxoacid (1600-3800 ngm-3) followed by wC3 and wC4. Although the concentrations of diacids and related compounds are 1-2 orders magnitude higher than those reported in ambient aerosols, this study

  3. MNEQA, an emissions model for photochemical simulations

    NASA Astrophysics Data System (ADS)

    Ortega, S.; Soler, M. R.; Alarcón, M.; Arasa, R.

    This study focuses on a new emissions model, Numerical Emissions Model for Air Quality (MNEQA), to be used in photochemical simulations and emission control strategies relating to tropospheric ozone pollutants. MNEQA processes available local information from external files and is easily adaptable to any desired spatial resolution. Top-down and bottom-up methodologies are combined to calculate emissions at the required resolution for photochemical simulations. It was used in conjunction with the MM5-CMAQ air quality modelling system and was applied to an episode of high ozone levels in June 2003. Emission results are widely analysed showing a difference of -8.8% with EMEP NOx emissions, and -18.7% with EMEP VOC emissions. Related to ozone simulations, comparative results between measurements and simulations indicated good behaviour of the model in reproducing diurnal ozone concentrations, as statistical values fall within the EPA and EU regulatory frameworks.

  4. Chemical kinetics and photochemical data for use in stratospheric modeling

    NASA Technical Reports Server (NTRS)

    Demore, W. B.; Margitan, J. J.; Molina, M. J.; Watson, R. T.; Golden, D. M.; Hampson, R. F.; Kurylo, M. J.; Howard, C. J.; Ravishankara, A. R.

    1985-01-01

    Rate constants and photochemical cross sections are presented. The primary application of the data is for modeling of the stratospheric processes, with particular emphasis on the ozone layer and its possible perturbation by anthropogenic and natural phenomena.

  5. Vertical profiles of ozone, water vapor and meteorological parameters and boundary-layer conditions at Summit, Greenland during June 2000

    NASA Astrophysics Data System (ADS)

    Helmig, D.; Alfieri, J. G.; Alfieri, J. G.; Boulter, J.; Boulter, J.; David, D.; Birks, J.; Cullen, N.; Cullen, N.; Steffen, K.; Steffen, K.; Johnson, B.; Oltmans, S.

    2001-12-01

    The temporal and spatial distribution of boundary-layer ozone was studied during June 2000 at Summit, Greenland by surface-level measurements and vertical profiling from a tethered balloon. Three weeks of continuous ozone surface data and 133 meteorological and 82 ozone vertical profile data sets were collected from the surface to a maximum altitude of 1400 m above ground. The lower atmosphere at Summit was characterized by the prevalence of high stability conditions with strong surface temperature inversions. These inversions succumbed to neutral to slightly unstable conditions between appr. 9.00 and 18.00 hrs local time with the formation of shallow mixing heights of typically 70-250 m above the surface. Surface ozone ranged from 39 to 68 ppbv and occasionally had rapid changes of up to 20 ppb in 12 hours. The diurnal mean ozone mixing ratio showed distinct cycles indicating meteorological and photochemical controls of surface ozone. Vertical profiles were within the range of 37 to 76 ppb and showed strong stratification in the lower troposphere. A high correlation of high ozone/low water vapor indicated the transport of high tropospheric/low stratospheric air into the lower boundary layer. An appr. 1 to 4 ppb decline of ozone towards the surface was frequently observed within the neutrally stable mixed layer during midday hours. These observations suggest that the boundary-layer ozone and ozone depletion/deposition to the snowpack are influenced by photochemical processes that follow diurnal dependencies.

  6. Optimal emission control strategies for photochemical smog

    SciTech Connect

    Costanza, V.; Seinfeld, J.H.

    1982-02-01

    A study of certain aspects of the selection of reactive hydrocarbon and nitrogen oxide emission reductions for photochemical oxidant abatement is carried out. Optimal emission control paths are defined as those minimizing a total cost function consisting of control cost and ozone dosage contributions. Los Angeles County ozone air quality and control cost data are used to formulate an optimal emission reduction path. The analysis is presented primarily to provide insight into the factors involved in designing oxidant control strategies.

  7. 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...

  8. 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...

  9. Ozone in the Atmosphere: II. The Lower Atmosphere.

    ERIC Educational Resources Information Center

    Phillips, Paul; Pickering, Pam

    1991-01-01

    Described are the problems caused by the increased concentration of ozone in the lower atmosphere. Photochemical pollution, mechanisms of ozone production, ozone levels in the troposphere, effects of ozone on human health and vegetation, ozone standards, and control measures are discussed. (KR)

  10. Ozone in the Atmosphere: II. The Lower Atmosphere.

    ERIC Educational Resources Information Center

    Phillips, Paul; Pickering, Pam

    1991-01-01

    Described are the problems caused by the increased concentration of ozone in the lower atmosphere. Photochemical pollution, mechanisms of ozone production, ozone levels in the troposphere, effects of ozone on human health and vegetation, ozone standards, and control measures are discussed. (KR)

  11. Greenhouse gases and recovery of the Earth's ozone layer

    NASA Astrophysics Data System (ADS)

    Dyominov, I. G.; Zadorozhny, A. M.

    A numerical two-dimension zonally average interactive dynamical radiative-photochemical model of the atmosphere is used for investigation the role of the greenhouse gases CO2, CH4, and N2O in the recovery of the Earth's ozone layer after reduction of anthropogenic discharges in the atmosphere of chlorine and bromine compounds. The model allows calculating self-consistently 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 types I and II. The scenarios of future changes of the greenhouse gases and chlorine and bromine species are taken from Climate Change 1995. The calculations show that expected cooling of the stratosphere caused by the increasing of the greenhouse gases, particularly CO2, enhances the ozone concentration in the stratosphere due to a weakness of the efficiencies of all catalytic cycles of the ozone destruction caused by temperature dependencies of photochemical reactions. The result of this effect is a significant acceleration of the ozone layer recovery after reduction of anthropogenic discharges in the atmosphere of chlorine and bromine species. On the other hand, the cooling of the stratosphere intensifies a formation of the polar stratospheric clouds in the lower stratosphere in the Polar Regions. Heterogeneous reactions on the polar stratospheric clouds, which are the key processes in the destruction of the ozone layer at the high latitudes, lead to more intensive ozone depletion here, which causes a delay of the ozone layer recovery. The calculations show that this effect is weaker than the first one so that the global ozone will recover faster under conditions of continuing anthropogenic growth of the greenhouse gases. The model predicts in this case that the annual average global ozone will reach its undisturbed level of 1980 by about 2040. If the growth of the

  12. Atmospheric Chemistry of 1H-Heptafluorocyclopentene (cyc-CF2CF2CF2CF═CH-): Rate Constant, Products, and Mechanism of Gas-Phase Reactions with OH Radicals, IR Absorption Spectrum, Photochemical Ozone Creation Potential, and Global Warming Potential.

    PubMed

    Liu, Dongpeng; Qin, Sheng; Li, Wei; Zhang, Di; Guo, Zhikai

    2016-12-08

    The rate constant for gas-phase reactions of OH radicals with 1H-heptafluorocyclopentene (cyc-CF2CF2CF2CF═CH-) was measured using a relative rate method at 298 K: (5.20 ± 0.09) × 10(-14) cm(3) molecule(-1) s(-1). The quoted uncertainty includes two standard deviations from the least-squares regression, the systematic error from the GC analysis, and the uncertainties of the rate constants of the reference compounds. The OH-radical-initiated oxidation of cyc-CF2CF2CF2CF═CH- gives the main products COF2, CO, and CO2, leading to negligible environmental impact. For consumptions of cyc-CF2CF2CF2CF═CH- of less than 54%, the yield of the formation of ([COF2] + [CO] + [CO2])/5 (based on the conservation of carbon) was 0.99 ± 0.02, which is very close to 100%. A possible degradation mechanism was proposed. The radiative efficiency (RE) of cyc-CF2CF2CF2CF═CH- measured at room temperature was 0.215 W m(-2) ppb(-1). The atmospheric lifetime of cyc-CF2CF2CF2CF═CH- was calculated as 0.61 year, and the photochemical ozone creation potential (POCP) was negligible. The 20-, 100-, and 500-year time horizon global warming potentials (GWPs) were estimated as 153, 42, and 12, respectively.

  13. Trends in photochemical smog in the Cape Peninsula and the implications for health.

    PubMed

    Bailie, R S; Ehrlich, R I; Truluck, T F

    1994-11-01

    There has been growing public concern over reports of increasing air pollution in the Cape Peninsula. Attention has been focused on the 'brown haze' and on photochemical smog. Because of deficiencies in the monitoring equipment, information on trends in photochemical smog levels over the past decade is limited. Trends in oxides of nitrogen, one of the main precursors of photochemical smog, and therefore an indicator of the potential for its formation, were examined for the period 1984-1993. Meaningful data for determining trends were available from only a single site. Increases in mean monthly levels, peak hourly levels and the number of times guidelines were exceeded were demonstrated. Given the dynamics of formation of photochemical smog and the particular role of motor vehicles, it is argued that the trends measured at this site are probably an underestimate of the trends in other parts of the Cape Town metropolitan area. Some of the precursors of photochemical smog, notably nitrogen dioxide, and some of its components, notably ozone, have been shown to be detrimental to respiratory health at levels close to, or below, current recommended guidelines. A continuing increase in these pollutants will therefore result in more respiratory illness, particularly among susceptible groups. This calls for an upgrading of monitoring of air pollution in Cape Town and for appropriate steps to prevent its further increase.

  14. Process analysis of regional ozone formation over the Yangtze River Delta, China using the Community Multi-scale Air Quality modeling system

    NASA Astrophysics Data System (ADS)

    Li, L.; Chen, C. H.; Huang, C.; Huang, H. Y.; Zhang, G. F.; Wang, Y. J.; Wang, H. L.; Lou, S. R.; Qiao, L. P.; Zhou, M.; Chen, M. H.; Chen, Y. R.; Fu, J. S.; Streets, D. G.; Jang, C. J.

    2012-06-01

    High ozone concentration has become an important issue in summer in most economically developed cities in Eastern China. In this paper, observations at an urban site within the Shanghai city are used to examine the typical high ozone episodes in August 2010, and the MM5-CMAQ modeling system is then applied to reproduce the typical high ozone episodes. In order to account for the contribution of different atmospheric processes during the high pollution episodes, the CMAQ integrated process rate (IPR) is used to assess the different atmospheric dynamics in rural and urban sites of Shanghai, Nanjing and Hangzhou, which are typical cities of the Yangtze River Delta (YRD) region. In order to study the contributions of the main atmospheric processes leading to ozone formation, vertical process analysis in layer 1 (0-40 m), layer 7 (350-500 m), layer 8 (500-900 m) and layer 10 (1400-2000 m) has been considered. The observations compare well with the results of the numerical model. IPR analysis shows that the maximum concentration of ozone occurs due to transport phenomena, including vertical diffusion and horizontal advective transport. The gas-phase chemistry producing O3 mainly occurs in the height of 300-1500 m, causing a strong vertical O3 transport from upper levels to the surface layer. The gas-phase chemistry is an important sink for O3 in the surface layer, coupled with dry deposition. The cloud processes, horizontal diffusion and heterogeneous chemistry contributions are negligible during the whole episode. In the urban Shanghai area, the average O3 production rates contributed by vertical diffusion and horizontal transport are 24.7 ppb h-1, 3.6 ppb h-1, accounting for 27.6% and 6.6% of net surface O3 change, respectively. The average contributions of chemistry, dry deposition and vertical advective transport to O3 production are -21.9, -4.3 and -2.1 ppb h-1, accounting for -25.3%, -5.0% and -3.7% of net O3 change, respectively. In the suburban and industrial

  15. Formation of aldehydes and carboxylic acids in ozonated surface water and wastewater: a clear relationship with fluorescence changes.

    PubMed

    Liu, Chen; Tang, Xiangyu; Kim, Jaeshin; Korshin, Gregory V

    2015-04-01

    This study examined the formation of aldehydes and carboxylic acids in ozonated surface water and municipal wastewater secondary effluent and addressed correlations between the generation of these compounds and concurrent changes of the fluorescence of natural/effluent organic matter (NOM/EfOM) substrates. Ozonation was effective in removing fluorophores in all excitation/emission matrix (EEM) regions, with those operationally assigned to humic- and protein-like species showing relatively higher reactivity than fulvic-like species. Examination of HO exposures and attendant changes of fluorescence-based parameters allows establishing strong linear relationships between formation of the aldehydes and carboxylic acids and the relative changes of integrated fluorescence (ΔIF/IF0). This demonstrates the feasibility of surrogate monitoring of the formation of biodegradable ozonation by-products via online measurements of water/wastewater EEM fluorescence. Copyright © 2014 Elsevier Ltd. All rights reserved.

  16. Towards A Quantitative Understanding of Nat Formation and Its Impact On Denitrification and Polar Ozone

    NASA Astrophysics Data System (ADS)

    Peter, Th.; Luo, B. P.; Fuglistaler, S.; Knopf, D.; Koop, T.; Buss, S.; Wernli, H.; Voigt, C.

    NAT (nitric acid trihydrate) particles play two important roles in polar ozone chem- istry: (i) heterogeneous reactions on their surface leads to activation of chlorine species, and (ii) sedimentation of large NAT particles may lead to denitrification and thus enhancement of chlorine-catalysed ozone depletion. Despite enormous labora- tory, field and modelling efforts, the formation of NAT particles is still highly contro- versial. While there is indication that small NAT particles at high number density, as observed downstream of ice clouds in mountain waves, might be explained as hetero- geneous NAT nucleation on ice, there is no precise understanding of the microphysics behind this process. Matters are complicated by the fact that ice nucleation, itself sub- ject to strong supercooling, requires a precision in temperature currently not provided by weather forecast models. The origin of large NAT particles at low number concen- trations, so-called NAT rocks, is even more uncertain. There is, however, laboratory evidence against homogeneous nucleation of NAT from supercooled solution droplets. While heterogeneous nucleation is in principle a possible pathway for NAT formation, there is observation-based modelling work suggesting that large NAT particles could be generated from high number density NAT clouds (mother clouds). The potential for predictions of denitrification in a colder future stratosphere will be discussed.

  17. 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.

  18. Investigating the pathway for the photochemical formation of VOCs in presence of an organic monolayer at the air/water interface.

    NASA Astrophysics Data System (ADS)

    Tinel, Liselotte; Rossignol, Stéphanie; Ciuraru, Raluca; George, Christian

    2015-04-01

    Investigating the pathway for the photochemical formation of VOCs in presence of an organic monolayer at the air/water interface. Liselotte Tinel, Stéphanie Rossignol, Raluca Ciuraru and Christian George Université de Lyon, Université Lyon 1, CNRS, UMR5256, IRCELYON, Institut de recherches sur la catalyse et l'environnement de Lyon, Villeurbanne, F-69626, France Recently the surface microlayer (SML) has received growing attention for its role in the deposition and emission of trace gases. This SML is presumably a highly efficient environment for photochemical reactions thanks to its physical and chemical properties, showing enrichment in chromophores [1]. Still, little is known about the possible photochemical processes that could influence the emission and deposition of volatile organic compounds (VOCs) in the SML. A recent study underlines the particularity of the presence of an organic microlayer, showing enhanced formation of peptide bonds at the air-water interface, although this reaction is thermodynamically disfavoured in bulk water [2]. Also, emissions of small gas phase carbonyl compounds formed photochemically by dissolved organic matter have been measured above natural water and glyoxal, for example, measured above the open ocean is thought to be photochemically produced [3, 4]. This study presents the results of a set of laboratory studies set up in order to better understand the role of the SML in the photochemical production of VOCs. Recently, our group has shown the formation of VOCs by light driven reactions in a small quartz reactor (14mL) containing aqueous solutions of humic acids (HA) in the presence of an organic (artificial or natural) microlayer [5]. The main VOCs produced were oxidized species, such as aldehydes, ketones and alcohols, as classically can be expected by the oxidation of the organics present at the interface initiated by triplet excited chromophores present in the HA. But also alkenes, dienes, including isoprene and

  19. Photochemical Reaction of OCSe with ClF in Argon Matrix: A Light-Driven Formation of XC(O)SeY (X, Y = F or Cl) Species.

    PubMed

    Gómez Castaño, Jovanny A; Romano, Rosana M; Della Védova, Carlos O; Willner, Helge

    2017-04-05

    The photochemistry of OCSe with ClF trapped together in argon matrices at cryogenic temperatures has been explored and the first interhalogen representatives of the elusive XC(O)SeY family, namely syn-ClC(O)SeF, anti-ClC(O)SeF, syn-FC(O)SeCl, and anti-FC(O)SeCl, as well as the hitherto triatomic species ClSeF complexed by a CO molecule, were obtained. Both ClC(O)SeF conformers appear to be produced independently by photolysis of the respective precursors; while formation of both FC(O)SeCl structures is ruled by the presence of an angular molecular complex OCSe···Cl-F formed prior to photolysis. This latter photochemical pathway seems to favor the formation of the less stable anti-FC(O)SeCl structure instead of the more stable syn- one. With the aid of quantum chemical calculations, using ab initio, DFT, TDDFT, and CASSCF methods, the mechanism for this photochemical reaction is rationalized both in terms of radical processes as well as a photoinduced electron transfer occurring into the OCSe···Cl-F complex. Also a singlet-triplet conical intersection between anti and syn rotamers of the FC(O)SeCl molecule is theoretically explored.

  20. Photochemical formation of H/sub 2/O/sub 2/ in natural waters exposed to sunlight

    SciTech Connect

    Cooper, W.J.; Zika, R.G.; Petasne, R.G.; Plane, J.M.C.

    1988-10-01

    Hydrogen peroxide is formed in most natural waters when they are exposed to sunlight. The rate at which H/sub 2/O/sub 2/ accumulates is related to the concentration of light-absorbing (>295 nm) organic substances in these waters. The photochemical accumulation rate of H/sub 2/O/sub 2/ in sunlight has been measured for several surface waters and ground waters and was found to be 2.7 /times/ 10/sup /minus/7/ to 48 /times/ 10/sup /minus/7/ mol L/sup /minus/1/ h/sup /minus/1/, in waters ranging from 0.53 to 18 mgL/sup -1/ dissolved organic carbon (DOC), respectively. These rates were determined in midday sunlight, 0.4 W m/sup /minus/2/ (295-385 nm), latitude 24.3/degrees/ N. Apparent quantum yields of H/sub 2/O/sub 2/ have been determined for natural waters at different wavelengths. These quantum yields decreased with increasing wavelength, from 10/sup /minus/3/ in the near-ultraviolet to 10/sup /minus/6/ in the visible spectral range. The quantum yields have been used in a photochemical model to calculate H/sub 2/O/sub 2/ accumulation rates of natural water samples. Model calculations agree with H/sub 2/O/sub 2/ accumulation rates obtained from exposing three different water samples to sunlight.

  1. Volatile organic compounds in pesticide formulations: Methods to estimate ozone formation potential

    NASA Astrophysics Data System (ADS)

    Zeinali, Mazyar; McConnell, Laura L.; Hapeman, Cathleen J.; Nguyen, Anh; Schmidt, Walter F.; Howard, Cody J.

    2011-05-01

    The environmental fate and toxicity of active ingredients in pesticide formulations has been investigated for many decades, but relatively little research has been conducted on the fate of pesticide co-formulants or inerts. Some co-formulants are volatile organic compounds (VOCs) and can contribute to ground-level ozone pollution. Effective product assessment methods are required to reduce emissions of the most reactive VOCs. Six emulsifiable concentrate pesticide products were characterized for percent VOC by thermogravimetric analysis (TGA) and gas chromatography-mass spectrometry (GC-MS). TGA estimates exceeded GC-MS by 10-50% in all but one product, indicating that for some products a fraction of active ingredient is released during TGA or that VOC contribution was underestimated by GC-MS. VOC profiles were examined using TGA-Fourier transform infrared (FTIR) evolved gas analysis and were compared to GC-MS results. The TGA-FTIR method worked best for products with the simplest and most volatile formulations, but could be developed into an effective product screening tool. An ozone formation potential ( OFP) for each product was calculated using the chemical composition from GC-MS and published maximum incremental reactivity ( MIR) values. OFP values ranged from 0.1 to 3.1 g ozone g -1 product. A 24-h VOC emission simulation was developed for each product assuming a constant emission rate calculated from an equation relating maximum flux rate to vapor pressure. Results indicate 100% VOC loss for some products within a few hours, while other products containing less volatile components will remain in the field for several days after application. An alternate method to calculate a product OFP was investigated utilizing the fraction of the total mass of each chemical emitted at the end of the 24-h simulation. The ideal assessment approach will include: 1) unambiguous chemical composition information; 2) flexible simulation models to estimate emissions under

  2. Bromide Sources and Loads in Swiss Surface Waters and Their Relevance for Bromate Formation during Wastewater Ozonation.

    PubMed

    Soltermann, Fabian; Abegglen, Christian; Götz, Christian; von Gunten, Urs

    2016-09-20

    Bromide measurements and mass balances in the catchments of major Swiss rivers revealed that chemical industry and municipal waste incinerators are the most important bromide sources and account for ∼50% and ∼20%, respectively, of the ∼2000 tons of bromide discharged in the Rhine river in 2014 in Switzerland. About 100 wastewater treatment plants (WWTPs) will upgrade their treatment for micropollutant abatement in the future to comply with Swiss regulations. An upgrade with ozonation may lead to unintended bromate formation in bromide-containing wastewaters. Measured bromide concentrations were <0.05 mg L(-1) in ∼75% of 69 WWTPs, while they ranged from 0.4 to ∼50 mg L(-1) in WWTPs with specific bromide sources (e.g., municipal waste incinerators, landfill leachate, and chemical industry). Wastewater ozonation formed little bromate at specific ozone doses of ≤0.4 mg O3/mg DOC, while the bromate yields were almost linearly correlated to the specific ozone dose for higher ozone doses. Molar bromate yields for typical specific ozone doses in wastewater treatment (0.4-0.6 mg O3/mg DOC) are ≤3%. In a modeled extreme scenario (in which all upgraded WWTPs release 10 μg L(-1) of bromate), bromate concentrations increased by <0.4 μg L(-1) in major Swiss rivers and by several micrograms per liter in receiving water bodies with a high fraction of municipal wastewater.

  3. Ozone, Tropospheric

    NASA Technical Reports Server (NTRS)

    Fishman, Jack

    1995-01-01

    In the early part of the 20th century, ground-based and balloon-borne measurements discovered that most of atmosphere's ozone is located in the stratosphere with highest concentrations located between 15 and 30 km (9,3 and 18.6 miles). For a long time, it was believed that tropospheric ozone originated from the stratosphere and that most of it was destroyed by contact with the earth's surface. Ozone, O3, was known to be produced by the photo-dissociation of molecular oxygen, O2, a process that can only occur at wavelengths shorter than 242 nm. Because such short-wave-length radiation is present only in the stratosphere, no tropospheric ozone production is possible by this mechanism. In the 1940s, however, it became obvious that production of ozone was also taking place in the troposphere. The overall reaction mechanism was eventually identified by Arie Haagen-Smit of the California Institute of Technology, in highly polluted southern California. The copious emissions from the numerous cars driven there as a result of the mass migration to Los Angeles after World War 2 created the new unpleasant phenomenon of photochemical smog, the primary component of which is ozone. These high levels of ozone were injuring vegetable crops, causing women's nylons to run, and generating increasing respiratory and eye-irritation problems for the populace. Our knowledge of tropospheric ozone increased dramatically in the early 1950s as monitoring stations and search centers were established throughout southern California to see what could be done to combat this threat to human health and the environment.

  4. Spring time photochemical air pollution in Osaka

    SciTech Connect

    Wakamatsu, Shinji; Uno, Itsushi; Ohara, Toshimasa

    1996-12-31

    High concentrations of nitrogen dioxide are frequently observed in Osaka area in spring season. To clarify this, a series of three dimensional field observation was conducted in April 1993 covering Osaka and surrounding area. Vertical and horizontal distributions of ozone, NO, NO{sub x}, SO{sub 2}, CO, aerosol species, hydrocarbon species and meteorological parameter such as temperature, uv radiation, wind speed, wind direction are measured on the ground and aloft. Covering the observational period yellow sand transportation from the continent and stratospheric ozone intrusion were also observed under the meteorological condition of moving high pressure system. During the aircraft observation of 19 to 21 April 1993 high concentration of photochemical air pollution was observed aloft over Osaka area. Maximum ozone concentration was me than 150 ppb. Vertical distribution of ozone showed uniform profile up to 2500m in day time. At Mt. Ikoma (600 m) ozone concentration had been almost constant ranging 80-100 ppb throughout the observational period. To clarify this phenomena three dimensional photochemical air pollution simulation model was applied based on the real meteorological and emission conditions. Simulated result showed photochemical reaction play an important role to form the spring time high concentrations of nitrogen dioxide in Osaka.

  5. Volatile organic compounds measured in summer in Beijing and their role in ground-level ozone formation

    NASA Astrophysics Data System (ADS)

    Shao, Min; Lu, Sihua; Liu, Ying; Xie, Xin; Chang, Chichung; Huang, Shan; Chen, Zhongmin

    2009-01-01

    Beijing has long suffered from serious ground-level ozone pollution, and volatile organic compounds (VOCs) play a key role in ozone formation. To understand the chemical speciation of VOCs in Beijing, nonmethane hydrocarbons (NMHCs) and oxygenated VOCs (OVOCs) were measured in summer in Beijing and nearby provinces (VOCs in this work means NMHCs+OVOCs). A variation of VOC mixing ratios and chemical speciation from 2004 to 2006 was observed at an urban site in Beijing. The typical VOC species, e.g., propane, propene, and toluene, had comparable or lower mixing ratios than levels found in other cities that previously hosted the Olympic Games, while the mixing ratios for isoprene were higher. The chemical compositions of VOCs within Beijing were heavily influenced by vehicular emissions and differed from those obtained in Tianjin and Hebei Province. OVOCs were an important component, accounting for 54% and 37% in the VOC mixing ratio in 2005 and 2006, respectively, and about 40% of the OH loss rates. The main reactive VOC compounds were aldehydes and alkenes. By using isoprene chemistry and the ratio of ethylbenzene to mp-xylene, the initial mixing ratios of VOCs were estimated. The VOCs had similar variation patterns to ambient ozone and peroxyacetyl nitrate (PAN) concentrations. The correlation between daily maximum ozone concentrations and initial VOCs revealed that ozone formation was sensitive to VOCs for both urban (Peking University, PKU) and rural (Yufa) sites. A reduction in NOx would lead to a decrease in ozone at Yufa, but would cause increased ozone at the PKU site.

  6. Ozone and meteorological boundary-layer conditions at Summit, Greenland, during 3-21 June 2000

    NASA Astrophysics Data System (ADS)

    Helmig, Detlev; Boulter, James; David, Donald; Birks, John W.; Cullen, Nicolas J.; Steffen, Konrad; Johnson, Bryan J.; Oltmans, Samuel J.

    The temporal and spatial distributions of boundary-layer ozone were studied during June 2000 at Summit, Greenland, using surface-level measurements and vertical profiling from a tethered balloon platform. Three weeks of continuous ozone surface data, 133 meteorological vertical profile data and 82 ozone vertical profile data sets were collected from the surface to a maximum altitude of 1400 m above ground. The lower atmosphere at Summit was characterized by the prevalence of strong stable conditions with strong surface temperature inversions. These inversions reversed to neutral to slightly unstable conditions between ˜9.00 and 18.00 h local time with the formation of shallow mixing heights of ˜70-250 m above the surface. The surface ozone mixing ratio ranged from 39 to 68 ppbv and occasionally had rapid changes of up to 20 ppb in 12 h. The diurnal mean ozone mixing ratio showed diurnal trends indicating meteorological and photochemical controls of surface ozone. Vertical profiles were within the range of 37-76 ppb and showed strong stratification in the lower troposphere. A high correlation of high ozone/low water vapor air masses indicated the transport of high tropospheric/low stratospheric air into the lower boundary layer. A ˜0.1-3 ppb decline of the ozone mixing ratio towards the surface was frequently observed within the neutrally stable mixed layer during midday hours. These data suggest that the boundary-layer ozone mixing ratio and ozone depletion and deposition to the snowpack are influenced by photochemical processes and/or transport phenomena that follow diurnal dependencies. With 37 ppb of ozone being the lowest mixing ratio measured in all data no evidence was seen for the occurrence of ozone depletion episodes similar to those that have been reported within the boundary layer at coastal Arctic sites during springtime.

  7. Speciated VOC emission inventory and spatial patterns of ozone formation potential in the Pearl River Delta, China.

    PubMed

    Zheng, Junyu; Shao, Min; Che, Wenwei; Zhang, Lijun; Zhong, Liuju; Zhang, Yuanhang; Streets, David

    2009-11-15

    The Pearl River Delta region (PRD) of China has long suffered from severe ground-level ozone pollution. Knowledge of the sources of volatile organic compounds (VOCs) is essential for ozone chemistry. In this work, a speciated VOC emission inventory was established on the basis of updated emissions and local VOC source profiles. The top 10 species, in terms of ozone formation potentials (OFPs), consisted of isoprene, mp-xylene, toluene, ethylene, propene, o-xylene, 1,2,4-trimethylbenzene, 2-methyl-2-butene, 1-butene, and alpha-pinene. These species contributed only 35.9% to VOCs emissions but accounted for 64.1% of the OFP in the region. The spatial patterns of the VOC source inventory agreed well with city-based source apportionment results, especially for vehicle emissions and industry plus VOC product-related emissions. Mapping of the OFPs and measured ozone concentrations indicated that the formation of higher ozone in the south and southeast of the PRD region differed from that in the Conghua area, a remote area in the north of the PRD. We recommend that the priorities for the control of VOC sources include motorcycles, gasoline vehicles, and solvent use because of their larger OFP contributions.

  8. Protein Cross-Linking and Oligomerization through Dityrosine Formation upon Exposure to Ozone.

    PubMed

    Kampf, Christopher J; Liu, Fobang; Reinmuth-Selzle, Kathrin; Berkemeier, Thomas; Meusel, Hannah; Shiraiwa, Manabu; Pöschl, Ulrich

    2015-09-15

    Air pollution is a potential driver for the increasing prevalence of allergic disease, and post-translational modification by air pollutants can enhance the allergenic potential of proteins. Here, the kinetics and mechanism of protein oligomerization upon ozone (O3) exposure were studied in coated-wall flow tube experiments at environmentally relevant O3 concentrations, relative humidities and protein phase states (amorphous solid, semisolid, and liquid). We observed the formation of protein dimers, trimers, and higher oligomers, and attribute the cross-linking to the formation of covalent intermolecular dityrosine species. The oligomerization proceeds fast on the surface of protein films. In the bulk material, reaction rates are limited by diffusion depending on phase state and humidity. From the experimental data, we derive a chemical mechanism and rate equations for a kinetic multilayer model of surface and bulk reaction enabling the prediction of oligomer formation. Increasing levels of tropospheric O3 in the Anthropocene may promote the formation of protein oligomers with enhanced allergenicity and may thus contribute to the increasing prevalence of allergies.

  9. 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.

  10. 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...

  11. 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...

  12. Formation potentials of bromate and brominated disinfection by-products in bromide-containing water by ozonation.

    PubMed

    Lin, Tao; Wu, Shouke; Chen, Wei

    2014-12-01

    The ozonation involved in drinking water treatment raises issues of water quality security when the raw water contains bromide (Br(-)). Br(-) ions may be converted to bromate (BrO3 (-)) during ozonation and some brominated disinfection by-products (Br-DBPs) in the following chlorination. In this study, the effects of ozone (O3) dosage, contact time, pH, and Br(-) and ammonia (NH3-N) concentrations on the formation of BrO3 (-) and Br-DBPs have been investigated. The results show that decreasing the initial Br(-) concentration is an effective means of controlling the formation of BrO3 (-). When the concentration of Br(-) was lower than 100 μg/L, by keeping the ratio of O3 dosage to dissolved organic carbon (DOC) concentration at less than 1, BrO3 (-) production was effectively suppressed. The concentration of BrO3 (-) steadily increased with increasing O3 dosage at high Br(-) concentration (>900 μg/L). Additionally, a longer ozonation time increased the concentrations of BrO3 (-) and total organic bromine (TOBr), while it had less impact on the formation potentials of brominated trihalomethanes (Br-THMFP) and haloacetic acids (Br-HAAFP). Higher pH value and the presence of ammonia may lead to an increase in the formation potential of BrO3 (-) and Br-DBPs.

  13. Origin of Ozone NO(x) in the Tropical Troposphere: A Photochemical Analysis of Aircraft Observations Over the South Atlantic Basin

    NASA Technical Reports Server (NTRS)

    Jacob, D. J.; Heikes, B. G.; Fan, S.-M.; Logan, J. A.; Mauzerall, D. L.; Bradshaw, J. D.; Singh, H. B.; Gregory, G. L.; Talbot, R. W.; Blake, D. R.; hide

    1996-01-01

    The photochemistry of the troposphere over the South Atlantic basin is examined by modeling of aircraft observations up to 12-km altitude taken during the TRACE A expedition in September-October 1992. A close balance is found in the 0 to 12-km column between photochemical production and loss Of O3, with net production at high altitudes compensating for weak net loss at low altitudes. This balance implies that O3 concentrations in the 0-12 km column can be explained solely by in situ photochemistry; influx from the stratosphere is negligible. Simulation of H2O2, CH3OOH, and CH2O concentrations measured aboard the aircraft lends confidence in the computations of O3 production and loss rates, although there appears to be a major gap in current understanding of CH2O chemistry in the marine boundary layer. The primary sources of NO(x) over the South Atlantic Basin appear to be continental (biomass burning, lightning, soils). There is evidence that NO(x) throughout the 0 to 12-km column is recycled from its oxidation products rather than directly transported from its primary sources. There is also evidence for rapid conversion of HNO3 to NO(x) in the upper troposphere by a mechanism not included in current models. A general representation of the O3 budget in the tropical troposphere is proposed that couples the large scale Walker circulation and in situ photochemistry. Deep convection in the rising branches of the Walker circulation injects NO(x) from combustion, soils, and lightning to the upper troposphere, leading to O3 production; eventually, the air subsides and net O3 loss takes place in the lower troposphere, closing the O3 cycle. This scheme implies a great sensitivity of the oxidizing power of the atmosphere to NO(x) emissions in the tropics.

  14. Formation of strong airway irritants in mixtures of isoprene/ozone and isoprene/ozone/nitrogen dioxide.

    PubMed Central

    Wilkins, C K; Clausen, P A; Wolkoff, P; Larsen, S T; Hammer, M; Larsen, K; Hansen, V; Nielsen, G D

    2001-01-01

    We evaluated the airway irritation of isoprene, isoprene/ozone, and isoprene/ozone/nitrogen dioxide mixtures using a mouse bioassay, from which we calculated sensory irritation, bronchial constriction, and pulmonary irritation. We observed significant sensory irritation (approximately 50% reduction of mean respiratory rate) by dynamically exposing the mice, over 30 min, to mixtures of isoprene and O3 or isoprene, O3, and NO2. The starting concentrations were approximately 4 ppm O3 and 500 ppm isoprene (+ approximately 4 ppm NO2. The reaction mixtures after approximately 30 sec contained < 0.2 ppm O3. Addition of the effects of the residual reactants and the identified stable irritant products (formaldehyde, formic acid, acetic acid, methacrolein, and methylvinyl ketone) could explain only partially the observed sensory irritation. This suggests that one or more strong airway irritants were formed. It is thus possible that oxidation reactions of common unsaturated compounds may be relevant for indoor air quality. PMID:11673123

  15. 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

  16. Identification of volatile organic compounds in suburban Bangkok, Thailand and their potential for ozone formation

    NASA Astrophysics Data System (ADS)

    Suthawaree, Jeeranut; Tajima, Yosuke; Khunchornyakong, Alisa; Kato, Shungo; Sharp, Alice; Kajii, Yoshizumi

    2012-02-01

    Measurement of Volatile Organic Compound (VOC) was carried out in suburban Bangkok during July 2-8, 2008. Analysis was performed using GC-FID and GC-MS. High mixing ratios of VOCs detected during the morning and evening are most likely due to vehicular emissions. Averaged VOC mixing ratios revealed distinct difference between mixing ratios of weekdays and weekend, which the latter were found to be lower. The most abundance species were propane and toluene. Ratios of benzene over toluene suggested that additional toluene mixing ratios was owing to industrial emission, which was particularly larger during weekdays. Comparison between C2Cl4 and CH3Cl mixing ratios obtained for suburban Tokyo reveal a relatively lower influence of biomass burning than suburban Bangkok. Elucidating by Ozone Formation Potential, toluene was found to contribute the most to O3 production followed by ethylene, m-,p-xylene, and propylene.

  17. Volatile organic compound emissions from green waste composting: Characterization and ozone formation

    NASA Astrophysics Data System (ADS)

    Kumar, Anuj; Alaimo, Christopher P.; Horowitz, Robert; Mitloehner, Frank M.; Kleeman, Michael J.; Green, Peter G.

    2011-04-01

    Composting of green waste separated from the disposed solid waste stream reduces biodegradable inputs into landfills, and contributes valuable soil amendments to agriculture. Agencies in regions with severe air quality challenges, such as California's San Joaquin Valley (SJV), have raised concerns about gases emitted during the composting process, which are suspected to contribute to persistent high levels of ground-level ozone formation. The goal of the current study is to thoroughly characterize volatile organic compound (VOC) emissions from green waste compost piles of different ages (fresh tipped piles, 3-6 day old windrows, and 2-3 week old windrows). Multiple sampling and analytical approaches were applied to ensure the detection of most gaseous organic components emitted. More than 100 VOCs were detected and quantified in this study, including aliphatic alkanes, alkenes, aromatic hydrocarbons, biogenic organics, aldehydes, ketones, alcohols, furans, acids, esters, ether, halogenated hydrocarbons and dimethyl disulfide (DMDS). Alcohols were found to be the dominating VOC in the emissions from a compost pile regardless of age, with fluxes ranging from 2.6 to 13.0 mg m -2 min -1 with the highest emissions coming from the younger composting windrows (3-6 days). Average VOC emissions other than alcohols were determined to be 2.3 mg m -2 min -1 from younger windows, which was roughly two times higher than either the fresh tipping pile (1.2 mg m -2 min -1) or the older windrows (1.4 mg m -2 min -1). It was also observed that the older windrows emit a slightly larger proportion of more reactive compounds. Approximately 90% of the total VOCs were found to have maximum incremental reactivity of less than 2. Net ozone formation potential of the emissions was also assessed.

  18. On the formation of ozone in oxygen-rich solar system ices via ionizing radiation.

    PubMed

    Ennis, Courtney P; Bennett, Chris J; Kaiser, Ralf I

    2011-05-28

    The irradiation of pure molecular oxygen (O(2)) and carbon dioxide (CO(2)) ices with 5 keV H(+) and He(+) ions was investigated experimentally to simulate the chemical processing of oxygen rich planetary and interstellar surfaces by exposure to galactic cosmic ray (GCR), solar wind, and magnetospheric particles. Deposited at 12 K under ultra-high vacuum conditions (UHV), the irradiated condensates were monitored on-line and in situ in the solid-state by Fourier transform infrared spectroscopy (FTIR), revealing the formation of ozone (O(3)) in irradiated oxygen ice; and ozone, carbon monoxide (CO), and cyclic carbon trioxide (c-CO(3)) in irradiated carbon dioxide. In addition to these irradiation products, evolution of gas-phase molecular hydrogen (H(2)), atomic helium (He) and molecular oxygen (O(2)) were identified in the subliming oxygen and carbon dioxide condensates by quadrupole mass spectrometry (QMS). Temporal abundances of the oxygen and carbon dioxide precursors and the observed molecular products were compiled over the irradiation period to develop reaction schemes unfolding in the ices. These reactions were observed to be dependent on the generation of atomic oxygen (O) by the homolytic dissociation of molecular oxygen induced by electronic, S(e), and nuclear, S(n), interaction with the impinging ions. In addition, the destruction of the ozone and carbon trioxide products back to the molecular oxygen and carbon dioxide precursors was promoted over an extended period of ion bombardment. Finally, destruction and formation yields were calculated and compared between irradiation sources (including 5 keV electrons) which showed a surprising correlation between the molecular yields (∼10(-3)-10(-4) molecules eV(-1)) created by H(+) and He(+) impacts. However, energy transfer by isoenergetic, fast electrons typically generated ten times more product molecules per electron volt (∼10(-2)-10(-3) molecules eV(-1)) than exposure to the ions. Implications of these

  19. Oxidation of Microcystis aeruginosa and Anabaena flos-aquae by ozone: impacts on cell integrity and chlorination by-product formation.

    PubMed

    Coral, Lucila A; Zamyadi, Arash; Barbeau, Benoit; Bassetti, Fatima J; Lapolli, Flávio R; Prévost, Michèle

    2013-06-01

    Pre-ozonation of cyanobacterial (CB) cells in raw water and inter-ozonation of settled water can cause CB cell damage. However, there is limited information about the level of lysis or changes in cell properties after ozonation, release of intracellular compounds and their contribution to the formation of disinfection by-products (DBPs). This study aims to: (1) assess the extent of the pre-ozonation effects on CB cell properties; (2) determine the CT (ozone concentration × detention time) values required for complete loss of cell viability; and (3) study the DBPs formation associated with the pre-ozonation of cyanobacterial cells in laboratorial suspensions. To these ends, both Microcystis aeruginosa and Anabaena flos-aquae suspensions were prepared at concentrations of 250,000 cells mL(-1) and 1,500,000 cells mL(-1) and were subjected to ozone dosages of 0.5, 2.0 and 4.0 mg L(-1) at pH 6 and pH 8. A quick and complete loss of viability was achieved for both CB species after exposure (CT) to ozone of <0.2 mg min L(-1), although no significant decrease in total cell numbers was observed. Maximum dissolved organic carbon (DOC) releases of 0.96 mg L(-1) and 1.63 mg L(-1) were measured after ozonation of 250,000 cells mL(-1) of M. aeruginosa and A. flos-aquae, respectively. DOC release was found to be pH and ozone dose dependent. Ozonation of CB cells increased formation of trihalomethanes (THM) and haloacetic acids (HAA), mainly for suspensions of A. flos-aquae at pH 8 (by 174% and 65% for THM and HAA respectively). Utilities considering using ozone for oxidising CB cells should weigh out the benefit of CB control with the potential increased formation of chlorinated DBPs.

  20. Secondary Organic Aerosol formation from the gas-phase reaction of catechol with ozone

    NASA Astrophysics Data System (ADS)

    Coeur-Tourneur, C.; Tomas, A.; Guilloteau, A.; Henry, F.; Ledoux, F.; Visez, N.; Riffault, V.; Wenger, J. C.; Bedjanian, Y.; Foulon, V.

    2009-04-01

    The formation of secondary organic aerosol from the gas-phase reaction of catechol (1,2-dihydroxybenzene) with ozone has been studied in two smog chambers (at the LPCA in France and at the CRAC in Ireland). Aerosol production was monitored using a scanning mobility particle sizer. The overall organic aerosol yield (Y) was determined as the ratio of the suspended aerosol mass corrected for wall losses (Mo) to the total reacted catechol concentrations, assuming a particle density of 1.4 g cm-3. Analysis of the data clearly shows that Y is a strong function of Mo and that secondary organic aerosol formation can be expressed by a one-product gas/particle partitioning absorption model. The aerosol formation is affected by the initial catechol concentration, which leads to aerosol yields ranging from 17% to 86%. The aerosol yields determined in the LPCA and CRAC smog chambers were comparable and were also in accordance with those determined in a previous study performed in EUPHORE (EUropean PHOto REactor, Spain).

  1. Potential impacts of climate change on tropospheric ozone in California: a preliminary episodic modeling assessment of the Los Angeles basin and the Sacramento valley

    SciTech Connect

    Taha, Haider

    2001-01-01

    In this preliminary and relatively short modeling effort, an initial assessment is made for the potential air quality implications of climate change in California. The focus is mainly on the effects of changes in temperature and related meteorological and emission factors on ozone formation. Photochemical modeling is performed for two areas in the state: the Los Angeles Basin and the Sacramento Valley.

  2. Increase in ozone due to the use of biodiesel fuel rather than diesel fuel.

    PubMed

    Thang, Phan Quang; Muto, Yusuke; Maeda, Yasuaki; Trung, Nguyen Quang; Itano, Yasuyuki; Takenaka, Norimichi

    2016-09-01

    The consumption of fuel by vehicles emits nitrogen oxides (NOx) and non-methane hydrocarbons (NMHCs) into the atmosphere, which are important ozone precursors. Ozone is formed as a secondary pollutant via photochemical processes and is not emitted directly into the atmosphere. In this paper, the ozone increase resulting from the use of biodiesel and diesel fuels was investigated, and the different ozone formation trends were experimentally evaluated. Known amounts of exhaust gas from a power generator operated using biodiesel and diesel fuels were added to ambient air. The quality of the ambient air, such as the initial NMHC and NOx concentrations, and the irradiation intensity have an effect on the ozone levels. When 30 cm(3) of biodiesel fuel exhaust gas (BFEG) or diesel fuel exhausted gas (DFEG) was added to 18 dm(3) of ambient air, the highest ratios of ozone increase from BFEG compared with DFEG in Japan and Vietnam were 31.2 and 42.8%, respectively, and the maximum ozone increases resulting from DFEG and BFEG compared with the ambient air in Japan were 17.4 and 26.4 ppb, respectively. The ozone increase resulting from the use of BFEG was large and significant compared to that from DFEG under all experimental conditions. The ozone concentration increased as the amount of added exhaust gas increased. The ozone increase from the Jatropha-BFEG was slightly higher than that from waste cooking oil-BFEG.

  3. Modeling and direct sensitivity analysis of biogenic emissions impacts on regional ozone formation in the Mexico-U.S. border area.

    PubMed

    Mendoza-Dominguez, A; Wilkinson, J G; Yang, Y J; Russell, A G

    2000-01-01

    A spatially and temporally resolved biogenic hydrocarbon and nitrogen oxides (NOx) emissions inventory has been developed for a region along the Mexico-U.S. border area. Average daily biogenic non-methane organic gases (NMOG) emissions for the 1700 x 1000 km2 domain were estimated at 23,800 metric tons/day (62% from Mexico and 38% from the United States), and biogenic NOx was estimated at 1230 metric tons/day (54% from Mexico and 46% from the United States) for the July 18-20, 1993, ozone episode. The biogenic NMOG represented 74% of the total NMOG emissions, and biogenic NOx was 14% of the total NOx. The CIT photochemical airshed model was used to assess how biogenic emissions impact air quality. Predicted ground-level ozone increased by 5-10 ppb in most rural areas, 10-20 ppb near urban centers, and 20-30 ppb immediately downwind of the urban centers compared to simulations in which only anthropogenic emissions were used. A sensitivity analysis of predicted ozone concentration to emissions was performed using the decoupled direct method for three dimensional air quality models (DDM-3D). The highest positive sensitivity of ground-level ozone concentration to biogenic volatile organic compound (VOC) emissions (i.e., increasing biogenic VOC emissions results in increasing ozone concentrations) was predicted to be in locations with high NOx levels, (i.e., the urban areas). One urban center--Houston--was predicted to have a slight negative sensitivity to biogenic NO emissions (i.e., increasing biogenic NO emissions results in decreasing local ozone concentrations). The highest sensitivities of ozone concentrations to on-road mobile source VOC emissions, all positive, were mainly in the urban areas. The highest sensitivities of ozone concentrations to on-road mobile source NOx emissions were predicted in both urban (either positive or negative sensitivities) and rural (positive sensitivities) locations.

  4. Dynamical Mechanisms of Ozone Anomalies Formation as Revealed by Global-Scale and Regional Simulations with PlanetWRF and CAM modelling systems

    NASA Astrophysics Data System (ADS)

    Barodka, Siarhei; Krasouski, Alexander; Svetashev, Alexander; Turishev, Leonid; Zhuchkevich, Veronika

    2013-04-01

    Local ozone anomalies, defined as synoptic-scale deviations in total ozone column (TOC) field from its average climatic values, constitute an important short-term component of stratospheric ozone variability. Their formation and evolution is a manifestation of subtle dynamical processes related to stratosphere-troposphere interactions. Various studies of local ozone anomalies attributed their formation to such mechanisms as northeast horizontal motions of air patches with low ozone content [1], uplift of air masses and the local tropopause resulting in decrease of the pressure thickness of the ozone layer [2], displacement with the ozone depleted stratospheric polar vortex [1] and the anticyclonic anomalies in the stratosphere [2, 3]. It has also been argued that the potential vorticity (PV) field can be used as a "proxy" for ozone if the latter is treated as a passive tracer. However, this is valid only for large-scale adiabatic processes, for which the PV is a conserved variable. To investigate the role of different processes and scales in formation, evolution and decay of local ozone anomalies we perform a series of comparative simulations with global, regional and mesoscale models. For global-scale modelling we use the standalone version of the Community Atmosphere Model (CAM) in several configurations suitable for simulating stratospheric ozone dynamics. On the other hand, we utilize a modified version of the Weather Research & Forecasting (WRF) system to evaluate the possible impact of finer-scale dynamics and mesoscale processes on ozone anomalies. For that purpose, we combine the PlanetWRF system with the WRF-Chem extension and introduce some further modifications to improve representation of stratospheric processes with simulation of ozone as an active tracer. Special attention is paid to radiative transfer parameterizations, since in situ radiation absorption by ozone and the associated heating plays a crucial role in the stratosphere and the radiation

  5. A better understanding of hydroxyl radical photochemical sources in cloud waters collected at the puy de Dôme station - experimental versus modelled formation rates

    NASA Astrophysics Data System (ADS)

    Bianco, A.; Passananti, M.; Perroux, H.; Voyard, G.; Mouchel-Vallon, C.; Chaumerliac, N.; Mailhot, G.; Deguillaume, L.; Brigante, M.

    2015-08-01

    The oxidative capacity of the cloud aqueous phase is investigated during three field campaigns from 2013 to 2014 at the top of the puy de Dôme station (PUY) in France. A total of 41 cloud samples are collected and the corresponding air masses are classified as highly marine, marine and continental. Hydroxyl radical (HO•) formation rates (RHO•f) are determined using a photochemical setup (xenon lamp that can reproduce the solar spectrum) and a chemical probe coupled with spectroscopic analysis that can trap all of the generated radicals for each sample. Using this method, the obtained values correspond to the total formation of HO• without its chemical sinks. These formation rates are correlated with the concentrations of the naturally occurring sources of HO•, including hydrogen peroxide, nitrite, nitrate and iron. The total hydroxyl radical formation rates are measured as ranging from approximately 2 × 10-11 to 4 × 10-10 M s-1, and the hydroxyl radical quantum yield formation (ΦHO•) is estimated between 10-4 and 10-2. Experimental values are compared with modelled formation rates calculated by the model of multiphase cloud chemistry (M2C2), considering only the chemical sources of the hydroxyl radicals. The comparison between the experimental and the modelled results suggests that the photoreactivity of the iron species as a source of HO• is overestimated by the model, and H2O2 photolysis represents the most important source of this radical (between 70 and 99 %) for the cloud water sampled at the PUY station (primarily marine and continental).

  6. Mobile source and livestock feed contributions to regional ozone formation in Central California.

    PubMed

    Hu, Jianlin; Howard, Cody J; Mitloehner, Frank; Green, Peter G; Kleeman, Michael J

    2012-03-06

    A three-dimensional air quality model with 8 km horizontal resolution was applied to estimate the summertime ozone (O(3)) production from mobile sources and fermented livestock feed in California's San Joaquin Valley (SJV) during years 2000, 2005, 2010, 2015, and 2020. Previous studies have estimated that animal feed emissions of volatile organic compounds (VOCs) have greater O(3) formation potential than mobile-source VOC emissions when averaging across the entire SJV. The higher spatial resolution in the current study shows that the proximity of oxides of nitrogen (NO(x)) and VOC emissions from mobile sources enhances their O(3) formation potential. Livestock feed VOC emissions contributed 3-4 ppb of peak O(3) (8-h average) in Tulare County and 1-2 ppb throughout the remainder of the SJV during the CCOS 2000 July-August episode. In total, livestock feed contributed ~3.5 tons of the ground level peak O(3) (8 h average) in the SJV region, and mobile VOC contributed ~12 tons in this episode. O(3) production from mobile sources is declining over time in response to emissions control plans that call for cleaner fuels and engines with advanced emissions controls. Projecting forward to the year 2020, mobile-source VOC emissions are predicted to produce ~3 tons of the ground level peak O(3)(8-h average) and livestock feed VOC emissions are predicted to contribute ~2.5 tons making these sources nearly equivalent.

  7. Effect of liquefied petroleum gas on ozone formation in Guadalajara and Mexico City.

    PubMed

    Jaimes-López, J Luis; Sandoval-Fernández, Julio; González-Ortíz, Emmanuel; Vázquez-García, Marcos; González-Macías, Uriel; Zambrano-García, Angel

    2005-06-01

    Leakages of liquefied petroleum gas (LPG) are suspected to contribute greatly to ozone (O3) formation in Mexico City. We tested such a hypothesis by outdoor captive-air irradiation (CAI) experiments in the two largest Mexican metropolitan areas: Guadalajara (GMA) in 1997 and Mexico City (MCMA) in 2000. O3 was monitored in each city for 20 days (8:00 a.m.-6:00 p.m.) in smog chambers containing unaltered morning air or morning air enriched with either commercial LPG or LPG synthetic mixture 60/40 (propane and butane). Tested additions of both components were 35% (by volume) in GMA and 60% (by volume) in MCMA. The addition effects on O3 (max) were compared with effects from diluting LPG components or total nonmethane hydrocarbons (tNMHCs) by 50%. Diluting tNMHCs had the greatest absolute effect at both cities: it lowered O3 (max) by 24% in GMA and 55% in MCMA. Adding commercial LPG increased O3 (max) by 6% in GMA and 28% in MCMA; whereas adding LPG synthetic mixture 60/40 caused a similar increase in O3 (max), 4 and 21% in GMA and MCMA, respectively. Compared with dilution of tNMHCs, dilution of LPG-associated compounds had a smaller decreasing effect on O3 (max), only 4% in GMA and 15% in MCMA. These results show that commercial LPG and LPG synthetic mixture 60/40 affect O3 formation to a lesser extent than estimated previously.

  8. [Chemical Loss of Volatile Organic Compounds and Its Impact on the Formation of Ozone in Shanghai].

    PubMed

    Wang, Hong-li

    2015-09-01

    The spatial characterization of ozone (O3) and its precursors was studied based on the field measurements in urban and rural areas of Shanghai during the summer of 2014. The chemical loss of volatile organic compounds (VOCs) was estimated by the parameterization method. The mixing ratio of VOCs was 20 x 10(-9) in urban area and 17 x 10(-9) in the west rural area during the measurements. The average values of the maximum incremental reactivity were comparable in urban and rural areas, namely 5. 0 mol.mol-1 (O3/VOCs). By contrast, the chemical loss of VOCs was 8. 3 x 10(-9) in west rural area, which was two times as that in urban area. The more chemical loss of VOCs was probably one of the important reasons leading to the higher O3 concentration in west rural area. The regional transport might be important reason of the variation of O3 in the eastern coastal rural area. The chemical loss of VOCs showed good agreement with the local formation of O3 in both urban and rural areas, suggesting a similar efficiency of O3 formation from the chemical loss of VOCs. Among the chemical loss, aromatics and alkenes are the dominant VOC species of the atmospheric chemistry which accounts for more than 90% . The diurnal profile of VOC chemical loss matched well with the production of O3 with one-hour postponement.

  9. Formation of the Antarctic ozone hole by the ClO dimer mechanism

    NASA Technical Reports Server (NTRS)

    Barrett, J. W.; Solomon, P. M.; De Zafra, R. L.; Jaramillo, M.; Emmons, L.

    1988-01-01

    New measurements of the low-altitude ClO profile, made during September 1987, are presented along with detailed observations of ozone depletion over McMurdo Station, Antarctica during the same period. The results show that both the rate and altitude range of ozone depletion can be quantitatively accounted for by a mechanism in which the ClO dimer is the important intermediary in the catalytic destruction of ozone. An alternative bromine mechanism appears capable of contributing only 5-15 percent to the ozone loss rate.

  10. 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.

  11. Explicit photochemical mechanism for atmospheric oxidation of n-butane

    SciTech Connect

    Wen, L.

    1992-01-01

    Alkanes, being an important component of atmosphere, serve as precursors to ozone formation in urban and rural air masses. An explicit photochemical oxidation mechanism for n-butane, which is the major hydrocarbon component of automobile exhaust, is created in this work. The yields of organic nitrates from n-butane, n-pentane, and methyl ethyl ketone photooxidations were studied in Teflon bag and smog chamber experiments. Comparing with the expression currently using the most atmospheric model studies, the total butyl nitrates yield obtained in this work is about 36% lower, and the ratio of primary to secondary butyl nitrates is slightly higher. It is shown in this work that the yields of hydroxyl and carbonyl butyl nitrates are very low, and can be ignored in the explicit photochemical mechanisms. The explicit photochemical oxidation mechanism for methyl ethyl ketone (MEK) was created first because it is the major product from photooxidation of n-butane. The explicit photochemical oxidation mechanism for n-butane, created later, draws on the MEK mechanism. The mechanisms were tested by comparing model predictions with experimental observations from smog chamber experiments. The comparisons were conducted for species which had experimental observation data, such as O[sub 3], NO, and NO[sub 2], n-butane, MEK, organic nitrates, and aldehydes species. The sixteen smog chamber experiments, used in model simulations, were conducted during 1978 to 1992. The mechanisms are mainly based on the available kinetic data in literature and the experimental result in this work. The rate constants for some reactions in the mechanisms were adjusted to make a better fit with the experimental observations. These reactions were: reaction of OH and n-butane to form secondary butyl peroxy radical, decomposition of secondary butoxy radical, and reaction of OH and MEK.

  12. Ozone in rural areas of the United States

    NASA Astrophysics Data System (ADS)

    Logan, Jennifer A.

    1989-06-01

    I present the results of an analysis of ozone data from rural locations in the United States. Ozone concentrations above 80 ppb are common in the east in spring and summer, but they are unusual in the west, and ozone shows considerably more day-to-day variability in the east. Variations in ozone levels are highly correlated over distances of several hundred kilometers in the east, indicating that high values are associated with episodes of large spatial scale, >600,000 km2. There were 10 and seven such episodes in 1978 and 1979 respectively, between the months of April and September; they persisted for 3-4 days, on average, with a range of 2-8 days, and were most common in June. Daily maximum ozone values exceeded 90 ppb at over half the sites during these episodes and were often greater than 120 ppb at one or more sites. An analysis of the meteorology for each episode shows that they occurred preferentially in the presence of weak, slow-moving, and persistent high-pressure systems. Two episodes that occurred outside the summer half of the year were associated with unseasonably warm weather; only one episode, in March 1978, appeared to reflect a major stratospheric intrusion. Concentrations of NOx at rural locations in the east are frequently high enough (>1 ppb) to permit significant photochemical formation of ozone. It is clear that rural ozone in the east in spring and summer is severely impacted by anthropogenic emissions of NOx and hydrocarbons, and that ozone episodes occur when the weather is particularly conducive to photochemical formation of ozone. Ozone episodes were present on 23% of days in May-August in the east in 1978-1979. The effect of these pollution episodes on vegetation cannot be assessed with current information on dose-response characteristics, which is based primarily on exposure of crops to a given level of ozone for 7 hours a day. The results presented here may be used to design studies that account for the periodic exposure of vegetation

  13. Mass-dependent and non-mass-dependent isotope effects in ozone photolysis: Resolving theory and experiments

    SciTech Connect

    Cole, Amanda S.; Boering, Kristie A.

    2006-11-14

    In addition to the anomalous {sup 17}O and {sup 18}O isotope effects in the three-body ozone formation reaction O+O{sub 2}+M, isotope effects in the destruction of ozone by photolysis may also play a role in determining the isotopic composition of ozone and other trace gases in the atmosphere. While previous experiments on ozone photolysis at 254 nm were interpreted as evidence for preferential loss of light ozone that is anomalous (or 'non-mass-dependent'), recent semiempirical theoretical calculations predicted a preferential loss of heavy ozone at that wavelength that is mass dependent. Through photochemical modeling results presented here, we resolve this apparent contradiction between experiment and theory. Specifically, we show that the formation of ozone during the UV photolysis experiments is not negligible, as had been assumed, and that the well-known non-mass-dependent isotope effects in ozone formation can account for the non-mass-dependent enrichment of the heavy isotopologs of ozone observed in the experiment. Thus, no unusual non-mass-dependent fractionation in ozone photolysis must be invoked to explain the experimental results. Furthermore, we show that theoretical predictions of a mass-dependent preferential loss of the heavy isotopologs of ozone during UV photolysis are not inconsistent with the experimental data, particularly if mass-dependent isotope effects in the chemical loss reactions of ozone during the photolysis experiments or experimental artifacts enrich the remaining ozone in {sup 17}O and {sup 18}O. Before the calculated fractionation factors can be quantitatively evaluated, however, further investigation of possible mass-dependent isotope effects in the reactions of ozone with O({sup 1}D), O({sup 3}P), O{sub 2}({sup 1}{delta}), and O{sub 2}({sup 1}{sigma}) is needed through experiments we suggest here.

  14. Characterization of ozone precursors in a regional background site of the Pearl River Delta by time series observation of non-methane hydrocarbons

    NASA Astrophysics Data System (ADS)

    Chang, C.; Wang, J.; Liu, S. C.; Lai, C.; Shao, M.; Zeng, L.; Zhang, Y.

    2009-12-01

    Continuous hourly measurements of C3-C12 non-methane hydrocarbons (NMHCs) were carried out in the period July 3 - 30, 2006 at a downwind site of Peal River Delta during the PRIDE-PRD2006 campaign. The measurements were intended to characterize the “residual composition” of ozone precursors through photochemical processing and to evaluate the photochemical relationship between oxidant (O3+NO2) and its precursors. An observation based method (OBM) of consumption concept is used to generate an ozone isopleth diagram that resembles the EKMA diagram, to examine the relationship of oxidant versus ozone precursors. A critical step in the method is to use observed concentrations of ethylbenzene and m,p-xylenes to estimate the degree of photochemical processing and amounts of photochemically consumed NOx and NMHCs by OH. The 3D OBM ozone isopleth diagram indicates that the observed oxidant level was sensitive to both of the consumed amounts of NMHCs and NOx. In addition, based on the 577 samples analyzed, toluene, benzene, isoprene, xylene and C3-C5 alkanes were found to be the most elevated species accounting for around 55% of the total measured NMHC abundance. After considering both the photochemical reactivities and mixing ratios of all the measured species, CO, isoprene, propene, xylene and toluene were calculated to have the highest ozone formation potentials (OFPs) accounting for 76.5% of total reactivity. Good correlation between NMHCs and 3-methylpentane, a proven good vehicular indicator, suggests vehicular emissions should be the major source for anthropogenic NMHCs. No correlation was found between isoprene and anthropogenic NMHCs, clearly supporting the existence of isoprene’s non-anthropogenic sources. Moreover, its diurnal pattern showed maximum mixing ratios around midday hours and minima at night, reflecting its biogenic properties which are both solar radiation and temperature dependent. Keywords: Age indicator; photochemical aging; NOx-control regime

  15. A reevaluation of the ozone budget with HALOE UARS data: No evidence for the ozone deficit

    SciTech Connect

    Crutzen, P.J.; Groob, J.U.; Bruehl, C.; Mueller, R.; Russell, J.M. III

    1995-05-05

    Recently, additional ozone production mechanisms have been proposed to resolve the ozone deficit problem, which arises from greater ozone destruction than production in several photochemical models of the upper stratosphere and lower mesosphere. A detailed ozone model budget analysis was performed with simultaneous observations of O{sub 3}, HCl, H{sub 2}O, CH{sub 4}, NO, and NO{sub 2} from the Halogen Occultation Experiment (HALOE) on the Upper Atmosphere Research Satellite (UARS) under conditions with the strongest photochemical control of ozone. The results indicate that an ozone deficit may not exist. On the contrary, the use of currently recommended photochemical parameters leads to insufficient ozone destruction in the model. 30 refs., 3 figs., 1 tab.

  16. Influence of ozone concentration and temperature on ultra-fine particle and gaseous volatile organic compound formations generated during the ozone-initiated reactions with emitted terpenes from a car air freshener.

    PubMed

    Lamorena, Rheo B; Lee, Woojin

    2008-10-30

    Experiments were conducted to identify the emissions from the car air freshener and to identify the formation of ultra-fine particles and secondary gaseous compounds during the ozone-initiated oxidations with emitted volatile organic compounds (VOCs). The identified primary constituents emitted from the car air freshener in this study were alpha-pinene, beta-pinene, p-cymene, and limonene. Formation of ultra-fine particles (4.4-160 nm) was observed when ozone was injected into the chamber containing emitted monoterpenes from the air freshener. Particle number concentrations, particle mass concentrations, and surface concentrations were measured in time dependent experiments to describe the particle formation and growth within the chamber. The irritating secondary gaseous products formed during the ozone-initiated reactions include formaldehyde, acetaldehyde, acrolein, acetone, and propionaldehyde. Ozone concentration (50 and 100 ppb) and temperature (30 and 40 degrees C) significantly affect the formation of particles and gaseous products during the ozone-initiated reactions. The results obtained in this study provided an insight on the potential exposure of particles and irritating secondary products formed during the ozone-initiated reaction to passengers in confined spaces.

  17. 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

  18. Simulation of the ozone formation in the northern part of the Po Valley

    NASA Astrophysics Data System (ADS)

    Martilli, A.; Neftel, A.; Favaro, G.; Kirchner, F.; Sillman, S.; Clappier, A.

    2002-11-01

    The formation of photooxidants and aerosols in the Milan area (Po Valley, Italy) has been simulated for 13 May 1998 with an Eulerian model. The high-pressure conditions and the weak synoptic circulation favor the formation of strongly enhanced photooxidants and aerosol levels downwind of the metropolitan area of Milan. The polluted air masses are transported northward where the highest ozone (O3) concentrations of up to 200 ppb are reached 30 to 40 km away from the city center of Milan. The core of the Milan plume has an extension of only 10 km in length and 15 km in width at 1600 LT. The focus of the simulation was the sensitivity of the O3 formation to the reduction of nitrogen oxides (NOx) and volatile organic compounds (VOC) emissions. The model results are compared to the measurements in order to evaluate the quality of the simulation. The spatial and temporal variations of the concentrations of O3 and other trace compounds are reasonably well reproduced. Several reasons for systematic deviations have been analyzed in order to understand their possible influence on the sensitivity analysis. Moreover, the simulation showed that indicator species such as the H2O2/HNO3 or O3/NOy ratio could be applied to characterize the VOC/NOx regime of the O3 production in the Milan area, but that it is necessary to modify the indicator ratios to include the aerosol nitrate. Highest O3 values appear at the transition from VOC to NOx sensitivity approximately 30 km downwind of the highest emissions.

  19. 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 ...

  20. 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 ...

  1. Formation and transport of secondary air pollutants: ozone and aerosols in the St. Louis urban plume.

    PubMed

    White, W H; Anderson, J A; Blumenthal, D L; Husar, R B; Gillani, N V; Husar, J D; Wilson, W E

    1976-10-08

    Emissions from metropolitan St. Louis caused reduced visibilities and concentrations of ozone in excess of the federal ambient standard (0.08 part per million) 160 kilometers or more downwind of the city on 18 July 1975. Atmospheric production of ozone and visibility-reducing aerosols continues long after their primary precursors have been diluted to low concentrations.

  2. Photochemical Formation of Hydroxyl Radical in Red-Soil-Polluted Seawater in Okinawa, Japan -Potential Impacts on Marine Organisms

    NASA Astrophysics Data System (ADS)

    Arakaki, T.; Hamdun, A. M.; Okada, K.; Kuroki, Y.; Ikota, H.; Fujimura, H.; Oomori, T.

    2004-12-01

    Development of pineapple farmlands and construction of recreational facilities caused runoff of red soil into coastal ocean (locally termed as red-soil-pollution) in the north of Okinawa Island, Japan. In an attempt to understand the impacts of red soil on oxidizing power of the seawater, we studied formation of hydroxyl radical (OH radical), the most potent oxidant in the environment, in red-soil-polluted seawaters, using 313 nm monochromatic light. Photo-formation rates of OH radical showed a good correlation with dissolved iron concentrations (R = 0.98). The major source of OH radical was found to be the Fenton reaction (a reaction between Fe(II) and HOOH). The un-filtered red-soil-polluted seawater samples exhibited faster OH radical formation rates than the filtered samples, suggesting that iron-bearing red soil particles enhanced formation of OH radical.

  3. Air Quality Modeling of Ozone Radical Precursors in Houston

    NASA Astrophysics Data System (ADS)

    Rappenglueck, B.; Czader, B.; Li, X.

    2013-05-01

    The Houston-Galveston area has one of the highest ozone concentrations in the U.S., often exceeding the U.S. National Ambient Air Quality Standard for ozone. Photochemical modeling of ozone formation in the Houston area generally underestimates the concentrations of free radical precursors contributing to ozone formation. Here we present modeling results using the Weather Research Forecast - Community Multiscale Air Quality (WRF-CMAQ) modeling system for the Houston-Galveston area. Meteorological parameters predicted by WRF are well simulated most of the time, including planetary boundary layer heights. Air quality simulations for the Houston-Galveston-Brazoria area using the combined WRF-SMOKE-CMAQ system showed overall good results for ozone and many other trace gases. HONO morning peaks are no longer underpredicted, on some occasions they are slightly overpredicted, which can be linked to NO2 overprediction. However, CMAQ mispredicts other trace gases like HO2, H2O2 and CH3OOH concentrations. The WRF-SMOKE-CMAQ system was also used to elucidate the relative importance of various photolysis processes as radical sources in the Houston atmosphere. Morning HOx formation is dominated by HONO while ozone contributes the most during midday. HONO contribution to HOx formation is more pronounced at the surface layer where most of it is formed. On the other hand, radical production from ozone is more important at elevated levels where higher concentrations of ozone are observed. Formaldehyde contributes up to 40% and also peaks during mid-day, but on days when high morning concentrations of formaldehyde are observed its contribution to HOx in the morning exceeds that of ozone. Photolysis of H2O2 is a minor contributor to radical levels. The process analysis tool available in CMAQ was utilized to analyze photochemical processes leading to ozone production and chemical transformations along trajectories linking a site at the Houston Ship Channel and the University of

  4. Characterizing the ozone formation potential of agricultural sources in California's San Joaquin Valley: A computational and experimental approach

    NASA Astrophysics Data System (ADS)

    Howard, Cody Jerome

    The global pattern of expanding urban centers and increasing agricultural intensity is leading to more frequent interactions between air pollution emissions from urban and agricultural sources. The confluence of these emissions that traditionally have been separated by hundreds of kilometers is creating new air quality challenges in numerous regions across the United States. An area of particular interest is California's San Joaquin Valley (SJV), which has an agricultural output higher than many countries, a rapidly expanding human population, and ozone concentrations that are already higher than many dense urban areas. New regulations in the SJV restrict emissions of reactive organic gases (ROG) from animal sources in an attempt to meet Federal and State ozone standards designed to protect human health. A transportable "smog" chamber was developed and tested to directly measure the ozone formation potential of a variety of agricultural emissions in representative urban and rural atmospheres. After validation of the experimental procedure, four animal types were examined: beef cattle, dairy cattle, swine, and poultry, as well as six commonly used animal feeds: cereal silage (wheat grain and oat grain), alfalfa silage, corn silage, high moisture ground corn, almond shells, almond hulls, and total mixed ration. The emitted ROG composition was also measured so that the theoretical incremental reactivity could be calculated for a variety of atmospheres and directly compared with the measured ozone formation potential (OFP) under the experimental conditions. A computational model was created based on a modified form of the Caltech Atmospheric Chemistry Mechanism and validated against experimental results. After validation, the computational model was used to predict OFP across a range of NOx and ROG concentrations. The ROG OFP measurements combined with adjusted agricultural ROG emissions inventory estimates were used to predict the actual ozone production in the SJV

  5. Catalysis of Photochemical Reactions.

    ERIC Educational Resources Information Center

    Albini, A.

    1986-01-01

    Offers a classification system of catalytic effects in photochemical reactions, contrasting characteristic properties of photochemical and thermal reactions. Discusses catalysis and sensitization, examples of catalyzed reactions of excepted states, complexing ground state substrates, and catalysis of primary photoproducts. (JM)

  6. Catalysis of Photochemical Reactions.

    ERIC Educational Resources Information Center

    Albini, A.

    1986-01-01

    Offers a classification system of catalytic effects in photochemical reactions, contrasting characteristic properties of photochemical and thermal reactions. Discusses catalysis and sensitization, examples of catalyzed reactions of excepted states, complexing ground state substrates, and catalysis of primary photoproducts. (JM)

  7. Kinetics of the formation of ozone and nitrogen oxides due to a pulsed microwave discharge in air

    NASA Astrophysics Data System (ADS)

    Larin, V. F.; Rumiantsev, S. A.

    1989-03-01

    The paper presents results of a numerical simulation of the kinetics of plasma-chemical processes induced by a single microwave pulse in the stratosphere. It is shown that the gas temperature is one of the main factors influencing the concentration ratio of ozone and nitrogen oxides formed under the effect of a microwave pulse. Long pulses, producing considerable gas heating, favor the formation of nitrogen oxides.

  8. Daytime ozone loss term in the mesopause region

    NASA Astrophysics Data System (ADS)

    Kulikov, Mikhail Y.; Belikovich, Mikhail V.; Grygalashvyly, Mykhaylo; Sonnemann, Gerd R.; Ermakova, Tatiana S.; Nechaev, Anton A.; Feigin, Alexander M.

    2017-05-01

    For the retrieval of atomic oxygen via ozone observations in the extended mesopause region under sunlight conditions, two assumptions are used: first, the photochemical equilibrium of ozone and, second, that the ozone losses are dominated by ozone's dissociation from solar UV radiation, silently ignoring the O3 destruction by atomic hydrogen. We verify both by 3-D modeling. We found that ozone approaches photochemical equilibrium at 75-100 km for daytime conditions. Hence, the first assumption is valid. However, the reaction of ozone with atomic hydrogen was found to be an important loss process and should not be omitted in retrieving atomic oxygen.

  9. Formation of haloacetic acids, halonitromethanes, bromate and iodate during chlorination and ozonation of seawater and saltwater of marine aquaria systems.

    PubMed

    Shi, Honglan; Qiang, Zhimin; Adams, Craig

    2013-03-01

    This manuscript addresses identification, analysis, formation and occurrence of key disinfection byproducts (DBPs) formed during chlorination and/or ozonation of both natural seawater (NSW), and synthetic high- and low-bromide saltwater (HBSW and LBSW, respectively). In this study, several groups of water disinfection byproducts were studied, including haloacetic acids (HAAs), halonitromethanes (HNMs), bromate and iodate. Three different water systems were studied including filtered natural seawater (NSW, ca. 64.9 mg L(-1) Br(-)), a high-bromide (Br(-)) saltwater (HBSW, ca. 24.8 mg L(-1) Br), and low-Br(-) saltwater (LBSW, ca. 4.3 mg L(-1)Br). Because ozone reacts with Cl(-) to form free chlorine in seawater and salt water systems, similar DBP patterns were observed for both chlorine and ozone oxidants. The results revealed that some HAAs and HNMs are formed at greater than 100 μg L(-1) concentrations and are greatly affected by water constituents and formulations when treated with chlorine and ozone. The results showed that in low-Br(-) water salt water, chlorinated HAAs and HNMs predominated, while much greater concentrations of brominated HAAs and HNMs were produced in both natural and synthetic higher Br(-) saltwater. Concentrations of bromate and iodate were strongly impacted by factors other than Br(-) and I(-) concentrations including whether the system was open or closed. Copyright © 2012 Elsevier Ltd. All rights reserved.

  10. 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).

  11. Summertime ozone formation in Xi'an and surrounding areas, China

    NASA Astrophysics Data System (ADS)

    Feng, Tian; Bei, Naifang; Huang, Ru-Jin; Cao, Junji; Zhang, Qiang; Zhou, Weijian; Tie, Xuexi; Liu, Suixin; Zhang, Ting; Su, Xiaoli; Lei, Wenfang; Molina, Luisa T.; Li, Guohui

    2016-04-01

    In this study, the ozone (O3) formation in China's northwest city of Xi'an and surrounding areas is investigated using the Weather Research and Forecasting atmospheric chemistry (WRF-Chem) model during the period from 22 to 24 August 2013, corresponding to a heavy air pollution episode with high concentrations of O3 and PM2.5. The model generally performs well compared to measurements in simulating the surface temperature, relative humidity, and wind speed and direction, near-surface O3 and PM2.5 mass concentrations, and aerosol constituents. High aerosol concentrations in Xi'an and surrounding areas significantly decrease the photolysis frequencies and can reduce O3 concentrations by more than 50 µg m-3 (around 25 ppb) on average. Sensitivity studies show that the O3 production regime in Xi'an and surrounding areas is complicated, varying from NOx to VOC (volatile organic compound)-sensitive chemistry. The industrial emissions contribute the most to the O3 concentrations compared to biogenic and other anthropogenic sources, but neither individual anthropogenic emission nor biogenic emission plays a dominant role in the O3 formation. Under high O3 and PM2.5 concentrations, a 50 % reduction in all the anthropogenic emissions only decreases near-surface O3 concentrations by about 14 % during daytime. The complicated O3 production regime and high aerosol levels pose a challenge for O3 control strategies in Xi'an and surrounding areas. Further investigation regarding O3 control strategies will need to be performed, taking into consideration the rapid changes in anthropogenic emissions that are not reflected in the current emission inventories and the uncertainties in the meteorological field simulations.

  12. 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.

  13. Ozone over the Western Mediterranean Sea - results from two years of shipborne measurements

    NASA Astrophysics Data System (ADS)

    Velchev, K.; Cavalli, F.; Hjorth, J.; Marmer, E.; Vignati, E.; Dentener, F.; Raes, F.

    2011-01-01

    Ozone, along with other air pollutants, has been measured for two years from a monitoring station placed on a cruise ship that follows a regular track in the Western Mediterranean between April and October. Conditions favouring high ozone levels have been studied by analysis of weather maps and back trajectories. This analysis was focused on a transect over the open sea in the South Western Mediterranean between Tunis and Palma de Mallorca. High ozone levels were found in situations with an anticyclonic circulation over the Western Mediterranean when subsidence brings air masses down from altitudes between 1000 and 3500 m a.s.l. Analysis of composite meteorological maps suggests a relevant contribution of breeze circulation to subsidence during events with high surface ozone concentrations; this points to an important contribution from local ozone formation. A detailed back trajectory analysis of the origin of air masses with high ozone concentrations was carried out for two "hot spots" for ozone pollution, in the Gulf of Genoa and between Naples and Palermo, respectively. The main cause of high ozone levels in the Gulf of Genoa was found to be outflow from the Po Valley and the Genoa area while such episodes along the Naples-Palermo transect were most often associated with trajectories from the Rome or Naples areas. Analysis of the relationship between measured concentrations of Black Carbon and ozone allowed to evaluate the degree of photochemical "ageing" of the air masses encountered along the route of the cruise ship.

  14. 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.

  15. 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

  16. Regulatory ozone modeling: status, directions, and research needs.

    PubMed Central

    Georgopoulos, P G

    1995-01-01

    The Clean Air Act Amendments (CAAA) of 1990 have established selected comprehensive, three-dimensional, Photochemical Air Quality Simulation Models (PAQSMs) as the required regulatory tools for analyzing the urban and regional problem of high ambient ozone levels across the United States. These models are currently applied to study and establish strategies for meeting the National Ambient Air Quality Standard (NAAQS) for ozone in nonattainment areas; State Implementation Plans (SIPs) resulting from these efforts must be submitted to the U.S. Environmental Protection Agency (U.S. EPA) in November 1994. The following presentation provides an overview and discussion of the regulatory ozone modeling process and its implications. First, the PAQSM-based ozone attainment demonstration process is summarized in the framework of the 1994 SIPs. Then, following a brief overview of the representation of physical and chemical processes in PAQSMs, the essential attributes of standard modeling systems currently in regulatory use are presented in a nonmathematical, self-contained format, intended to provide a basic understanding of both model capabilities and limitations. The types of air quality, emission, and meteorological data needed for applying and evaluating PAQSMs are discussed, as well as the sources, availability, and limitations of existing databases. The issue of evaluating a model's performance in order to accept it as a tool for policy making is discussed, and various methodologies for implementing this objective are summarized. Selected interim results from diagnostic analyses, which are performed as a component of the regulatory ozone modeling process for the Philadelphia-New Jersey region, are also presented to provide some specific examples related to the general issues discussed in this work. Finally, research needs related to a) the evaluation and refinement of regulatory ozone modeling, b) the characterization of uncertainty in photochemical modeling, and c

  17. Total ozone, ozone vertical distributions, and stratospheric temperatures at South Pole, Antarctica, in 1986 and 1987

    NASA Technical Reports Server (NTRS)

    Komhyr, W. D.; Grass, R. D.; Reitelbach, P. J.; Franchois, P. R.; Kuester, S. E.

    1988-01-01

    Seventy-six electrochemical cell (ECC) ozonesondes were flown at South Pole, Antarctica, during 1987 in a continuing program to document year-round changes in Antarctica ozone that are dynamically and photochemically induced. Dobson spectrophotometer total ozone observations were also made. For the twilight months of March and September when Dobson instrument observations cannot be made at South Pole, total ozone amounts were deduced from the ECC ozonesonde soundings. ECC sonde total ozone data obtained during the polar night (April to August), supplemented the sparse total ozone data obtained from Dobson instrument moon observations. Similar ozone profile and total ozone observations were made at South Pole in 1986.

  18. Ozone formation along the California-Mexican border region during Cal-Mex 2010 field campaign

    NASA Astrophysics Data System (ADS)

    Li, Guohui; Bei, Naifang; Zavala, Miguel; Molina, Luisa T.

    2014-05-01

    The purpose of this study is to evaluate the ozone (O3) formation along the California-Mexico border region using the WRF-CHEM model in association with the Cal-Mex 2010 field campaign. Four two-day episodes in 2010 are chosen based on plume transport patterns: 1) May 15-16 (plume north), 2) May 29-30 (plume southwest), 3) June 4-5 (plume east), and 4) June 13-14 (plume southeast). Generally, the predicted O3 spatial patterns and temporal variations agree well with the observations at the ambient monitoring sites in the San Diego-Tijuana region, but in the Calexico-Mexicali region, the model frequently underestimates the observation. In the San Diego-Tijuana region, the morning anthropogenic precursor emissions in the urbanized coastal plain are carried inland and mixed with the local biogenic emissions during transport, causing the high O3 level over the mountain region. Biogenic emissions enhance the O3 concentrations by up to 40 ppb over the mountain region in the afternoon. The factor separation approach is used to evaluate the contributions of trans-boundary transport of emissions from California and Baja California to the O3 level in the California-Mexico border region. The Baja California emissions play a minor role in the O3 formation in the San Diego region and do not seem to contribute to the O3 exceedances in the region, but have large potential to cause O3 exceedances in the Calexico region. The California emissions can considerably enhance the O3 level in the Tijuana region. Generally, the California emissions play a more important role than the Baja California emissions on O3 formation in the border region (within 40 km to the California-Mexico border). On average, the O3 concentrations in the border region are decreased by 2-4 ppb in the afternoon due to the interactions of emissions from California and Baja California. Further studies need to be conducted to improve the sea breeze simulations in the border region for evaluating O3 formation.

  19. 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.

  20. Ozone Formation Potentials from Different Anthropogenic Emission Sources of Volatile Organic Compounds in California's South Coast Air Basin

    NASA Astrophysics Data System (ADS)

    Chen, J.; Luo, D.; Croes, B.

    2010-12-01

    Different volatile organic compounds (VOC) exhibit different propensities for ozone formation. Two approaches were used to study the relative ozone formation potentials (source reactivities) of different anthropogenic VOC emission source categories in California’s South Coast Air Basin (SoCAB). The first approach combined emission speciation profiles for total organic gases (TOG) with maximum incremental reactivity (MIR) scales for VOC species. The second approach quantified ozone impacts from different sources by performing 3-dimensional air quality model sensitivity analyses involving increased TOG emissions from particular sources. The source reactivities for 58 VOC emission categories in SoCAB derived from these two approaches agree reasonably well (R2 = ~0.9). Both approaches revealed the two emissions source types with the highest TOG reactivity were mobile sources and managed forest burning. Also, a reactivity-based TOG emission inventory for SoCAB in 2005 was produced by combining the source reactivities from both approaches with TOG emissions from anthropogenic source categories. The top five reactivity-based source categories are: light-duty passenger cars, off-road equipments, consumer products, light-duty trucks, and recreational boats. This is in contrast to the mass-based TOG emission inventory, which indicates that farming operations (mainly from animal waste) was one of the five largest mass-based anthropogenic TOG emission sources. Compared to the mass-based TOG emission inventory, the reactivity-based TOG emission inventory more appropriately represents the ozone formation potentials from emission sources, and highlights those sources that should be targeted for future regulations.

  1. Ozone formation potentials of organic compounds from different emission sources in the South Coast Air Basin of California

    NASA Astrophysics Data System (ADS)

    Chen, Jianjun; Luo, Dongmin

    2012-08-01

    Different organic compounds exhibit different propensities for ozone formation. Two approaches were used to study the ozone formation potentials or source reactivities of different anthropogenic organic compounds emission categories in California's South Coast Air Basin (SoCAB). The first approach was based on the combination of total organic gases (TOG) emission speciation profiles and the maximum incremental reactivity (MIR) scale of organic species. The second approach quantified ozone impacts from different emission sources by performing 3-dimensional air quality model sensitivity analysis involving increased TOG emissions from particular sources. The source reactivities derived from these two approaches agree reasonably well for 58 anthropogenic organic compounds emission categories in the SoCAB. Both approaches identify TOG emissions from mobile sources as having the highest reactivity. Source reactivities from both approaches were also combined with TOG emissions from each source category to produce a 2005 reactivity-based anthropogenic TOG emission inventory for the SoCAB. The top five reactivity-based anthropogenic TOG emission sources in the SoCAB during 2005 were: light-duty passenger cars, off-road equipment, consumer products, light-duty trucks category 2 (i.e., 3751-5750 lb), and recreational boats. This is in contrast to the mass-based TOG emission inventory, which indicates that livestock waste and composting emission categories were two of the five largest mass-based anthropogenic TOG emission sources. The reactivity-based TOG emission inventory is an important addition to the mass-based TOG emission inventory because it represents the ozone formation potentials from emission sources and can be used to assist in determining targeted sources for developing organic compounds reduction policies.

  2. Photochemical oxidants: state of the science.

    PubMed

    Kley, D; Kleinmann, M; Sanderman, H; Krupa, S

    1999-01-01

    Atmospheric photochemical processes resulting in the production of tropospheric ozone (O(3)) and other oxidants are described. The spatial and temporal variabilities in the occurrence of surface level oxidants and their relationships to air pollution meteorology are discussed. Models of photooxidant formation are reviewed in the context of control strategies and comparisons are provided of the air concentrations of O(3) at select geographic locations around the world. This overall oxidant (O(3)) climatology is coupled to human health and ecological effects. The discussion of the effects includes both acute and chronic responses, mechanisms of action, human epidemiological and plant population studies and briefly, efforts to establish cause-effect relationships through numerical modeling. A short synopsis is provided of the interactive effects of O(3) with other abiotic and biotic factors. The overall emphasis of the paper is on identifying the current uncertainties and gaps in our understanding of the state of the science and some suggestions as to how they may be addressed.

  3. Secondary organic aerosol formation from photochemical aging of light-duty gasoline vehicle exhausts in a smog chamber

    NASA Astrophysics Data System (ADS)

    Liu, T.; Wang, X.; Deng, W.; Hu, Q.; Ding, X.; Zhang, Y.; He, Q.; Zhang, Z.; Lü, S.; Bi, X.; Chen, J.; Yu, J.

    2015-04-01

    In China, fast increase in passenger vehicles has procured the growing concern about vehicle exhausts as an important source of anthropogenic secondary organic aerosols (SOA) in megacities hard-hit by haze. However, there are still no chamber simulation studies in China on SOA formation from vehicle exhausts. In this study, the SOA formation of emissions from two idling light-duty gasoline vehicles (LDGVs) (Euro 1 and Euro 4) in China was investigated in a 30 m3 smog chamber. Five photo-oxidation experiments were carried out at 25 °C with the relative humidity around 50%. After aging at an OH exposure of 5 × 106 molecules cm-3 h, the formed SOA was 12-259 times as high as primary OA (POA). The SOA production factors (PF) were 0.001-0.044 g kg-1 fuel, comparable with those from the previous studies at the quite similar OH exposure. This quite lower OH exposure than that in typical atmospheric condition might however lead to the underestimation of the SOA formation potential from LDGVs. Effective SOA yield data in this study were well fit by a one-product gas-particle partitioning model and quite lower than those of a previous study investigating SOA formation form three idling passenger vehicles (Euro 2-Euro 4). Traditional single-ring aromatic precursors and naphthalene could explain 51-90% of the formed SOA. Unspeciated species such as branched and cyclic alkanes might be the possible precursors for the unexplained SOA. A high-resolution time-of-flight aerosol mass spectrometer was used to characterize the chemical composition of SOA. The relationship between f43 (ratio of m/z 43, mostly C2H3O+, to the total signal in mass spectrum) and f44 (mostly CO2+) of the gasoline vehicle exhaust SOA is similar to the ambient semi-volatile oxygenated organic aerosol (SV-OOA). We plot the O : C and H : C molar ratios of SOA in a Van Krevelen diagram. The slopes of ΔH : C/ΔO : C ranged from -0.59 to -0.36, suggesting that the oxidation chemistry in these experiments was a

  4. Uncertainty Analysis of Ozone Formation and Response to Emission Controls Using Higher-Order Sensitivities

    EPA Science Inventory

    Understanding ozone response to its precursor emissions is crucial for effective air quality management practices. This nonlinear response is usually simulated using chemical transport models, and the modeling results are affected by uncertainties in emissions inputs. In this stu...

  5. Uncertainty Analysis of Ozone Formation and Response to Emission Controls Using Higher-Order Sensitivities

    EPA Science Inventory

    Understanding ozone response to its precursor emissions is crucial for effective air quality management practices. This nonlinear response is usually simulated using chemical transport models, and the modeling results are affected by uncertainties in emissions inputs. In this stu...

  6. Ozone uptake and formation of reactive oxygen intermediates on glassy, semi-solid and liquid organic matter

    NASA Astrophysics Data System (ADS)

    Berkemeier, Thomas; Steimer, Sarah S.; Krieger, Ulrich K.; Peter, Thomas; Pöschl, Ulrich; Ammann, Markus; Shiraiwa, Manabu

    2016-04-01

    Heterogeneous and multiphase reactions of ozone are important pathways for chemical ageing of atmospheric organic aerosols (Abbatt, Lee and Thornton, 2012). The effects of particle phase state on the reaction kinetics are still not fully elucidated and cannot be described by classical models assuming a homogeneous condensed phase (Berkemeier et al., 2013). We apply a kinetic multi-layer model, explicitly resolving gas adsorption, condensed phase diffusion and condensed phase chemistry (Shiraiwa et al., 2010), to systematic measurements of ozone uptake onto proxies for secondary organic aerosols (SOA). Our findings show how moisture-induced phase changes affect the gas uptake and chemical transformation of organic matter through change in the physicochemical properties of the substrate: the diffusion coefficients are found to be low under dry conditions, but increase by several orders of magnitude toward higher relative humidity (RH). The solubility of ozone in the dry organic matrix is found to be one order of magnitude higher than in the dilute aqueous solution. The model simulations reveal that at high RH, ozone uptake is mainly controlled by reaction throughout the particle bulk, whereas at low RH, bulk diffusion is retarded severely and reaction at the surface becomes the dominant pathway, with ozone uptake being limited by replenishment of unreacted organic molecules from the bulk phase. The experimental results can only be reconciled including a pathway for ozone self-reaction, which becomes especially important under dry and polluted conditions. Ozone self-reaction can be interpreted as formation and recombination of long-lived reactive oxygen intermediates at the aerosol surface, which could also explain several kinetic parameters and has implications for the health effects of organic aerosol particles. This study hence outlines how kinetic modelling can be used to gain mechanistic insight into the coupling of mass transport, phase changes, and chemical

  7. Ozone inhibits endothelial cell cyclooxygenase activity through formation of hydrogen peroxide.

    PubMed

    Madden, M C; Eling, T E; Friedman, M

    1987-09-01

    We have previously demonstrated that a 2H exposure of cultured pulmonary endothelial cells to ozone (0.0-1.0 ppm) in-vitro resulted in a concentration-dependent reduction of endothelial prostacyclin production (90% decrease at the 1.0 ppm level). Ozone-exposed endothelial cells, incubated with 20 uM arachidonate, also demonstrated a significant inhibition of prostacyclin synthesis. To further examine the mechanisms of the inhibition of prostacyclin synthesis, bovine pulmonary endothelial cells were exposed to 1.0 ppm ozone for 2H. A significant decrease in prostacyclin synthesis was found within 5 min of exposure (77 +/- 36% of air-exposed control values, p less than 0.05). Endothelial prostacyclin synthesis returned to baseline levels by 12H after ozone exposure, a time point which was similar to the recovery time of unexposed endothelium treated with 0.5 uM acetylsalicylic acid. Incubation of endothelial cells, previously exposed to 1.0 ppm ozone for 2 hours, with 4 uM PGH2 resulted in restoration of essentially normal prostacyclin synthesis. When endothelial cells were co-incubated with catalase (5 U/ml) during ozone exposure, no inhibition of prostacyclin synthesis was observed. Co-incubation with either heat-inactivated catalase or superoxide dismutase (10 U/ml) did not affect the ozone-induced inhibition of prostacyclin synthesis. These data suggest that H2O2 is a major toxic species produced in endothelial cells during ozone exposure and responsible for the inhibition of endothelial cyclooxygenase activity.

  8. Ozone inhibits endothelial cell cyclooxygenase activity through formation of hydrogen peroxide

    SciTech Connect

    Madden, M.C.; Eling, T.E.; Friedman, M.

    1987-09-01

    We have previously demonstrated that a 2H exposure of cultured pulmonary endothelial cells to ozone (0.0-1.0 ppm) in-vitro resulted in a concentration-dependent reduction of endothelial prostacyclin production (90% decrease at the 1.0 ppm level). Ozone-exposed endothelial cells, incubated with 20 uM arachidonate, also demonstrated a significant inhibition of prostacyclin synthesis. To further examine the mechanisms of the inhibition of prostacyclin synthesis, bovine pulmonary endothelial cells were exposed to 1.0 ppm ozone for 2H. A significant decrease in prostacyclin synthesis was found within 5 min of exposure (77 +/- 36% of air-exposed control values, p less than 0.05). Endothelial prostacyclin synthesis returned to baseline levels by 12H after ozone exposure, a time point which was similar to the recovery time of unexposed endothelium treated with 0.5 uM acetylsalicylic acid. Incubation of endothelial cells, previously exposed to 1.0 ppm ozone for 2 hours, with 4 uM PGH2 resulted in restoration of essentially normal prostacyclin synthesis. When endothelial cells were co-incubated with catalase (5 U/ml) during ozone exposure, no inhibition of prostacyclin synthesis was observed. Co-incubation with either heat-inactivated catalase or superoxide dismutase (10 U/ml) did not affect the ozone-induced inhibition of prostacyclin synthesis. These data suggest that H/sub 2/O/sub 2/ is a major toxic species produced in endothelial cells during ozone exposure and responsible for the inhibition of endothelial cyclooxygenase activity.

  9. Sensitivities of ozone and fine particulate matter formation to emissions under the impact of potential future climate change.

    PubMed

    Liao, Kuo-Jen; Tagaris, Efthimios; Manomaiphiboon, Kasemsan; Napelenok, Sergey L; Woo, Jung-Hun; He, Shan; Amar, Praveen; Russell, Armistead G

    2007-12-15

    Impact of climate change alone and in combination with currently planned emission control strategies are investigated to quantify effectiveness in decreasing regional ozone and PM2.5 over the continental U.S. using MM5, SMOKE, and CMAQ with DDM-3D. Sensitivities of ozone and PM2.5 formation to precursor emissions are found to change only slightly in response to climate change. In many cases, mass per ton sensitivities to NO(x) and SO2 controls are predicted to be greater in the future due to both the lower emissions as well as climate, suggesting that current control strategies based on reducing such emissions will continue to be effective in decreasing ground-level ozone and PM2.5 concentrations. SO2 emission controls are predicted to be most beneficial for decreasing summertime PM2.5 levels, whereas controls of NO(x) emissions are effective in winter. Spatial distributions of sensitivities are also found to be only slightly affected assuming no changes in land-use. Contributions of biogenic VOC emissions to PM2.5 formation are simulated to be more important in the future because of higher temperatures, higher biogenic emissions, and lower anthropogenic NO(x) and SO2 emissions.

  10. Simulated changes in biogenic VOC emissions and ozone formation from habitat expansion of Acer Rubrum (red maple)

    DOE PAGES

    Drewniak, Beth A.; Snyder, Peter K.; Steiner, Allison L.; ...

    2014-01-17

    A new vegetation trend is emerging in northeastern forests of the United States, characterized by an expansion of red maple at the expense of oak. This has changed emissions of biogenic volatile organic compounds (BVOCs), primarily isoprene and monoterpenes. Oaks strongly emit isoprene while red maple emits a negligible amount. This species shift may impact nearby urban centers because the interaction of isoprene with anthropogenic nitrogen oxides can lead to tropospheric ozone formation and monoterpenes can lead to the formation of particulate matter. Here in this study the Global Biosphere Emissions and Interactions System was used to estimate the spatialmore » changes in BVOC emission fluxes resulting from a shift in forest composition between oak and maple. A 70% reduction in isoprene emissions occurred when oak was replaced with maple. Ozone simulations with a chemical box model at two rural and two urban sites showed modest reductions in ozone concentrations of up to 5–6 ppb resulting from a transition from oak to red maple, thus suggesting that the observed change in forest composition may benefit urban air quality. This study illustrates the importance of monitoring and representing changes in forest composition and the impacts to human health indirectly through changes in BVOCs.« less

  11. Simulated changes in biogenic VOC emissions and ozone formation from habitat expansion of Acer Rubrum (red maple)

    NASA Astrophysics Data System (ADS)

    Drewniak, Beth A.; Snyder, Peter K.; Steiner, Allison L.; Twine, Tracy E.; Wuebbles, Donald J.

    2014-01-01

    A new vegetation trend is emerging in northeastern forests of the United States, characterized by an expansion of red maple at the expense of oak. This has changed emissions of biogenic volatile organic compounds (BVOCs), primarily isoprene and monoterpenes. Oaks strongly emit isoprene while red maple emits a negligible amount. This species shift may impact nearby urban centers because the interaction of isoprene with anthropogenic nitrogen oxides can lead to tropospheric ozone formation and monoterpenes can lead to the formation of particulate matter. In this study the Global Biosphere Emissions and Interactions System was used to estimate the spatial changes in BVOC emission fluxes resulting from a shift in forest composition between oak and maple. A 70% reduction in isoprene emissions occurred when oak was replaced with maple. Ozone simulations with a chemical box model at two rural and two urban sites showed modest reductions in ozone concentrations of up to 5-6 ppb resulting from a transition from oak to red maple, thus suggesting that the observed change in forest composition may benefit urban air quality. This study illustrates the importance of monitoring and representing changes in forest composition and the impacts to human health indirectly through changes in BVOCs.

  12. Secondary organic aerosol formation from photochemical aging of light-duty gasoline vehicle exhausts in a smog chamber

    NASA Astrophysics Data System (ADS)

    Liu, T.; Wang, X.; Deng, W.; Hu, Q.; Ding, X.; Zhang, Y.; He, Q.; Zhang, Z.; Lü, S.; Bi, X.; Chen, J.; Yu, J.

    2015-08-01

    In China, a rapid increase in passenger vehicles has led to the growing concern of vehicle exhaust as an important source of anthropogenic secondary organic aerosol (SOA) in megacities hard hit by haze. In this study, the SOA formation of emissions from two idling light-duty gasoline vehicles (LDGVs) (Euro 1 and Euro 4) operated in China was investigated in a 30 m3 smog chamber. Five photo-oxidation experiments were carried out at 25 °C with relative humidity at around 50 %. After aging at an OH exposure of 5 × 106 molecules cm-3 h, the formed SOA was 12-259 times as high as primary organic aerosol (POA). The SOA production factors (PF) were 0.001-0.044 g kg-1 fuel, comparable with those from the previous studies at comparable OH exposure. This quite lower OH exposure than that in typical atmospheric conditions might however lead to the underestimation of the SOA formation potential from LDGVs. Effective SOA yields in this study were well fit by a one-product gas-particle partitioning model but quite lower than those of a previous study investigating SOA formation from three idling passenger vehicles (Euro 2-4). Traditional single-ring aromatic precursors and naphthalene could explain 51-90 % of the formed SOA. Unspeciated species such as branched and cyclic alkanes might be the possible precursors for the unexplained SOA. A high-resolution time-of-flight aerosol mass spectrometer was used to characterize the chemical composition of SOA. The relationship between f43 (ratio of m/z 43, mostly C2H3O+, to the total signal in mass spectrum) and f44 (mostly CO2+) of the gasoline vehicle exhaust SOA is similar to the ambient semi-volatile oxygenated organic aerosol (SV-OOA). We plot the O : C and H : C molar ratios of SOA in a Van Krevelen diagram. The slopes of ΔH : C / ΔO : C ranged from -0.59 to -0.36, suggesting that the oxidation chemistry in these experiments was a combination of carboxylic acid and alcohol/peroxide formation.

  13. Boundary-layer processes responsible for the formation of anomalous ozone profiles over the North Atlantic

    SciTech Connect

    Doran, J.C.; Zhong, S.; Berkowitz, C.M.

    1996-12-31

    In the summer of 1992, a series of ozone profiles were obtained with an airplane flying over the western North Atlantic Ocean as part of the North Atlantic Regional Experiment (NARE). Over the course of the experiment, ozone profiles with widely divergent characteristics were obtained, and concurrent measurements and analyses of meteorological data and other chemistry data suggested a number of mechanisms that could contribute to the observed behavior. In one intriguing category of ozone profiles observed on several days, the ozone values were generally low (<25--30 ppb) in the first 1--1.5 km above the surface but jumped rather sharply above that height to concentration values two or more times greater. These higher ozone values remained nearly constant to a height of approximately 2.5 km, the normal maximum sampling altitude for the airplane on these flights. The jump in ozone concentrations coincided closely with a sudden increase of potential temperature {theta}; below the level of the jump {theta} was nearly constant with height.

  14. The 2010 Antarctic ozone hole: observed reduction in ozone destruction by minor sudden stratospheric warmings.

    PubMed

    de Laat, A T J; van Weele, M

    2011-01-01

    Satellite observations show that the 2010 Antarctic ozone hole is characterized by anomalously small amounts of photochemical ozone destruction (40-60% less than the 2005-2009 average). Observations from the MLS instrument show that this is mainly related to reduced photochemical ozone destruction between 20-25 km altitude. Lower down between 15-20 km the atmospheric chemical composition and photochemical ozone destruction is unaffected. The modified chemical composition and chemistry between 20-25 km altitude in 2010 is related to the occurrence of a mid-winter minor Antarctic Sudden Stratospheric Warming (SSW). The measurements indicate that the changes in chemical composition are related to downward motion of air masses rather than horizontal mixing, and affect stratospheric chemistry for several months. Since 1979, years with similar anomalously small amounts of ozone destruction are all characterized by either minor or major SSWs, illustrating that their presence has been a necessary pre-condition for reduced Antarctic stratospheric ozone destruction.

  15. Study using a three-dimensional photochemical smog formation model under conditions of complex flow: Application of the Urban Airshed Model to the Tokyo Metropolitan Area. Rept. for Jan 85-Jan 91

    SciTech Connect

    Wakamatsu, S.; Schere, K.L.

    1991-03-01

    The purpose of the study is to evaluate the Urban Airshed Model (UAM), a three-dimensional photochemical urban air quality simulation model, using field observations from the Tokyo Metropolitan Area. Emphasis was placed on the photochemical smog formation mechanism under stagnant meteorological conditions. The UAM produced reasonable calculated results for the diurnal, areal and vertical distributions of O3 concentrations covering the Tokyo Metropolitan Area. The role and significance of the previous day's secondary pollutants on O3 formation mechanisms were also investigated. During the night time, high values of secondary pollutant concentrations were predicted above the radiation inversion layer. These aged pollutants were then entrained into the mixing layer during the day in accordance with the elevation of the lid. These characteristic features were also observed in the field study.

  16. Indirect synthesis of Al{sub 2}O{sub 3}via radiation- or photochemical formation of its hydrated precursors

    SciTech Connect

    Barta, Jan Pospisil, Milan; Cuba, Vaclav

    2014-01-01

    Graphical abstract: - Highlights: • Al{sub 2}O{sub 3} precursors were produced by UV/e-beam irradiation of aqueous solutions. • Depending on the aluminium salt (Cl{sup −} or NO{sub 3}{sup −}), either γ-AlOOH or Al(OH){sub 3} is formed. • The mechanism involved strongly depends on the presence of formate anion. • Prepared mesoporous solid phase has high specific surface area (<190 m{sup 2} g{sup −1}). • Calcination of the precursor leads to the formation of γ-/η-, θ- and α-Al{sub 2}O{sub 3}. - Abstract: γ-, θ- and α-modifications of aluminium oxide (alumina) were successfully prepared by calcination of precursor solid phase obtained by irradiation of clear aqueous solutions by UV light or electron beam. For the precipitate to form, formate anion must be present in the solution in sufficient concentration. According to X-ray diffraction, the precipitate was found to consist of γ-AlOOH or a mixture of γ- and α-Al(OH){sub 3}, when aluminium chloride or aluminium nitrate was used, respectively. The addition of hydrogen peroxide as a ·OH radical source and sensitizer markedly improved the efficiency of the preparation. Some hints for the apparently very complex mechanism involved were listed and discussed. Calcination of the dried precipitate at 500–800 °C produced highly porous γ-alumina with high specific surface area (ca. 150 m{sup 2} g{sup −1}). Mixture of γ- and θ-transition aluminas was obtained at 1000 °C and pure, stable corundum α-Al{sub 2}O{sub 3} formed at 1200 °C. Samples were further investigated by means of scanning electron microscopy and specific surface area or porosity measurement. According to N{sub 2} adsorption isotherm, the precipitate contains mostly mesopores with average pore size 7 nm with specific surface area of ca. 100 m{sup 2} g{sup −1}. Possible applications of the material as sorbent or catalyst as well as a pure matrix for thermoluminescence dosimetry were briefly contemplated. Strong light

  17. 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

  18. 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.

  19. 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.

  20. Fate of three anti-influenza drugs during ozonation of wastewater effluents - degradation and formation of transformation products.

    PubMed

    Fedorova, Ganna; Grabic, Roman; Nyhlen, Jonas; Järhult, Josef D; Söderström, Hanna

    2016-05-01

    Anti-influenza drugs constitute a key component of pandemic preparedness plans against influenza. However, the occurrence of such drugs in water environments, the potential of resistance development in the natural hosts, and the risk for transmission of antiviral resistance to humans call for measures to increase removal in wastewater treatment plants (WWTPs). In this study, removal of three anti-influenza drugs; amantadine (AM), oseltamivir carboxylate (OC) and zanamivir (ZA), and formation/removal of their transformation products during ozonation of wastewater effluents from two Swedish WWTPs in Uppsala and Stockholm were studied. The removal profile of target antivirals and formation/removal of their transformation products were studied by liquid chromatography/high resolution mass spectrometry. 3.5 h of ozone exposure (total dose of ozone 5.95 g) led to complete removal of the three anti-influenza drugs with a degradation in the following order ZA > OC > AM. Two, five and one transformation products were identified and semi-quantified for AM, OC and ZA, respectively. Increasing and later decreasing transformation products concentration followed the decrease in concentration of target compounds. All transformation products detected, except one of AM in wastewater from Stockholm WWTP, were removed at the end of the experiment. The removal efficiency was higher for all studied compounds in wastewater from Uppsala WWTP, which had lower TOC and COD values, less phosphorus, and also higher pH in the water. Ozonation thus offers multiple benefits through its potential to degrade influenza antivirals, hence decrease the risk of environmental resistance development, in addition to degrading other pharmaceuticals and resistant microorganisms. Copyright © 2015. Published by Elsevier Ltd.

  1. Singlet oxygen in surface waters. 3. Photochemical formation and steady-state concentrations in various types of waters

    SciTech Connect

    Haag, W.R.; Hoigne, J.

    1986-04-01

    For prediction of the rate with which organic compounds are oxidized and photoproducts formed in the aquatic environment by the /sup 1/O/sub 2/ route, the steady-state concentrations of O/sub 2/ in various waters were determined by using furfuryl alcohol as a trapping agent. Under noon, summer sunlight (Switzerland) in lake, river, and wastewaters, surface concentrations were (0.3-3) x 10/sup -14/ M /sup 1/O/sub 2/ per mg of DOC/L. Separation of natural aquatic organic compounds by gel permeation chromatography resulted in fractions showing little correlation between /sup 1/O/sub 2/ production efficiency and molecular weight, indicating that large macromolecular structures are not a prerequisite for the sensitization of /sup 1/O/sub 2/ formation. 26 references, 8 figures, 3 tables.

  2. Modeling study of ozone seasonal cycle in lower troposphere over east Asia

    NASA Astrophysics Data System (ADS)

    Li, Jie; Wang, Zifa; Akimoto, Hajime; Gao, Chao; Pochanart, Pakpong; Wang, Xiquan

    2007-11-01

    On the basis of three mountain sites (Mount Tai, Hua and Huang) newly founded in east-central China and several other sites from the Acid Deposition Monitoring Network in east Asia (EANET) and WMO World Data Centre for Greenhouse Gases (WDCGG), we investigate seasonal cycle of ozone over east Asia and its budgets in east-central China by using a regional chemical transport model (NAQPMS). The observations show a striking ozone pattern of two sharp peaks in May-June and September-October at three mountain sites in east-central China which are higher than those observed at other mountain sites in Europe and North America. Ozone budgets analysis by the model confirms that maximum of net photochemical productions reaches 31.8, 15.1, and 11.4 ppbv/d at Mount Tai, Hua, and Huang, respectively. The net photochemical production dominates the formation of ozone maximums at Mount Tai and Hua in June, and the importing transport also plays a comparable importance at Mount Huang. In comparison with those in the western North Pacific, east-central China shows stronger net photochemical productions, which are comparable to anthropogenic sources regions in Europe and North America.

  3. Plasmadynamic ozone generator

    NASA Astrophysics Data System (ADS)

    Gordeev, Yu. N.; Ogurechnikov, V. A.; Chizhov, Yu. L.

    2009-10-01

    The formation of ozone in a low-temperature supersonic flow of a mixture of air and partly dissociated oxygen supplied from a discharge plasmatron has been experimentally studied. For an oxygen mass fraction of 1.1% in the total gas flow supplied to this ozone generator, an ozone-air mixture containing 4.88 × 10-3 kg/m3 ozone is obtained at a specific energy consumption of 25.8 MJ/(kg ozone). In this regime, the ozone generator could operate for several dozen minutes.

  4. Terminating pre-ozonation prior to biological activated carbon filtration results in increased formation of nitrogenous disinfection by-products upon subsequent chlorination.

    PubMed

    Chu, Wenhai; Li, Changjun; Gao, Naiyun; Templeton, Michael R; Zhang, Yanshen

    2015-02-01

    Previous research demonstrated that ozone dosed before biological activated carbon (BAC) filtration reduces the formation of disinfection by-products (DBPs) upon subsequent chlorination. The current work aimed to evaluate the impact of terminating this pre-ozonation on the ability of the BAC to remove the precursors of N-DBPs. More N-DBP precursors passed into the post-BAC water when the pre-ozonation was terminated, resulting in greater formation of N-DBPs when the water was subsequently chlorinated, compared to a parallel BAC filter when the pre-ozonation was run continuously. Moreover, the N-DBP formation potential was significantly increased in the effluent of the BAC filter after terminating pre-ozonation, compared with the influent of the BAC filter (i.e. the effluent from the sand filter). Therefore, while selectively switching pre-ozonation on/off may have cost and other operational benefits for water suppliers, these should be weighed against the increased formation of N-DBPs and potential associated health risks. Copyright © 2014 Elsevier Ltd. All rights reserved.

  5. Chemical kinetics and photochemical data for use in stratospheric modeling: Evaluation number 5

    NASA Technical Reports Server (NTRS)

    Demore, W. B.

    1982-01-01

    Sets of rate constants and photochemical cross sections compiled which were evaluated. The primary application of the data is in the modeling of stratospheric processes on the ozone layer and its possible perturbation by anthropogenic and natural phenomena are emphasized.

  6. Chemical kinetics and photochemical data for use in stratospheric modeling. Evaluation number 6

    NASA Technical Reports Server (NTRS)

    Demore, W. B.; Molina, M. J.; Watson, R. T.; Golden, D. M.; Hampson, R. F.; Kurylo, M. J.; Howard, C. J.; Ravishankara, A. R.

    1983-01-01

    Evaluated sets of rate constants and photochemical cross sections are presented. The primary application of the data is in the modeling of stratospheric processes, with particular emphasis on the ozone layer and its possible perturbation by anthropogenic and natural phenomena.

  7. Photochemical grid model implementation and application of VOC, NOx, and O3 source apportionment

    EPA Science Inventory

    For the purposes of developing optimal emissions control strategies, efficient approaches are needed to identify the major sources or groups of sources that contribute to elevated ozone (O3) concentrations. Source-based apportionment techniques implemented in photochemical grid m...

  8. Photochemical grid model implementation and application of VOC, NOx, and O3 source apportionment

    EPA Science Inventory

    For the purposes of developing optimal emissions control strategies, efficient approaches are needed to identify the major sources or groups of sources that contribute to elevated ozone (O3) concentrations. Source-based apportionment techniques implemented in photochemical grid m...

  9. APPLICATION OF BAYESIAN MONTE CARLO ANALYSIS TO A LAGRANGIAN PHOTOCHEMICAL AIR QUALITY MODEL. (R824792)

    EPA Science Inventory

    Uncertainties in ozone concentrations predicted with a Lagrangian photochemical air quality model have been estimated using Bayesian Monte Carlo (BMC) analysis. Bayesian Monte Carlo analysis provides a means of combining subjective "prior" uncertainty estimates developed ...

  10. Formation of known and unknown disinfection by-products from natural organic matter fractions during chlorination, chloramination, and ozonation.

    PubMed

    Li, Chunmei; Wang, Donghong; Xu, Xiong; Wang, Zijian

    2017-06-01

    Natural organic matter (NOM) is the main precursor of disinfection by-products (DBPs) formed during drinking water treatment processes. Previous studies of the relationships between DBP formation and NOM fractionation have mainly been focused on currently regulated DBPs and a few certain emerging DBPs. In this work, the Suwannee River NOM solution was fractionated into groups with different hydrophobicities using DAX-8 resins, and volatile and semi-volatile DBPs formed during the chlorination, chloramination and ozonation of the NOM fractions were examined by a nontargeted screening of comprehensive two-dimensional gas chromatography-quadrupole mass spectrometry procedure. The results showed that a total of 302 DBPs representing nine chemical classes were detected, of which 266 were possibly newly detected, based on library searching with NIST 08 library (using similarity and reverse values of at least 600 and 700, respectively) and linear retention indices. The characterization of DBP precursors suggests that hydrophobic (HPO) NOM contains the major fraction of precursor for the formation of nitrogenous DBPs (contributing about 60% of the total nitrogenous DBPs) during all three disinfection processes. Much larger amounts of heterocyclic DBPs were formed from the HPO fraction than from the hydrophilic fraction during chlorination. During chloramination and ozonation, 5-15 times more ketones were formed from the hydrophilic fraction than from the HPO fraction. During ozonation, more than twice the amounts of esters and alcohols were formed from the hydrophilic fraction than from the HPO fraction. Three-dimensional excitation-emission matrix spectra suggest that similar to the formation of regulated DBPs, humic acid-like substances are probably the precursors of halogen-containing DBPs. Relatively higher nitrogenous DBPs formation from the HPO fraction might be because of the existence of protein-like materials.

  11. 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.

  12. Impact of pre-ozonation on disinfection by-product formation and speciation from chlor(am)ination of algal organic matter of Microcystis aeruginosa.

    PubMed

    Zhu, Mingqiu; Gao, Naiyun; Chu, Wenhai; Zhou, Shiqing; Zhang, Zhengde; Xu, Yaqun; Dai, Qi

    2015-10-01

    The increasing use of algal-impacted source waters is increasing concerns over exposure to disinfection byproducts (DBPs) in drinking water disinfection, due to the higher concentrations of DBP precursors in these waters. The impact of pre-ozonation on the formation and speciation of DBPs during subsequent chlorination and chloramination of algal organic matter (AOM), including extracellular organic matter (EOM) and intracellular organic matter (IOM), was investigated. During subsequent chlorination, ozonation pretreatment reduced the formation of haloacetonitriles from EOM, but increased the yields of trihalomethanes, dihaloacetic acid and trichloronitromethane from both EOM and IOM. While in chloramination, pre-ozonation remarkably enhanced the yields of several carbonaceous DBPs from IOM, and significantly minimized the nitrogenous DBP precursors. Also, the yield of 1,1-dichloro-2-propanone from IOM was decreased by 24.0% after pre-ozonation during chloramination. Both increases and decreases in the bromine substitution factors (BSF) of AOM were observed with ozone pretreatment at the low bromide level (50μg/L). However, pre-ozonation played little impact on the bromide substitution in DBPs at the high bromide level (500μg/L). This information was used to guide the design and practical operation of pre-ozonation in drinking water treatment plants using algae-rich waters.

  13. The influence of aerosols on photochemical smog in Mexico City

    NASA Astrophysics Data System (ADS)

    Castro, T.; Madronich, S.; Rivale, S.; Muhlia, A.; Mar, B.

    Aerosols in the Mexico City atmosphere can have a non-negligible effect on the ultraviolet radiation field and hence on the formation of photochemical smog. We used estimates of aerosol optical depths from sun photometer observations in a detailed radiative transfer model, to calculate photolysis rate coefficients ( JNO 2) for the key reaction NO 2+ hν→NO+O ( λ<430 nm). The calculated values are in good agreement with previously published measurements of JNO 2 at two sites in Mexico City: Palacio de Minerı´a (19°25'59″N, 99°07'58″W, 2233 masl), and IMP (19°28'48″N, 99°11'07″W, 2277 masl) and in Tres Marias, a town near Mexico City (19°03'N, 99°14'W, 2810 masl). In particular, the model reproduces very well the contrast between the two urban sites and the evidently much cleaner Tres Marias site. For the measurement days, reductions in surface JNO 2 by 10-30% could be attributed to the presence of aerosols, with considerable uncertainty due largely to lack of detailed data on aerosol optical properties at ultraviolet wavelengths (esp. the single scattering albedo). The potential impact of such large reductions in photolysis rates on surface ozone concentrations is illustrated with a simple zero-dimensional photochemical model.

  14. Oxidation of cetirizine, fexofenadine and hydrochlorothiazide during ozonation: Kinetics and formation of transformation products.

    PubMed

    Borowska, Ewa; Bourgin, Marc; Hollender, Juliane; Kienle, Cornelia; McArdell, Christa S; von Gunten, Urs

    2016-05-01

    The efficiency of wastewater ozonation for the abatement of three nitrogen-containing pharmaceuticals, two antihistamine drugs, cetirizine (CTR) and fexofenadine (FXF), and the diuretic drug, hydrochlorothiazide (HCTZ), was investigated. Species-specific second-order rate constants for the reactions of the molecular, protonated (CTR, FXF) or deprotonated (HCTZ) forms of these compounds with ozone were determined. All three compounds are very reactive with ozone (apparent second order rate constants at pH 7: kO3,pH7 = 1.7·10(5) M(-1)s(-1), 8.5·10(4) M(-1)s(-1) and 9.0·10(3) M(-1)s(-1) for CTR, HCTZ and FXF, respectively). Transformation product (TP) structures were elucidated using liquid chromatography coupled with high-resolution tandem mass spectrometry, including isotope-labeled standards. For cetirizine and hydrochlorothiazide 8 TPs each and for fexofenadine 7 TPs were identified. The main TPs of cetirizine and fexofenadine are their respective N-oxides, whereas chlorothiazide forms to almost 100% from hydrochlorothiazide. In the bacteria bioluminescence assay the toxicity was slightly increased only during the ozonation of cetirizine at very high cetirizine concentrations. The main TPs detected in bench-scale experiments were also detected in full-scale ozonation of a municipal wastewater, for >90% elimination of the parent compounds.

  15. Sensitivity Study of Halogen Chemistry on Ozone Formation under Moderate Polluted Concditions

    NASA Astrophysics Data System (ADS)

    Kraut, Isabel; Vogel, Heike; Vogel, Bernhard; Chance, Rosie; von Glasow, Roland

    2013-04-01

    In order to quantify the interaction of halogen species with ozone the gas phase mechanism RADMKA was extended by a halogen mechanism. This mechanism handles the most important reactions dealing with halogen species in the troposphere. Box model runs are used to explore the sensitivity of the ozone concentration to the individual compounds and for different chemical regimes. The halogen mechanism was also included to the model system COSMO-ART (Vogel et al., 2009). COSMO-ART is an enhanced model system to simulate the spatial and temporal distributions of reactive gaseous and particulate matter. It is used to quantify the feedback processes between aerosols and the state of the atmosphere on the continental to the regional scale with two-way interactions between different atmospheric processes. The model system is applied to an ozone episode in Europe in June 2006 to investigate the impact of iodine emissions on ozone. In contrast to previous applications where only iodine emissions from macroalgal species were taken into account the emissions of iodine are calculated using the new parameterization of Carpenter et al., 2012. In this parameterization the marine iodine emissions are dependent ozone concentration, the surface ocean iodide concentration and on the wind speed.

  16. On the summertime air quality and related photochemical processes in the megacity Shanghai, China.

    PubMed

    Chan, Ka Lok; Wang, Shanshan; Liu, Cheng; Zhou, Bin; Wenig, Mark O; Saiz-Lopez, Alfonso

    2017-02-15

    Summertime surface ozone (O3) and related secondary formation of fine particles are the major air quality concerns in the megacity of Shanghai. We performed mobile Cavity Enhanced Differential Optical Absorption Spectroscopy (CE-DOAS) measurements to investigate the spatial distribution of on-road nitrogen dioxide (NO2) concentrations along the Inner Ring Elevated Road (IRER) in Shanghai. The observations show a ratio of 4 between CE-DOAS averaged on-road NO2 and the in-situ ambient measurements, illustrating the strong impact of vehicle emissions over the urban area. The air mass transport analysis suggests that the observed episodic ozone events arise from both the abundance of volatile organic compounds (VOCs) precursors in the sampled plume and the regional transport of ozone-rich air masses. Analysis of the sources of PM2.5 shows that the secondary heterogeneous gas-to-particle conversion of sulfate and nitrate from sulfur dioxide (SO2) and nitrogen oxides (NOx) is the largest source of PM2.5 contributing 44.8±9.2% of the total PM2.5. Ozone-related photochemical formation of fine particles is estimated to contribute about 22.5±11.9% of the total PM2.5, which is strongly facilitated by solar radiation in summer. According to our results, nitrous acid (HONO) is the major precursor of hydroxyl radicals (OH) accounting for 40% to 80% of the total OH production during daytime. A significant correlation is found between the HONO levels in the early morning and the daily O3 and PM2.5 levels. The summertime measurements indicate that the photolytic reaction of HONO after sunrise increased the abundance of daytime OH and oxidative capacity, resulting in an enhancement of ground level ozone and secondary organic aerosol formation. This study provides quantitative information to better understand photochemical formation of ozone and fine particles in Shanghai during summertime, which is useful for designing collaborative strategies to mitigate emissions of precursor

  17. Observed suppression of ozone formation at extremely high temperatures due to chemical and biophysical feedbacks

    PubMed Central

    Steiner, Allison L.; Davis, Adam J.; Sillman, Sanford; Owen, Robert C.; Michalak, Anna M.; Fiore, Arlene M.

    2010-01-01

    Ground level ozone concentrations ([O3]) typically show a direct linear relationship with surface air temperature. Three decades of California measurements provide evidence of a statistically significant change in the ozone-temperature slope (ΔmO3-T) under extremely high temperatures (> 312 K). This ΔmO3-T leads to a plateau or decrease in [O3], reflecting the diminished role of nitrogen oxide sequestration by peroxyacetyl nitrates and reduced biogenic isoprene emissions at high temperatures. Despite inclusion of these processes in global and regional chemistry-climate models, a statistically significant change in ΔmO3-T has not been noted in prior studies. Future climate projections suggest a more frequent and spatially widespread occurrence of this ΔmO3-T response, confounding predictions of extreme ozone events based on the historically observed linear relationship. PMID:21041679

  18. Volatile organic compounds speciation and their influence on ozone formation potential in an industrialized urban area in Brazil.

    PubMed

    Galvão, Elson Silva; Santos, Jane Meri; Reis Junior, Neyval Costa; Stuetz, Richard Michael

    2016-09-01

    Speciation and the influence on the ozone formation potential (OFP) from volatile organic compounds (VOCs) have been studied between February June 2013 in Vitória, ES, Brazil. Passive samplers were installed at three air-quality monitoring stations and a total of 96 samplings were collected. A total of 78 VOCs were characterized by gas chromatograph-mass spectrometer. The predominant group was organic acids, followed by alcohols and substituted aromatics and 14 precursor species were quantified. An analysis correlating concentrations with wind direction was conducted to identify possible sources. The OFP was calculated applying the scale of maximum incremental reactivity proposed by Carter.[ 23 ] Ozone precursors with the greatest OFP such as undecane, toluene, ethylbenzene and m, p-xylene compounds were the most abundant with means of 0.855, 0.365, 0.259 and 0.289 µg m(-3), respectively. The benzene, toluene, ethylbenzene and xylene (BTEX) group was found below the limits considered harmful to the health of the population living in Vitória. The OFP calculated for the precursors group was 22.55 µg m(-3) for the rainy season and 32.11 µg m(-3) for the dry season. The VOC/NOx ratio in Vitória is approximately 1.71, indicating that the region has a VOC-limiting condition for the production of ozone.

  19. Three air quality studies: Great Lakes ozone formation and nitrogen dry deposition; and Tucson aerosol chemical characterization

    NASA Astrophysics Data System (ADS)

    Foley, Theresa

    The Clean Air Act of 1970 was promulgated after thousands of lives were lost in four catastrophic air pollution events. It authorized the establishment of National Ambient Air Quality Standards or (NAAQS) for six pollutants that are harmful to human health and welfare: carbon monoxide, lead, nitrogen dioxide, particulate matter, ozone and sulfur dioxide. The Clean Air Act also led to the establishment of the United Stated Environmental Protection Agency (US EPA) to set and enforce regulations. The first paper in this dissertation studies ozone in the Lake Michigan region (Foley, T., Betterton, E.A., Jacko, R., Hillery, J., 2011. Lake Michigan air quality: The 1994-2003 LADCO Aircraft Project (LAP). Atmospheric Environment 45, 3192-3202.) The Chicago-Milwaukee-Gary metropolitan area has been unable to meet the ozone NAAQS since the Clean Air Act was implemented. The Lake Michigan Air Directors' Consortium (LADCO) hypothesized that land breezes transport ozone precursor compounds over the lake, where a large air/water temperature difference creates a shallow conduction layer, which is an efficient reaction chamber for ozone formation. In the afternoon, lake breezes and prevailing synoptic winds then transport ozone back over the land. To further evaluate this hypothesis, LADCO sponsored the 1994-2003 LADCO Aircraft Project (LAP) to measure the air quality over Lake Michigan and the surrounding areas. This study has found that the LAP data supports this hypothesis of ozone formation, which has strong implications for ozone control strategies in the Lake Michigan region. The second paper is this dissertation (Foley, T., Betterton, E.A., Wolf, A.M.A., 2012. Ambient PM10 and metal concentrations measured in the Sunnyside Unified School District, Tucson, Arizona. Journal of the Arizona-Nevada Academy of Science, 43, 67-76) evaluated the airborne concentrations of PM10 (particulate matter with an aerodynamic diameter of 10 microns or less) and eight metalloids and metals

  20. 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.

  1. The photochemical smog pollution in Beijing

    SciTech Connect

    Xiaoyan Tang

    1996-12-31

    The photochemical smog pollution in summer time has been studied in Beijing area. The systematic field measurements associated with meteorological observation was conducted in 1986, 1987 and 1993. The spatial and temporal distribution of O{sub 3} and specific formation condition of photochemical smog, including vehicle emission sources and meteorological factors etc. in summer were studied and discussed. The prediction of O{sub 3} ambient air concentration in Beijing area in 2000, 2005 and 2010 by model simulation were also discussed.

  2. Photochemical Production of Alkyl Nitrates in the Tropical Pacific Ocean

    NASA Astrophysics Data System (ADS)

    Dahl, E. E.; Yvon-Lewis, S. A.; Saltzman, E. S.

    2005-12-01

    Alkyl nitrates are important to the tropospheric NOx/ozone cycle because they represent a significant fraction of the reactive nitrogen (NOy). Previous work has shown that there is an oceanic source of alkyl nitrates. A photochemical mechanism for the formation of alkyl nitrates in seawater has been proposed. This mechanism involves the reaction of ROO and NO, where ROO is an alkyl peroxy radical. ROO and NO radicals in seawater are derived from the photolysis of DOM and nitrite, respectively. In this study, the photochemical production of low molecular weight alkyl nitrates (C1-C3) was observed in shipboard incubation experiments in the tropical Pacific during the PHASE 1 cruise. Seawater samples from several regions, including high and low-chlorophyll areas, were collected and incubated. Alkyl nitrate production rates as high as 2 nM/hour were observed. The production rate of alkyl nitrates was clearly dependent upon the initial concentration of nitrite, most likely as the source for NO radicals. While the magnitude of production varied between sample locations, the ratios of the production rates of the various alkyl nitrates remained relatively constant. The observed production ratios of methyl, ethyl, isopropyl, and n-propyl nitrate were 5.9:1.0:0.1:0.2. These ratios presumably reflect the speciation of peroxy radicals formed in seawater, and the yield of alkyl nitrates from the ROO+NO reaction. The observed production rate ratios are similar to the concentration ratios of alkyl nitrates observed in ambient seawater and the overlying atmosphere during the study. A comparison of the measured production rates and the observed concentrations, suggests that photochemically produced alkyl nitrates are a major source of atmospheric alkyl nitrates in the surface ocean and marine atmosphere.

  3. Diagnostic analysis of two-dimensional monthly average ozone balance with Chapman chemistry

    NASA Astrophysics Data System (ADS)

    Stolarski, Richard S.; Jackman, Charles H.; Kaye, Jack A.

    1986-12-01

    Chapman chemistry has been used in a two-dimensional model to simulate ozone balance phenomenology. The similarity between regions of ozone production and loss calculated using Chapman chemistry and those computed using LIMS and SAMS data with a photochemical equilibrium model indicate that such simplified chemistry is useful in studying gross features in stratospheric ozone balance. Net ozone production or loss rates are brought about by departures from the photochemical equilibrium (PCE) condition. If transport drives ozone above its PCE condition, then photochemical loss dominates production. If transport drives ozone below its PCE condition, then photochemical production dominates loss. Gross features of ozone loss/production (L/P) inferred for the real atmosphere from data are also simulated using only eddy diffusion. This indicates that one must be careful in assigning a transport scheme for a two-dimensional model that mimics only behavior of the observed ozone L/P.

  4. Diagnostic analysis of two-dimensional monthly average ozone balance with Chapman chemistry

    NASA Technical Reports Server (NTRS)

    Stolarski, Richard S.; Jackman, Charles H.; Kaye, Jack A.

    1986-01-01

    Chapman chemistry has been used in a two-dimensional model to simulate ozone balance phenomenology. The similarity between regions of ozone production and loss calculated using Chapman chemistry and those computed using LIMS and SAMS data with a photochemical equilibrium model indicate that such simplified chemistry is useful in studying gross features in stratospheric ozone balance. Net ozone production or loss rates are brought about by departures from the photochemical equilibrium (PCE) condition. If transport drives ozone above its PCE condition, then photochemical loss dominates production. If transport drives ozone below its PCE condition, then photochemical production dominates loss. Gross features of ozone loss/production (L/P) inferred for the real atmosphere from data are also simulated using only eddy diffusion. This indicates that one must be careful in assigning a transport scheme for a two-dimensional model that mimics only behavior of the observed ozone L/P.

  5. Ozone impacts of natural gas development in the Haynesville Shale.

    PubMed

    Kemball-Cook, Susan; Bar-Ilan, Amnon; Grant, John; Parker, Lynsey; Jung, Jaegun; Santamaria, Wilson; Mathews, Jim; Yarwood, Greg

    2010-12-15

    The Haynesville Shale is a subsurface rock formation located beneath the Northeast Texas/Northwest Louisiana border near Shreveport. This formation is estimated to contain very large recoverable reserves of natural gas, and during the two years since the drilling of the first highly productive wells in 2008, has been the focus of intensive leasing and exploration activity. The development of natural gas resources within the Haynesville Shale is likely to be economically important but may also generate significant emissions of ozone precursors. Using well production data from state regulatory agencies and a review of the available literature, projections of future year Haynesville Shale natural gas production were derived for 2009-2020 for three scenarios corresponding to limited, moderate, and aggressive development. These production estimates were then used to develop an emission inventory for each of the three scenarios. Photochemical modeling of the year 2012 showed increases in 2012 8-h ozone design values of up to 5 ppb within Northeast Texas and Northwest Louisiana resulting from development in the Haynesville Shale. Ozone increases due to Haynesville Shale emissions can affect regions outside Northeast Texas and Northwest Louisiana due to ozone transport. This study evaluates only near-term ozone impacts, but the emission inventory projections indicate that Haynesville emissions may be expected to increase through 2020.

  6. The formation of ultra-fine particles during ozone-initiated oxidations with terpenes emitted from natural paint.

    PubMed

    Lamorena, Rheo B; Jung, Sang-Guen; Bae, Gwi-Nam; Lee, Woojin

    2007-03-06

    The formation of secondary products during the ozone-initiated oxidations with biogenic VOCs emitted from natural paint was investigated in this study. Mass spectrometry and infrared spectroscopy measurements have shown that the major components of gas-phase chemicals emitted from natural paint are monoterpenes including alpha- and beta-pinenes, camphene, p-cymene, and limonene. A significant formation of gaseous carbonyl products and nano-sized particles (4.4-168nm) was observed in the presence of ozone. Carboxylic acids were also observed to form during the reactions (i.e. formic acid at 0.170ppm and acetic acid at 0.260ppm). The formation of particles increased as the volume of paint introduced into a reaction chamber increased. A secondary increase in the particle number concentration was observed after 440min, which suggests further partitioning of oxidation products (i.e. carboxylic acids) into the particles previously existing in the reaction chamber. The growth of particles increased as the mean particle diameter and particle mass concentrations increased during the reaction. The experimental results obtained in this study may provide insight into the potential exposure of occupants to irritating chemical compounds formed during the oxidations of biogenic VOCs emitted from natural paint in indoor environments.

  7. ISOTOPIC (14C) AND CHEMICAL COMPOSITION OF ATMOSPHERIC VOLATILE ORGANIC COMPOUND FRACTIONS - PRECURSORS TO OZONE FORMATION

    EPA Science Inventory

    Atmospheric volatile organic compounds (VOCs) are an important factor in the production of ozone near ground level [3]. Many hydrocarbons originate from auto exhaust. However, a number of VOCs, e.g., isoprene, are known to be natural in origin. To develop reliable models for un...

  8. OZONE-ISOPRENE REACTION: RE-EXAMINATION OF THE FORMATION OF SECONDARY ORGANIC AEROSOL

    EPA Science Inventory

    The reaction of ozone and isoprene has been studied to examine physical and chemical characteristics of the secondary organic aerosol formed. Using a scanning mobility particle sizer, the volume distribution of the aerosol was found in the range 0.05 - 0.2 µm. The aerosol yield w...

  9. ISOTOPIC (14C) AND CHEMICAL COMPOSITION OF ATMOSPHERIC VOLATILE ORGANIC COMPOUND FRACTIONS - PRECURSORS TO OZONE FORMATION

    EPA Science Inventory

    Atmospheric volatile organic compounds (VOCs) are an important factor in the production of ozone near ground level [3]. Many hydrocarbons originate from auto exhaust. However, a number of VOCs, e.g., isoprene, are known to be natural in origin. To develop reliable models for un...

  10. OZONE-ISOPRENE REACTION: RE-EXAMINATION OF THE FORMATION OF SECONDARY ORGANIC AEROSOL

    EPA Science Inventory

    The reaction of ozone and isoprene has been studied to examine physical and chemical characteristics of the secondary organic aerosol formed. Using a scanning mobility particle sizer, the volume distribution of the aerosol was found in the range 0.05 - 0.2 µm. The aerosol yield w...

  11. Non-methane hydrocarbons (NMHCs) and their contribution to ozone formation potential in a petrochemical industrialized city, Northwest China

    NASA Astrophysics Data System (ADS)

    Jia, Chenhui; Mao, Xiaoxuan; Huang, Tao; Liang, Xiaoxue; Wang, Yanan; Shen, Yanjie; Jiang, Wanyanhan; Wang, Huiqin; Bai, Zhilin; Ma, Minquan; Yu, Zhousuo; Ma, Jianmin; Gao, Hong

    2016-03-01

    Hourly air concentrations of fifty-three non-methane hydrocarbons (NMHCs) were measured at downtown and suburb of Lanzhou, a petrochemical industrialized city, Northwest China in 2013. The measured data were used to investigate the seasonal characteristics of NMHCs air pollution and their contributions to the ozone formation in Lanzhou. Annually averaged NMHCs concentration was 38.29 ppbv in downtown Lanzhou. Among 53 NMHCs, alkanes, alkenes, and aromatics accounted for 57%, 23% and 20% of the total NMHCs air concentration, respectively. The atmospheric levels of toluene and propane with mean values of 4.62 and 4.56 ppbv were higher than other NMHCs, respectively. The ambient levels of NMHCs in downtown Lanzhou were compared with measured NMHCs data collected at a suburban site of Lanzhou, located near a large-scale petrochemical industry. Results show that the levels of alkanes, alkenes, and aromatics in downtown Lanzhou were lower by factors of 3-11 than that in west suburb of the city. O3-isopleth plots show that ozone was formed in VOCs control area in downtown Lanzhou and NOx control area at the west suburban site during the summertime. Propylene-equivalent (Prop-Equiv) concentration and the maximum incremental reactivity (MIR) in downtown Lanzhou indicate that cis-2-butene, propylene, and m/p-xylene were the first three compounds contributing to ozone formation potentials whereas in the petrochemical industrialized west suburb, ethane, propene, and trans-2-Butene played more important role in the summertime ozone formation. Principal component analysis (PCA) and multiple linear regression (MLR) were further applied to identify the dominant emission sources and examine their fractions in total NMHCs. Results suggest that vehicle emission, solvent usage, and industrial activities were major sources of NMHCs in the city, accounting for 58.34%, 22.19%, and 19.47% of the total monitored NMHCs in downtown Lanzhou, respectively. In the west suburb of the city

  12. Formation of N-nitrosamines by chloramination or ozonation of amines listed in Pollutant Release and Transfer Registers (PRTRs).

    PubMed

    Yoon, Suchul; Tanaka, Hiroaki

    2014-01-01

    We determined whether or not the chloramination or ozonation of amines and hydrazines listed in Pollutant Release and Transfer Registers (PRTRs) results in the formation of N-nitrosamines when reacted in secondary wastewater effluent. We selected 12 primary, 2 secondary, 2 tertiary amines and 3 hydrazines from the PRTRs of Japan, the USA, and Korea. In this study, based on the assumption that there is a production of N-nitrosamines by not only the original selected amines and hydrazines but also the intermediate products in case of chloramination and ozonation, it was examined whether precursors were identified by selected amines and hydrazines based on the gap of the N-nitrosamines formation potential between day 0 and day 10 rather than analyzing the contribution depending on the concentration of selected amines and hydrazines. Many of the primary amines (notably 2,6-xylidine) and all of the secondary and tertiary amines produced N-nitrosodimethylamine (NDMA) by chloramination. Furthermore, the primary amines 2,6-xylidine, 3,3'-dimethylbenzidine, 4,4'-methylenebis(2-chloroaniline), 4-aminoazobenzene, p-chloroaniline, and p-cresidine produced more NDMA than did the secondary amines. The secondary amines produced mainly NDMA. Ozonation produced NDMA only from the hydrazine 1,1-dimethylhydrazine, and at a higher concentration than by chloramination. We identified 2,6-xylidine, 3,3'-dimethylbenzidine, 4,4'-methylenebis(2-chloroaniline), 4-aminoazobenzene, p-chloroaniline, p-cresidine, 1,1-dimethylhydrazine, diethylamine, 4,4'-methylenebis(N,N-dimethyl)benzenamine, and chinomethionat as warranting further study.

  13. 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.

  14. Assessment of ozone photochemistry in the western North Pacific as inferred from PEM-West A observations during the fall 1991

    NASA Astrophysics Data System (ADS)

    Davis, D. D.; Crawford, J.; Chen, G.; Chameides, W.; Liu, S.; Bradshaw, J.; Sandholm, S.; Sachse, G.; Gregory, G.; Anderson, B.; Barrick, J.; Bachmeier, A.; Collins, J.; Browell, E.; Blake, D.; Rowland, S.; Kondo, Y.; Singh, H.; Talbot, R.; Heikes, B.; Merrill, J.; Rodriguez, J.; Newell, R. E.

    1996-01-01

    This study examines the influence of photochemical processes on ozone distributions in the western North Pacific. The analysis is based on data generated during NASA's western Pacific Exploratory Mission (PEM-West A) during the fall of 1991. Ozone trends were best described in terms of two geographical domains: the western North Pacific rim (WNPR) and the western tropical North Pacific (WTNP). For both geographical regions, ozone photochemical destruction, D(O3), decreased more rapidly with altitude than did photochemical formation, F(O3). Thus the ozone tendency, P(O3), was typically found to be negative for z < 6 km and positive for z > 6-8 km. For nearly all altitudes and latitudes, observed nonmethane hydrocarbon (NMHC) levels were shown to be of minor importance as ozone precursor species. Air parcel types producing the largest positive values of P(O3) included fresh continental boundary layer (BL) air and high-altitude (z > 7 km) parcels influenced by deep convection/lightning. Significant negative P(O3) values were found when encountering clean marine BL air or relatively clean lower free-tropospheric air. Photochemical destruction and formation fluxes for the Pacific rim region were found to exceed average values cited for marine dry deposition and stratospheric injection in the northern hemisphere by nearly a factor of 6. This region was also found to be in near balance with respect to column-integrated O3 photochemical production and destruction. By contrast, for the tropical regime column-integrated O3 showed photochemical destruction exceeding production by nearly 80%. Both transport of O3 rich midlatitude air into the tropics as well as very high-altitude (10-17 km) photochemical O3 production were proposed as possible additional sources that might explain this estimated deficit. Results from this study further suggest that during the fall time period, deep convection over Asia and Malaysia/Indonesia provided a significant source of high-altitude NOx

  15. Modelling the photochemical pollution over the metropolitan area of Porto Alegre, Brazil

    NASA Astrophysics Data System (ADS)

    Borrego, C.; Monteiro, A.; Ferreira, J.; Moraes, M. R.; Carvalho, A.; Ribeiro, I.; Miranda, A. I.; Moreira, D. M.

    2010-01-01

    The main purpose of this study is to evaluate the photochemical pollution over the Metropolitan Area of Porto Alegre (MAPA), Brazil, where high concentrations of ozone have been registered during the past years. Due to the restricted spatial coverage of the monitoring air quality network, a numerical modelling technique was selected and applied to this assessment exercise. Two different chemistry-transport models - CAMx and CALGRID - were applied for a summer period, driven by the MM5 meteorological model. The meteorological model performance was evaluated comparing its results to available monitoring data measured at the Porto Alegre airport. Validation results point out a good model performance. It was not possible to evaluate the chemistry models performance due to the lack of adequate monitoring data. Nevertheless, the model intercomparison between CAMx and CALGRID shows a similar behaviour in what concerns the simulation of nitrogen dioxide, but some discrepancies concerning ozone. Regarding the fulfilment of the Brazilian air quality targets, the simulated ozone concentrations surpass the legislated value in specific periods, mainly outside the urban area of Porto Alegre. The ozone formation is influenced by the emission of pollutants that act as precursors (like the nitrogen oxides emitted at Porto Alegre urban area and coming from a large refinery complex) and by the meteorological conditions.

  16. Simulation of ozone formation at different elevations in mountainous area of Hong Kong using WRF-CMAQ model.

    PubMed

    Wang, N; Guo, H; Jiang, F; Ling, Z H; Wang, T

    2015-02-01

    Field measurements were simultaneously conducted at a mountain (Mt.) site (Tai Mao Shan, TMS) and an urban site (Tsuen Wan, TW) at the foot of the Mt. TMS in Hong Kong. An interesting event with consecutive high-ozone (O₃) days from 08:00 on 28 Oct. to 23:00 on 03 Nov., 2010 was observed at Mt. TMS, while no such polluted event was found at the foot of the mountain. The Weather Research and Forecasting (WRF)-Community Multiscale Air Quality (CMAQ) models were used to understand this event. Model performance evaluation showed that the simulated meteorological parameters and air pollutants were well in agreement with the observations. The index of agreement (IOA) of temperature, relative humidity, wind direction and wind speed were 0.93, 0.83, 0.46 and 0.60, respectively. The multi-day high O₃ episode at Mt. TMS was also reasonably reproduced (IOA=0.68). Horizontally, the photochemical processes determined the O₃ levels in southwestern Pearl River Delta (PRD) and the Pearl River Estuary (PRE), while in eastern and northern PRD, the O₃ destruction was over the production during the event. Vertically, higher O₃ values at higher levels were found at both Mt. TMS and TW, indicating a vertical O₃ gradient over Hong Kong. With the aid of the process analysis module, we found positive contribution of vertical transport including advection and diffusion to O₃ mixing ratios at the two sites, suggesting that O₃ values at lower locations could be affected by O₃ at higher locations via vertical advection and diffusion over Hong Kong.

  17. 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.

  18. Biochemical basis of ozone toxicity

    SciTech Connect

    Mustafa, M.G. )

    1990-01-01

    Ozone (O3) is the major oxidant of photochemical smog. Its biological effect is attributed to its ability to cause oxidation or peroxidation of biomolecules directly and/or via free radical reactions. A sequence of events may include lipid peroxidation and loss of functional groups of enzymes, alteration of membrane permeability, and cell injury or death. An acute exposure to O3 causes lung injury involving the ciliated cell in the airways and the type 1 epithelial cell in the alveolar region. The effects are particularly localized at the junction of terminal bronchioles and alveolar ducts, as evident from a loss of cells and accumulation of inflammatory cells. In a typical short-term exposure the lung tissue response is biphasic: an initial injury-phase characterized by cell damage and loss of enzyme activities, followed by a repair-phase associated with increased metabolic activities, which coincide with a proliferation of metabolically active cells, for example, the alveolar type 2 cells and the bronchiolar Clara cells. A chronic exposure to O3 can cause or exacerbate lung diseases, including perhaps an increased lung tumor incidence in susceptible animal models. Ozone exposure also causes extrapulmonary effects involving the blood, spleen, central nervous system, and other organs. A combination of O3 and NO2, both of which occur in photochemical smog, can produce effects which may be additive or synergistic. A synergistic lung injury occurs possibly due to a formation of more powerful radicals and chemical intermediates. Dietary antioxidants, for example, vitamin E, vitamin C, and selenium, can offer a protection against O3 effects. 324 refs.

  19. Biochemical basis of ozone toxicity.

    PubMed

    Mustafa, M G

    1990-01-01

    Ozone (O3) is the major oxidant of photochemical smog. Its biological effect is attributed to its ability to cause oxidation or peroxidation of biomolecules directly and/or via free radical reactions. A sequence of events may include lipid peroxidation and loss of functional groups of enzymes, alteration of membrane permeability, and cell injury or death. An acute exposure to O3 causes lung injury involving the ciliated cell in the airways and the type 1 epithelial cell in the alveolar region. The effects are particularly localized at the junction of terminal bronchioles and alveolar ducts, as evident from a loss of cells and accumulation of inflammatory cells. In a typical short-term exposure the lung tissue response is biphasic: an initial injury-phase characterized by cell damage and loss of enzyme activities, followed by a repair-phase associated with increased metabolic activities, which coincide with a proliferation of metabolically active cells, for example, the alveolar type 2 cells and the bronchiolar Clara cells. A chronic exposure to O3 can cause or exacerbate lung diseases, including perhaps an increased lung tumor incidence in susceptible animal models. Ozone exposure also causes extrapulmonary effects involving the blood, spleen, central nervous system, and other organs. A combination of O3 and NO2, both of which occur in photochemical smog, can produce effects which may be additive or synergistic. A synergistic lung injury occurs possibly due to a formation of more powerful radicals and chemical intermediates. Dietary antioxidants, for example, vitamin E, vitamin C, and selenium, can offer a protection against O3 effects.

  20. Observation of summertime enhanced ozone over the middle troposphere in the vicinity of the Middle East by spaceborne TES instrument

    NASA Astrophysics Data System (ADS)

    Liu, Jane; Jones, Dylan; Worden, John; Parrington, Mark; Kar, Jayanta

    We used a global chemical transport model, namely GEOS-Chem, to interpret recent observations of tropospheric ozone from the Tropospheric Emissions Spectrometer (TES) onboard of on the NASA EOS Aura satellite. TES observations reveal elevated ozone in the middle troposphere ( 500-400 hPa, 5-7 km) over a large area of the eastern Mediterranean, the Middle East, and Central Asia in summer 2005 and 2006. This enhancement has some similarities to and differences from the "Middle East ozone maximum" that was previously suggested in a model study, revealing complexity of the feature. We found, based on the TES data, that although there is general enhancement of ozone at 400-500 hPa over the Middle East and surrounding areas, no one single maximum is centralized in the Middle East as described in the previous modelling work. Instead, localized maxima are seen within the ozone-enhanced area. The location and intensity of these maxima vary from year to year. We found that the region of elevated ozone is closely associated with the location of the subtropical westerly jet and anticyclones over North Africa and the Persian Gulf. The ozone distribution in the region is greatly influenced by the seasonal evolution of these systems. We examined the influence of photochemical production and transport on the ozone budget in the region. A tagged ozone simulation was conducted to track ozone in the region from its origins in Asia, Africa, North America, and European. The outcome shows that long-range transport and in situ chemical production both contribute to the formation of the ozone enhancement. Our results suggests that accurately simulating the magnitude and spatial distribution of the ozone enhancement requires properly reproducing ozone production rate in the upper troposphere and the atmospheric response to Asian monsoon heating that is reflected in the strengths of the anticyclones over North Africa and the Persian Gulf.

  1. Chemical kinetics and photochemical data for use in stratospheric modeling

    NASA Technical Reports Server (NTRS)

    Demore, W. B.; Sander, S. P.; Golden, D. M.; Hampson, R. F.; Kurylo, M. J.; Howard, C. J.; Ravishankara, A. R.; Kolb, C. E.; Molina, M. J.

    1992-01-01

    As part of a series of evaluated sets, rate constants and photochemical cross sections compiled by the NASA Panel for Data Evaluation are provided. The primary application of the data is in the modeling of stratospheric processes, with particular emphasis on the ozone layer and its possible perturbation by anthropogenic and natural phenomena. Copies of this evaluation are available from the Jet Propulsion Laboratory.

  2. Chemical kinetic and photochemical data for use in stratospheric modelling

    NASA Technical Reports Server (NTRS)

    Demore, W. B.; Stief, L. J.; Kaufman, F.; Golden, D. M.; Hampton, R. F.; Kurylo, M. J.; Margitan, J. J.; Molina, M. J.; Watson, R. T.

    1979-01-01

    An evaluated set of rate constants and photochemical cross sections were compiled for use in modelling stratospheric processes. The data are primarily relevant to the ozone layer, and its possible perturbation by anthropogenic activities. The evaluation is current to, approximately, January, 1979.

  3. Modeling of simulated photochemical smog with kinetic mechanisms. Volume 1. Final report, July 1978-September 1979

    SciTech Connect

    Whitten, G.Z.; Killus, J.P.; Hogo, H.

    1980-02-01

    Mechanisms that describe the formation of photochemical smog are developed using a computer modeling technique directed toward the simulation of data collected in two smog chambers: an indoor chamber and a dual outdoor chamber. The results of simulating 164 different experiments are presented in Vol. 1. Individual compounds for which specific experiments were simulated and mechanisms developed include the following: formaldehyde, acetaldehyde, ethylene, propylene, butane, and toluene. Experiments in both chambers were simulated for all these compounds. The mechanisms reported describe the decay of the precursor organic compound, formation and decay of secondary organic compounds, conversion of nitrogen oxides, formation of nitrates, and the appearance and decay of ozone. Special emphasis is given to the chemistry of toluene. Also included is a study of a generalized smog-based or carbon-bond mechanism developed in a previous study.

  4. 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.

  5. The Antarctic ozone minimum - Relationship to odd nitrogen, odd chlorine, the final warming, and the 11-year solar cycle

    NASA Technical Reports Server (NTRS)

    Callis, L. B.; Natarajan, M.

    1986-01-01

    Photochemical calculations along 'diabatic trajectories' in the meridional phase are used to search for the cause of the dramatic springtime minimum in Antarctic column ozone. The results indicate that the minimum is principally due to catalytic destruction of ozone by high levels of total odd nitrogen. Calculations suggest that these levels of odd nitrogen are transported within the polar vortex and during the polar night from the middle to upper stratosphere and lower mesosphere to the lower stratosphere. The possibility that these levels are related to the 11-year solar cycle and are increased by enhanced formation in the thermosphere and mesosphere during solar maximum conditions is discussed.

  6. Ozone sensitivity to isoprene chemistry and emissions and anthropogenic emissions in central California

    NASA Astrophysics Data System (ADS)

    Dunker, Alan M.; Koo, Bonyoung; Yarwood, Greg

    2016-11-01

    Ozone formation in California in year 2017 was simulated using three chemical mechanisms: the Statewide Air Pollution Research Center 2007 mechanism with updated toxics and isoprene chemistry (S07TIC); the Carbon Bond 6, revision 2 (CB6r2) mechanism; a modified CB6r2 mechanism with increased hydroxyl radical (OH) production from isoprene oxidation at low nitrogen oxide (NOx) concentrations (CB6r2OH). The simulations with a photochemical grid model (PGM) showed little difference in ozone between CB6r2 and CB6r2OH. Further analysis with a box model found little sensitivity of ozone to OH production in the isoprene chemistry of all three mechanisms under conditions representative of California. The S07TIC generally predicts greater ozone than the CB6r2, and the difference in the predicted concentrations exceeds the uncertainty estimated from uncertainties in the emissions inventory. The sensitivity of ozone to anthropogenic volatile organic compound (VOC), NOx and carbon monoxide (CO) emissions and to isoprene emissions was also calculated with the PGM. Accounting for uncertainties in the emissions inventory, the sensitivity to NOx emissions is significantly different between S07TIC and CB6r2 in central and northern California; the sensitivity to isoprene emissions is significantly different in southern California. All mechanisms give a negative sensitivity of ozone to isoprene emissions in areas of northern California where NOx emissions are small. The CB6r2 and S07TIC differ in the sensitivity of ozone to organic nitrate (ON) formation from isoprene oxidation, likely because all ONs recycle to NOx in the S07TIC mechanism but only first-generation ONs do so in the CB6r2. For current California conditions, uncertainties in OH production from isoprene have little impact on ozone, but the extent to which isoprene ONs recycle NOx does impact ozone concentration and ozone sensitivity to NOx emissions.

  7. Reduction of trihalomethane formation and detoxification of microcystins in tap water by ozonation.

    PubMed

    Thapsingkaew, Orapin; Ruangyuttikarn, Werawan; Kijjanapanich, Vilailuck

    2008-06-01

    The efficiency of ozonation in comparison to chlorination for removal of microcystins and production of trihalomethanes (THMs) in water was investigated. One hundred and ninety water samples of ozone and chlorine treated water were collected at a water treatment plant between August 2004 and March 2005. The level of THMs, total organic carbon and residual chlorine were determined. Protein phosphatase 2A inhibition assay was used to detect microcystins and the presence of microcystins was confirmed by HPLC. The results show that 91.5% of the THM species in treated water was chloroform and 8.5% was bromodichloromethane. The mean THM level+/- standard error of mean in chlorinated water (CW) (45.1+/-3.0 microg/L) was higher than the mean of THM level in ozonated water (OW) (18.6+/-2.2 microg/L). In addition, no OW sample exceeded the first stage U.S. EPA maximum THM contaminant level for drinking water (80 microg/L) and only 8% of these samples exceeded the second stage level (40 microg/L). On the other hand, 3% of CW samples exceeded 80 microg/L and 68% exceeded the 40 microg/L level. The microcystin level in all water samples was below the WHO guideline value (1 microg/L) for drinking water.

  8. Photochemical Effects of Sunlight

    PubMed Central

    Daniels, Farrington

    1972-01-01

    The importance of sunlight in bringing about not only photosynthesis in plants, but also other photochemical effects, is reviewed. More effort should be devoted to photochemical storage of the sun's energy without the living plant. There is no theoretical reason to believe that such reactions are impossible. Ground rules for searching for suitable solar photochemical reactions are given, and a few attempts are described, but nothing successful has yet been found. Future possibilities are suggested. Photogalvanic cells which convert sunlight into electricity deserve further research. Eugene Rabinowitch has been an active pioneer in these fields. PMID:5037333

  9. Photochemical effects of sunlight.

    PubMed

    Daniels, F

    1972-07-01

    The importance of sunlight in bringing about not only photosynthesis in plants, but also other photochemical effects, is reviewed. More effort should be devoted to photochemical storage of the sun's energy without the living plant. There is no theoretical reason to believe that such reactions are impossible. Ground rules for searching for suitable solar photochemical reactions are given, and a few attempts are described, but nothing successful has yet been found. Future possibilities are suggested. Photogalvanic cells which convert sunlight into electricity deserve further research. Eugene Rabinowitch has been an active pioneer in these fields.

  10. Distribution of total ozone and stratospheric ozone in the tropics - Implications for the distribution of tropospheric ozone

    NASA Technical Reports Server (NTRS)

    Fishman, Jack; Larsen, Jack C.

    1987-01-01

    Climatologies of total columnar ozone and integrated stratospheric ozone amounts at low latitudes (15 deg N to 15 deg S), derived from satellite observations, are presented. A significant longitudinal variability in total ozone is present, with highest values generally located between 60 deg W and 60 deg E. The integrated stratospheric component of total ozone, on the other hand, does not exhibit a longitudinal preference for high values. Therefore it is hypothesized that the climatological longitudinal distribution of total ozone reflects the variability of the abundance of tropospheric ozone at low latitudes. Furthermore, it is speculated that in situ photochemical production of ozone resulting from biomass burning may be responsible for the observed enhancement of total ozone at these longitudes.

  11. Ozone Observations using Ozonesonde over the Himalaya from Pokhara, Nepal.

    NASA Astrophysics Data System (ADS)

    Dhungel, S.; Cullis, P.; Johnson, B.; Thompson, A. M.; Witte, J. C.; Panday, A. K.

    2016-12-01

    In recent years, transport of emissions from the Indo-Gangetic Plains (IGP), which covers parts of Pakistan, Nepal, India, Bangladesh has increased. Ozone pre-cursors like methane, nitrogen oxides, volatile organic carbons, and carbon monoxide from diesel based vehicular emission, biofuel and biomass burning, agricultural activities dominate the total emissions from the IGP. Synoptic circulation patterns along with local weather systems transport pollutants from the IGP up the Himalayan valleys to the Tibetan plateau. After being emitted, these pollutants are photochemically converted into tropospheric ozone - a short-lived climate pollutant that can increase atmospheric warming, alter processes of cloud formation, and in turn, influence precipitation levels and reduce carbon absorptivity in plants leading to decline in crop yields. However, little is known about vertical profiles of ozone concentration on the southern slopes of the Himalaya. Vertical ozone profiles were sampled from December 18th, 2015 to January 8th, 2016 from Pokhara (28.23°N, 83.99°E, 827m asl), Nepal using ozonesondes. Pokhara is located about 30km south of the Annapurna Himalaya, thus providing an ideal location to profile vertical ozone concentration south of the Himalaya. We launched one, two or four ozonesondes per day to examine the vertical resolution of ozone south of the Himalaya for the first time, and to understand the contribution of tropospheric and stratospheric sources. Here we present results from the 37 ozonesonde launches from Pokhara to examine: (i) how emissions from the IGP contribute to the vertical resolution of ozone, and (ii) if Himalayan orography provides an efficient path for stratosphere-troposphere air mass exchange under dry conditions. Our results show no signals of stratospheric air mass exchange. The results indicate higher levels of ozone within the boundary layer and lower troposphere. These higher values in the lower troposphere during winter seasons may

  12. Ozone Layer Observations

    NASA Technical Reports Server (NTRS)

    McPeters, Richard; Bhartia, P. K. (Technical Monitor)

    2002-01-01

    The US National Aeronautics and Space Administration (NASA) has been monitoring the ozone layer from space using optical remote sensing techniques since 1970. With concern over catalytic destruction of ozone (mid-1970s) and the development of the Antarctic ozone hole (mid-1980s), long term ozone monitoring has become the primary focus of NASA's series of ozone measuring instruments. A series of TOMS (Total Ozone Mapping Spectrometer) and SBUV (Solar Backscatter Ultraviolet) instruments has produced a nearly continuous record of global ozone from 1979 to the present. These instruments infer ozone by measuring sunlight backscattered from the atmosphere in the ultraviolet through differential absorption. These measurements have documented a 15 Dobson Unit drop in global average ozone since 1980, and the declines in ozone in the antarctic each October have been far more dramatic. Instruments that measure the ozone vertical distribution, the SBUV and SAGE (Stratospheric Aerosol and Gas Experiment) instruments for example, show that the largest changes are occurring in the lower stratosphere and upper troposphere. The goal of ozone measurement in the next decades will be to document the predicted recovery of the ozone layer as CFC (chlorofluorocarbon) levels decline. This will require a continuation of global measurements of total column ozone on a global basis, but using data from successor instruments to TOMS. Hyperspectral instruments capable of measuring in the UV will be needed for this purpose. Establishing the relative roles of chemistry and dynamics will require instruments to measure ozone in the troposphere and in the stratosphere with good vertical resolution. Instruments that can measure other chemicals important to ozone formation and destruction will also be needed.

  13. Impact of greenhouse gases on the Earth's ozone layer

    NASA Astrophysics Data System (ADS)

    Zadorozhny, Alexander

    A numerical 2-D zonally averaged interactive dynamical radiative-photochemical model of the ozonosphere including aerosol physics is used to examine the role of the greenhouse gases CO2 , CH4 , and N2 O in the future long-term changes of the Earth's ozone layer, in particular in its recovery after reduction of anthropogenic discharges of chlorine and bromine compounds into the atmosphere. The model allows calculating self-consistently 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 (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 abundance of the greenhouse gases on the dynamics of recovery of the Earth's ozone layer, 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 weakness 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