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Sample records for photochemical ozone formation

  1. Photochemically consumed hydrocarbons and their relationship with ozone formation in two megacities of China

    NASA Astrophysics Data System (ADS)

    Chang, C.; Wang, J.; Liu, S.; Shao, M.; Zhang, Y.; Zhu, T.; Shiu, C.; Lai, C.

    2010-12-01

    Two on-site continuous measurements of ozone and its precursors in two megacities of China were carried out in an urban site of Beijing and a suburban site near Guangzhou in the Pearl River Delta (PRD) to estimate precursor consumption and to assess its relationship with oxidant (O3+NO2) formation level. An observation-based method (OBM) with the precursor consumption concept was adopted to assess the relationship between oxidant production and amounts of photochemically consumed non-methane hydrocarbons (NMHCs). In this approach, the ratio of ethylbenzene to m,p-xylenes was used to estimate the degree of photochemical processing, as well as the amounts of photochemically consumed NMHCs by reacting with OH. By trying to correlate the observed oxidant with the observed NMHC concentration, the two areas both revealed nearly no to low correlation between them. However, it existed fair to good correlations (R2=0.68 for Beijing, 0.53 for PRD) between the observed oxidant level and the degree of photochemical processing (ethylbenzene/m,p-xylenes). Furthermore, after taking the approach of consumption to estimate the consumed amounts of NMHCs, an interesting finding reveals that the definite correlation existed between the observed oxidant level and the total consumed NMHCs. The good correlations (R2=0.83 for Beijing, 0.81 for PRD) implies that the ambient oxidant level correlated to the amount of consumed NMHCs. The results of the two megacities in China by using the OBM with the precursor consumption concept can provide another pathway to explore the relationship between photochemically produced oxidant and consumed precursors, and will be helpful to validate model results and to reduce uncertainty of model predictions. However, the method has some room for uncertainty, as injection of fresh precursor emissions and additional boundary ozone involved, etc. could affect the estimation of consumed NMHCs and observed oxidant levels. Assistance of approaches in assessing the

  2. 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

  3. The formation and inhibition of photochemical smog.

    PubMed

    Heicklen, J

    1987-01-01

    Photochemical smog is caused by a free-radical chain mechanism which converts NO to NO2. The NO2 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.

  4. 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

  5. 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.

  6. 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.

  7. 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.

  8. 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...

  9. Estimate of biogenic VOC emissions in Japan and their effects on photochemical formation of ambient ozone and secondary organic aerosol

    NASA Astrophysics Data System (ADS)

    Chatani, Satoru; Matsunaga, Sou N.; Nakatsuka, Seiji

    2015-11-01

    A new gridded database has been developed to estimate the amount of isoprene, monoterpene, and sesquiterpene emitted from all the broadleaf and coniferous trees in Japan with the Model of Emissions of Gases and Aerosols from Nature (MEGAN). This database reflects the vegetation specific to Japan more accurately than existing ones. It estimates much lower isoprene emitted from other vegetation than trees, and higher sesquiterpene emissions mainly emitted from Cryptomeria japonica, which is the most abundant plant type in Japan. Changes in biogenic emissions result in the decrease in ambient ozone and increase in organic aerosol simulated by the air quality simulation over the Tokyo Metropolitan Area in Japan. Although newly estimated biogenic emissions contribute to a better model performance on overestimated ozone and underestimated organic aerosol, they are not a single solution to solve problems associated with the air quality simulation.

  10. 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...

  11. 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.

  12. 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.

  13. 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.

  14. Photochemical production of ozone and control strategy for Southern Taiwan

    NASA Astrophysics Data System (ADS)

    Shiu, Chein-Jung; Liu, Shaw Chen; Chang, Chih-Chung; Chen, Jen-Ping; Chou, Charles C. K.; Lin, Chuan-Yao; Young, Chea-Yuan

    An observation-based method (OBM) is developed to evaluate the ozone (O 3) production efficiency (O 3 molecules produced per NO x molecule consumed) and O 3 production rate ( P(O 3)) during a field campaign in southern Taiwan. The method can also provide an estimate of the concentration of OH. A key step in the method is to use observed concentrations of two aromatic hydrocarbons, namely ethylbenzene and m, p-xylene, to estimate the degree of photochemical processing and amounts of photochemically consumed NO x and NMHCs by OH. In addition, total oxidant (O 3+NO 2) instead of O 3 itself turns out to be very useful for representing ozone production in the OBM approach. The average O 3 production efficiency during the field campaign in Fall (2003) is found to be about 10.2±3.9. The relationship of P(O 3) with NO x is examined and compared with a one-dimensional (1D) photochemical model. Values of P(O 3) derived from the OBM are slightly lower than those calculated in the 1D model. However, OH concentrations estimated by the OBM are about a factor of 2 lower than the 1D model. Fresh emissions, which affect the degree of photochemical processing appear to be a major cause of the underestimate. We have developed a three-dimensional (3D) OBM O 3 production diagram that resembles the EKMA ozone isopleth diagram to study the relationship of the total oxidant versus O 3 precursors. The 3D OBM O 3 production diagram suggests that reducing emissions of NMHCs are more effective in controlling O 3 than reducing NO x. However, significant uncertainties remain in the OBM, and considerable more work is required to minimize these uncertainties before a definitive control strategy can be reached. The observation-based approach provides a good alternative to measuring peroxy radicals for evaluating the production of O 3 and formulating O 3 control strategy in urban and suburban environments.

  15. Photochemical trajectory modeling of ozone concentrations in Hong Kong.

    PubMed

    Cheng, H R; Saunders, S M; Guo, H; Louie, P K K; Jiang, F

    2013-09-01

    In this study, tropical cyclones over the East and South China Seas were found to be the most predominant weather conditions associated with the occurrence of high ozone (O3) episodes in Hong Kong in 2005-2009. A photochemical trajectory model coupled with Master Chemical Mechanism (MCM) was adapted to simulate the O3 concentrations during two O3 pollution episodes. The results agreed well with the observed data. A representative backward air mass trajectory was used to determine the contribution of each volatile organic compound (VOC) to the O3 levels. After taking into account both reactivity and mass emission of each VOC, 10 species were found to be the key O3 precursors in Hong Kong. Further analysis identified solvent related products accounting for 70% of the modeled O3 concentration in Hong Kong. The results highlight the importance of considering together reactivity and source sector emissions in developing targeted VOC reduction for O3 abatement strategies.

  16. 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.

  17. 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.

  18. Matrix isolation study of the photochemical reaction of cyclohexane, cyclohexene, and cyclopropane with ozone

    NASA Astrophysics Data System (ADS)

    Hoops, Michael D.; Ault, Bruce S.

    2009-07-01

    The matrix isolation technique, combined with infrared spectroscopy, has been used to characterize the products of the photochemical reactions of cyclohexane, cyclohexene, and cyclopropane with ozone. While initial twin jet deposition of the reagents led to no visible changes in the recorded spectra, strong product bands were noted following irradiation with light of λ > 200 nm. Irradiation of matrices containing ozone and cyclohexane led to O atom reactions with insertion into a C sbnd H bond and a C sbnd C bond to form cyclohexanol and oxacycloheptane, respectively. Irradiation of matrices containing ozone and cyclohexene led to a mixture of products formed through oxidation of the double bond, including cyclohexanone and cyclohexene oxide. Cyclopropane and ozone were codeposited into argon matrices followed by irradiation, leading to the formation of both cyclopropanal through insertion into a C sbnd H bond and aldehydes through ring-opening and oxidation. These conclusions were supported by isotopic labeling ( 18O), by comparison to authentic infrared spectra, and by B3LYP/6-311G++(d,2p) density functional calculations.

  19. 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.

  20. 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.

  1. Sources of ambient volatile organic compounds and their contributions to photochemical ozone formation at a site in the Pearl River Delta, southern China.

    PubMed

    Ling, Z H; Guo, H; Cheng, H R; Yu, Y F

    2011-10-01

    The Positive Matrix Factorization (PMF) receptor model and the Observation Based Model (OBM) were combined to analyze volatile organic compound (VOC) data collected at a suburban site (WQS) in the PRD region. The purposes are to estimate the VOC source apportionment and investigate the contributions of these sources and species of these sources to the O(3) formation in PRD. Ten VOC sources were identified. We further applied the PMF-extracted concentrations of these 10 sources into the OBM and found "solvent usage 1", "diesel vehicular emissions" and "biomass/biofuel burning" contributed most to the O(3) formation at WQS. Among these three sources, higher Relative Incremental Reactivity (RIR)-weighted values of ethene, toluene and m/p-xylene indicated that they were mainly responsible for local O(3) formation in the region. Sensitivity analysis revealed that the sources of "diesel vehicular emissions", "biomass/biofuel burning" and "solvent usage 1" had low uncertainties whereas "gasoline evaporation" showed the highest uncertainty. PMID:21616570

  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. 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...

  4. 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...

  5. 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.

  6. 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.

  7. 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

  8. A photochemical modeling study of ozone and formaldehyde generation and budget in the Po basin

    NASA Astrophysics Data System (ADS)

    Liu, L.; Andreani-Aksoyoglu, S.; Keller, J.; OrdóñEz, C.; Junkermann, W.; Hak, C.; Braathen, G. O.; Reimann, S.; Astorga-Llorens, C.; Schultz, M.; PréVôT, A. S. H.; Isaksen, I. S. A.

    2007-11-01

    In this work, a photochemical dispersion model, CAMx (Comprehensive Air quality Model with eXtensions) was used to simulate a high ozone episode observed in the Po basin during the 2003 FORMAT (Formaldehyde as a Tracer of Oxidation in the Troposphere) campaign. The study focuses on formaldehyde and ozone, and a budget analysis was set up for interpreting the importance of different processes, namely emission, chemistry, transport and deposition, for three different areas (urban, downwind, suburban) around the Milan metropolitan region. In addition, a sensitivity study was carried out based on 11 different VOC emission scenarios. The results of the budget study show that the strongest O3 production rate (4 ppbv/hour) occurs in the downwind area of the city of Milan, and that accumulated O3 is transported back to Milan city during nighttime. More than 80% of the HCHO concentration over the Milan metropolitan region is secondary, i.e., photochemically produced from other VOCs. The sensitivity study shows that the emissions of isoprene are not, on average, a controlling factor for the peak concentrations of O3 and HCHO over the model domain because of very few oak trees in this region. Although the paraffinic (PAR) emissions are fairly large, a 20% reduction of PAR yields only 1.7% of HCHO reduction and 2.7% reduction of the O3 peak. The largest reduction of O3 levels can be obtained by reduced xylene (XYL) emissions. A 20% reduction of the total anthropogenic VOC emissions leads to 15.5% (20.3 ppbv) reduction of O3 peak levels over the Milan metropolitan region.

  9. 76 FR 72919 - Draft Integrated Science Assessment for Ozone and Related Photochemical Oxidants

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-11-28

    ... published on September 30, 2011 (76 FR 60820). This assessment document was developed by the National Center... instructions provided in the SUPPLEMENTARY INFORMATION section of Federal Register Notice (76 FR 60820). For... AGENCY Draft Integrated Science Assessment for Ozone and Related Photochemical Oxidants...

  10. 76 FR 17121 - Draft Integrated Science Assessment for Ozone and Related Photochemical Oxidants

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-03-28

    ... published on February 28, 2011 (76 FR 10893). This assessment document was developed by the National Center... provided in the SUPPLEMENTARY INFORMATION section of Federal Register Notice (76 FR 10893). For information... AGENCY Draft Integrated Science Assessment for Ozone and Related Photochemical Oxidants...

  11. 76 FR 60820 - Draft Integrated Science Assessment for Ozone and Related Photochemical Oxidants

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-09-30

    ... Assessment for Ozone and Related Photochemical Oxidants'' will be available primarily via the Internet on the... which, among other things, ``cause or contribute to air pollution which may reasonably be anticipated to... the independent scientific review of EPA's air quality criteria. On September 29, 2008 (73 FR...

  12. 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...

  13. 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...

  14. 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 ...

  15. Recent laboratory photochemical studies and their relationship to the photochemical formation of cometary radicals

    NASA Technical Reports Server (NTRS)

    Jackson, William M.

    1991-01-01

    Experimental laboratory techniques used in studying the photochemistry of stable and unstable molecules are discussed. The laboratory evidence for the photochemical formation of C2 from C2H, C3 from C3H2, and NH from NH2 is presented. Other recent results obtained in laboratory studies of H2O, H2S, NH3, and HCN are reported.

  16. 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.

  17. 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

  18. Ozone and photochemical pollutants: status after 25 years

    SciTech Connect

    Speizer, F.E.

    1985-03-01

    Data related to the health effects of air pollution are discussed in this editorial. Three kinds of studies - animal experimentation, controlled chamber experiments in both animals and humans and population-based epidemiological investigations are reported from a seminar held at the University of California, Davis. Each is summarized as to whether it proved to be a health effect for ozone or NO/sub 2/. The role of physicians in the interpretation of the data and in public policy decision-making is examined.

  19. 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.

  20. 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

  1. 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

  2. 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.

  3. Effects of photochemical formation of mercuric oxide

    SciTech Connect

    Granite, E.J.; Pennline, H.W.; Hoffman, J.S.

    1999-12-01

    The photochemistry of elemental mercury and oxygen was examined using quartz flow reactors. Germicidal bulbs were used as the source of 253.7-nm ultraviolet radiation. The formation of mercuric oxide, as visually detected by yellow-brown stains on the quartz walls, was confirmed by both ICP-AES and SEM-EDX analyses. In addition, a high surface area calcium silicate sorbent was used to capture the mercuric oxide in one of the experiments. The implications of mercuric oxide formation with respect to analysis of gases for mercury content, atmospheric reactions, and direct ultraviolet irradiation of flue gas for mercury sequestration are discussed.

  4. A Comparison of a Photochemical Model with SHIMMER hydroxyl and SABER ozone data

    NASA Astrophysics Data System (ADS)

    Siskind, D. E.; Stevens, M. H.; Englert, C. R.; Marsh, D. R.

    2011-12-01

    Mesospheric ozone photochemistry is primarily dominated by a catalytic loss cycle involving odd hydrogen (HOx). In principal, this comparatively simple chemistry could be tested with simultaneous comparison of a model with ozone and odd hydrogen data. Until recently, such comparisons could not be made because such simultaneous data did not exist. However, with the recent conclusion of the successful 30 month mission of The Spatial Heterodyne Image for Mesospheric Radicals (SHIMMER) on a Space Test Program satellite (STPSat-1) , we now have the data with which to perform these studies. SHIMMER made high quality, high vertical resolution measurements measurements of hydroxyl (OH) from 60-80 km for a wide range of local times. The ozone data comes from measurements made by the Sounding of the Atmosphere with Broadband Emission Radiometry (SABER) on the NASA TIMED satellite. Since TIMED and STPSat observed the atmosphere simultaneously but at different local times, these OH and ozone data are studied using a diurnal photochemical model as a "transfer standard" that was sampled for lighting conditions appropriate to each experiment. We have used the eddy diffusion coefficient as a free parameter to be constrained by the model-data comparison. The results suggest very good general agreement with SHIMMER OH, except for a puzzling overestimate by the model of the data in the late afternoon at the highest altitudes. By contrast, the comparison with SABER ozone shows persistent large discrepancies whereby the model falls below the data; reasons for this will be offered.

  5. 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.

  6. 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…

  7. 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

  8. 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

  9. Photochemical ozone creation potentials for oxygenated volatile organic compounds: sensitivity to variations in kinetic and mechanistic parameters

    NASA Astrophysics Data System (ADS)

    Jenkin, Michael E.; Hayman, Garry D.

    The sensitivity of Photochemical Ozone Creation Potentials (POCP) to a series of systematic variations in the rates and products of reactions of radical intermediates and oxygenated products is investigated for the C 4 alcohols, 1-butanol ( n-butanol) and 2-methyl-1-propanol ( i-butanol), using the recently developed Master Chemical Mechanism (MCM) as the base case. The POCP values are determined from the calculated formation of ozone in the boundary layer over a period of approximately five days along an idealised straight line trajectory, using a photochemical trajectory model and methodology described in detail previously. The results allow the relative impacts on calculated ozone formation of various classes of chemical reaction within the degradation chemistry to be assessed. The calculated POCP is found to be very insensitive to many of the changes investigated. However, it is found to be sensitive to variations in the rate coefficient for the initiating reaction with OH ( kOH), although the sensitivity decreases with increasing kOH. The POCP appears to vary approximately linearly with kOH at low values (i.e. kOH less than ca. 4×10 -13 cm 3 molecule -1 s -1), whereas at high reactivities (i.e. kOH greater than ca. 4×10 -11 cm 3 molecule -1 s -1), the calculated POCP value is comparatively insensitive to the precise value of kOH. The POCP is also very sensitive to mechanistic changes which influence the yields of unreactive oxygenated products (i.e. those with OH reactivities below ca. 10 -12 cm 3 molecule -1 s -1), for example acetone. The propensity of the organic compound to produce organic nitrates (which act as comparatively unreactive reservoirs for free radicals and NO x) also appears to have a notable influence on the calculated POCP. Recently reported information relevant to the degradation of oxygenated VOCs is then used to update the chemical schemes for the 17 alcohols and glycols, 10 ethers and glycol ethers, and 8 esters included in the MCM

  10. 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.

  11. 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

  12. 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 ...

  13. Atmospheric iodine abates smog ozone.

    PubMed

    HAMILTON, W F; LEVINE, M; SIMON, E

    1963-04-12

    Traces of iodine in test samples of irradiated photochemical smog atmospheres either inhibit ozone formation or lower its concentration. Eye and respiratory irritation are reduced qualitatively. Iodine is more effective in suppressing ozone in a photochemical smog atmosphere than it is in purified air.

  14. 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.

  15. 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.

  16. Indicators of photochemistry in DISCOVER-AQ observations: Implications for diagnosing ozone production and photochemical intensity from space

    NASA Astrophysics Data System (ADS)

    Crawford, J. H.; Olson, J. R.; Chen, G.; Kleb, M. M.; Weinheimer, A. J.; Knapp, D. J.; Montzka, D.; Fried, A.; Walega, J.; Diskin, G. S.; Sachse, G. W.; Wisthaler, A.; Mikoviny, T.; Barrick, J. D.; Janz, S. J.; Kowalewski, M. G.; Yang, M. M.; Pickering, K. E.

    2013-12-01

    The DISCOVER-AQ series of field studies aims to collect observations that will improve the ability of satellites to diagnose surface air quality. A related goal is to evaluate and optimize future observing strategies combining ground-based and satellite observations. To date, detailed repetitive observations of atmospheric composition in the lower atmosphere have been collected over three locations: the Baltimore-Washington corridor, the southern San Joaquin Valley, and Houston. These observations include remotely-sensed column abundances as well as detailed in situ chemical soundings of ozone and its precursors in the lowest 3 km. Satellite observations are limited to a few key constituents controlling ozone production, e.g., ozone, NO2, and CH2O. If available, space-based observations of CO, CO2, and CH4 may also be useful for understanding the relative importance of anthropogenic and biogenic hydrocarbons. An analysis of cross-correlations between observations of ozone, NO2, and formaldehyde columns along with photochemical modeling of the more detailed DISCOVER-AQ observations is presented to determine what behaviors are likely to be detectable from space and how they might be used to diagnose how photochemical transformation and transport of emissions influence local air quality related to ozone.

  17. 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.

  18. 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

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. Photochemical oxidation of chloride ion by ozone in acid aqueous solution.

    PubMed

    Levanov, Alexander V; Isaykina, Oksana Ya; Amirova, Nazrin K; Antipenko, Ewald E; Lunin, Valerii V

    2015-11-01

    The experimental investigation of chloride ion oxidation under the action of ozone and ultraviolet radiation with wavelength 254 nm in the bulk of acid aqueous solution at pH 0-2 has been performed. Processes of chloride oxidation in these conditions are the same as the chemical reactions in the system O3 - OH - Cl(-)(aq). Despite its importance in the environment and for ozone-based water treatment, this reaction system has not been previously investigated in the bulk solution. The end products are chlorate ion ClO3(-) and molecular chlorine Cl2. The ions of trivalent iron have been shown to be catalysts of Cl(-) oxidation. The dependencies of the products formation rates on the concentrations of O3 and H(+) have been studied. The chemical mechanism of Cl(-) oxidation and Cl2 emission and ClO3(-) formation has been proposed. According to the mechanism, the dominant primary process of chloride oxidation represents the complex interaction with hydroxyl radical OH with the formation of Cl2(-) anion-radical intermediate. OH radical is generated on ozone photolysis in aqueous solution. The key subsequent processes are the reactions Cl2(-) + O3 → ClO + O2 + Cl(-) and ClO + H2O2 → HOCl + HO2. Until the present time, they have not been taken into consideration on mechanistic description and modelling of Cl(-) oxidation. The final products are formed via the reactions 2ClO → Cl2O2, Cl2O2 + H2O → 2H(+) + Cl(-) + ClO3(-) and HOCl + H(+) + Cl(-) ⇄ H2O + Cl2. Some portion of chloride is oxidized directly by O3 molecule with the formation of molecular chlorine in the end.

  4. Photochemical oxidation of chloride ion by ozone in acid aqueous solution.

    PubMed

    Levanov, Alexander V; Isaykina, Oksana Ya; Amirova, Nazrin K; Antipenko, Ewald E; Lunin, Valerii V

    2015-11-01

    The experimental investigation of chloride ion oxidation under the action of ozone and ultraviolet radiation with wavelength 254 nm in the bulk of acid aqueous solution at pH 0-2 has been performed. Processes of chloride oxidation in these conditions are the same as the chemical reactions in the system O3 - OH - Cl(-)(aq). Despite its importance in the environment and for ozone-based water treatment, this reaction system has not been previously investigated in the bulk solution. The end products are chlorate ion ClO3(-) and molecular chlorine Cl2. The ions of trivalent iron have been shown to be catalysts of Cl(-) oxidation. The dependencies of the products formation rates on the concentrations of O3 and H(+) have been studied. The chemical mechanism of Cl(-) oxidation and Cl2 emission and ClO3(-) formation has been proposed. According to the mechanism, the dominant primary process of chloride oxidation represents the complex interaction with hydroxyl radical OH with the formation of Cl2(-) anion-radical intermediate. OH radical is generated on ozone photolysis in aqueous solution. The key subsequent processes are the reactions Cl2(-) + O3 → ClO + O2 + Cl(-) and ClO + H2O2 → HOCl + HO2. Until the present time, they have not been taken into consideration on mechanistic description and modelling of Cl(-) oxidation. The final products are formed via the reactions 2ClO → Cl2O2, Cl2O2 + H2O → 2H(+) + Cl(-) + ClO3(-) and HOCl + H(+) + Cl(-) ⇄ H2O + Cl2. Some portion of chloride is oxidized directly by O3 molecule with the formation of molecular chlorine in the end. PMID:26077317

  5. 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).

  6. Design considerations for ozone and acid aerosol exposure and health investigations: the Fairview Lake summer camp - photochemical smog case study

    SciTech Connect

    Lioy, P.J.; Spektor, D.; Thurston, G.; Citak, K.; Lippmann, M.; Bock, N.; Speizer, F.E.; Hayes, C.

    1987-01-01

    The health effects associated with ozone and acidic particulate sulfate exposures to active children have been and are being addressed in field epidemiological studies at summer camps in rural areas of the Northeastern US. The rationale and study design for studies, which have been conducted in Pennsylvania and New Jersey, are developed and reviewed. As background, results are summarized for human clinical and epidemiological studies and animal studies. These provided the basis for selection of health outcomes measured results from chemical characterization and transport studies are reviewed to define the criteria used for selection of a site which is effected by high ozone and acid species during photochemical smog episodes. The integration of the study design is discussed in detail by reviewing its application to the 1984 - Fairview Lake Camp Study (July 8 to August 4). The features of the camp study are reviewed, including the study population, pulmonary function procedures and analyses, air pollution monitoring instrumentation, and the site characteristics. The pollution exposure data are presented, for ozone and acidic sulfates and examined for the range and distribution concentration. Further information is provided on the intensity and duration of episodes encountered over the course of the study. Episodes occurred which had ozone and acid sulfates, ozone alone, and acid sulfates alone. 56 references, 9 figures.

  7. 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.

  8. 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

  9. Ozone and secondary aerosol formation — Analysis of particle observations in the 2009 SHARP campaign

    NASA Astrophysics Data System (ADS)

    Cowin, J.; Yu, X.; Laulainen, N.; Iedema, M.; Lefer, B. L.; Anderson, D.; Pernia, D.; Flynn, J. H.

    2010-12-01

    Particulate matters (PM) play important roles in the formation and transformation of ozone. Although photooxidation of volatile organic compounds with respect to ozone formation in the gas phase is well understood, many unknowns still exist in heterogeneous mechanisms that process soot, secondary aerosols (both inorganic and organic), and key radical precursors such as formaldehyde and nitrous acid. Our main objective is to answer two key science questions: 1) will reduction of fine PM reduce ozone formation? 2) What sources of PM are most culpable? Are they from local chemistry or long-range transport? The field data collected in the 2009 Study of Houston Atmospheric Radical Precursors (SHARP) by our group at the Moody Tower consist of 1) real-time photolysis rates of ozone precursors, 2) particle size distributions, 3) organic carbon and elemental carbon, and 4) an archive of single particle samples taken with the Time Resolved Aerosol Collector (TRAC) sampler. The time resolution of the TRAC sampler is 30 minutes for routine measurements, and 15 minutes during some identified “events” (usually in the mid-afternoon) of high ozone and secondary organic or sulfate particle formation. The latter events last typically about an hour. Five ozone exceedance days occurred during the 6 weeks of deployment. Strong correlation between photochemical activities and organic carbon was observed. Initial data analysis indicates that secondary organic aerosol is a major component of the carbonaceous aerosols observed in Houston. Soot, secondary sulfate, seal salt, and mineral dust particles are determined from single particle analysis using scanning electron microscope and transmission electron microcopy coupled with energy dispersive X-ray spectroscopy. Compared with observations in 2000, the mass percentage of organics is higher (60 vs. 30%), and lower for sulfate (20% vs. 32%). On-going data analysis will focus on the composition, sources, and transformation of primary and

  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. 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.

  12. 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.

  13. 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.

  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. PMID:20434908

  15. 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.

  16. 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

  17. Comparison of the SAPRC07 and SAPRC99 photochemical mechanisms during a high ozone episode in Texas: Differences in concentrations, OH budget and relative response factors

    NASA Astrophysics Data System (ADS)

    Li, Jingyi; Zhang, Hongliang; Ying, Qi

    2012-07-01

    The latest SAPRC photochemical mechanism SAPRC07 (S07), an update from SAPRC99 (S99), is implemented into the Community Multi-scale Air Quality (CMAQ) model and applied to simulate a high ozone episode during the Texas Air Quality Study 2000 (TexAQS 2000). The results from the S07 mechanism are compared with those from the S99 mechanism. In general, the predicted O3 concentrations by S07 are lower than those of S99 with maximum difference as high as 20%. The two mechanisms also show significant differences in the predicted OH, HNO3, PAN and HCHO concentrations. S99 predicts higher OH concentration by 7-20%, higher PAN by approximately 20-25% and higher HCHO by approximately 15% than S07. OH budget analysis suggests that OH propagation factor (POH) is higher in urban and industrial areas but lower in rural areas. Although S07 generally predicts similar or higher POH, S99 predicts higher new OH formation rate from H2O + O(1D) and leads to higher OH and thus higher O3 in most part of the domain. OH reactions with VOCs and CO accounts for a majority part of reacted OH. Secondary VOCs photolysis is not a main path of regenerated OH. New OH mainly comes from H2O + O(1D) reaction. Although the two mechanisms predict different ozone concentrations, the relative response factor (RRF) of ozone at rural, urban and industrial sites under emission controls of anthropogenic NOx and VOC controls by factors 0.6-1.4 predicted by the two mechanisms are very similar. This suggests that although the absolute predictions are different, both models will provide nearly identical attainment assessment in regulatory applications.

  18. Results of photochemical modeling sensitivity analyses in the Lake Michigan region: Current status of Lake Michigan Ozone Control Program (LMOP) modeling

    SciTech Connect

    Dolwick, P.D.; Kaleel, R.J.; Majewski, M.A.

    1994-12-31

    The four states that border Lake Michigan are cooperatively applying a state-of-the-art nested photochemical grid model to assess the effects of potential emission control strategies on reducing elevated tropospheric ozone concentrations in the region to levels below the national ambient air quality standard. In order to provide an extensive database to support the application of the photochemical model, a substantial data collection effort known as the Lake Michigan Ozone Study (LMOS) was completed during the summer of 1991. The Lake Michigan Ozone Control Program (LMOP) was established by the States of Illinois, Wisconsin, Michigan, and Indiana to carry out the application of the modeling system developed from the LMOS, in terms of developing the attainment demonstrations required from this area by the Clean Air Act Amendments of 1990.

  19. 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.

  20. Ozone formation due to interaction of meteoroids with Earth's atmosphere

    NASA Technical Reports Server (NTRS)

    Bibarsov, R. SH.

    1987-01-01

    In a previous paper, it was shown that concentration of atomic oxygen in overdense meteor trails may exceed that of the normal atmosphere by a factor of several hundred times. This may lead to the formation of meteoric ozone. Therefore, it is imperative to estimate the concentration of ozone in the trails of meteor bodies with different masses. It seems that meteoric ozone must be taken into account when studying the balance of ionization in the meteor trails formed by particles with masses more than .01 g. The predicted levels of atomic oxygen and ozone seem sufficient to greatly influence the rate of meteoric plasma deionization.

  1. Dobson spectrophotometer total ozone measurement errors caused by interfering absorbing species such as SO2, NO2, and photochemically produced O3 in polluted air

    NASA Astrophysics Data System (ADS)

    Komhyr, W. D.; Evans, R. D.

    1980-02-01

    Total ozone measurements made with Dobson spectrophotometers in polluted air are subject to errors caused by interfering trace gas species that absorb solar ultraviolet radiation. While such interference is probably non-existent or small at the majority of Dobson instrument stations throughout the world, errors of up to 25% and 5%, resulting from absorption by SO2 and NO2 respectively, may occur occasionally at a few stations located in extremely polluted atmospheres. Interference by other absorbers, including N2O5, H2O2, HNO3, acetyldehyde, acetone, and acrolein has been found to be negligible. Ozone produced photochemically in polluted near-surface air may occasionally constitute from 5% to 10% of the atmospheric total ozone column. Such ozone interferes with measurements of atmospheric background total ozone.

  2. 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

  3. 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.

  4. 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. PMID:25070769

  5. 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.

  6. 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.

  7. 76 FR 10893 - Draft Integrated Science Assessment for Ozone and Related Photochemical Oxidants

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-02-28

    ... in the development of the ISA (75 FR 42085). The first external review draft ISA for Ozone and... criteria. On Sep 29, 2008 (73 FR 56581), EPA formally initiated its current review of the air quality... via a publicly accessible teleconference consultation on November 13, 2009 (74 FR 54562). In...

  8. 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.

  9. Air Quality Criteria for Ozone and Related Photochemical Oxidants (2006 Final)

    EPA Science Inventory

    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 t...

  10. [Study on bromate formation of catalytic ozonation process].

    PubMed

    Wu, Lin; Yang, Hong-Wei; Yang, Shao-Xia; Lü, Miao; Cheng, Wen

    2011-08-01

    In a batch reactor, the BrO3(-) formation was investigated in the ozonation and catalytic ozonation of Br(-)-containing Yellow river water, using the different heterogeneous catalysts. The results showed that BrO3(-) minimization was achieved in the catalytic ozonation with NiO, CuO, Fe3O4 and Al2O3 as catalysts and the percent reductions of BrO3(-) were 34.0%, 32.8%, 29.2% and 20.8% respectively. In the reaction R(ct), the ratio of concentration of *OH to O3, decreased with the reaction time, and the range of R(ct) was from 10(-8) to 10(-6). In the ozonation process, one of the main reaction pathways of BrO3(-) formation was the combination oxidation of Br(-) by *OH and then O3, another was the combination oxidation of Br(-) by O3 and then *OH. In the catalytic ozonation with Fe3O4 catalyst, the main pathway was the combination oxidation by *OH and then O3. Moreover, about 60.7% removal for UV254 was obtained after 20 min in the catalytic ozonation reaction. In our study, it was found that the catalytic ozonation process can effectively minimize the formation of BrO3(-) and also oxidize organic compounds. PMID:22619950

  11. Photochemical formation of oligopepides in the space processes modeling experiments

    NASA Astrophysics Data System (ADS)

    Gontareva, N.; Kuzicheva, E.

    The origin of life may be considered as a sequence of events, each of which adds to the molecular complexity and order. Abundance of chemical building blocks synthesized previously is a prerequisite for the beginning of the next evolutionary step. That's why the availability of chemical building blocks for peptides and nucleic acids, their formation and resistance towards destructive impacts should not be underestimated. At the number of our previous publications it was reported about the oligopeptides and nucleotides formation promoted by cosmic energy sources at the terrestrial orbit. The next important question to solve was whether mineral beds could have protected these biological important substances from the destructive action of space radiation. Minerals of extraterrestrial origin, such as lunar soil, Allende and Murchison meteorites, were tested with respect of their protective properties. UV radiation of short wavelength (the most abundant and powerful source of energy during the period of early chemical evolution) was taken as the energy supplier triggering the solid phase synthesis process. Solid films consisting out of two aminoacids (Gly + Phe) were irradiated by UV 254 in course of the experiment - free or associat ed with minerals. As the result of exposure process, both dipeptides and tripeptides of certain aminoacids were identified. Presence of inorganic beds during irradiation increased the yield of oligopeptides. For lunar soil, the yield increased by 3.8 times, while in case of meteorite beds the rate between free and associated with clay samples was 1.4. These data correlate with our previous results on VUV 145 irradiation of the same mixture (Gly + Phe), irradiation dose 2.12*106 J m-2. The same set of products was traced in both experimental cases, while the quantitative yield of products was one order of magnitude less for the case of UV254 and the relevant irradiation dosage much higher - 2.64*107 J m -2. It should be considered, that at

  12. 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.

  13. 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.

  14. 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.

  15. Applications of the Regional Atmospheric Modeling System (RAMS) to provide input to photochemical grid models for the Lake Michigan Ozone Study (LMOS)

    SciTech Connect

    Lyons, W.A.; Tremback, C.J.; Pielke, R.A.; Eastman, J.L.

    1994-12-31

    In spite of stringent emission controls, numerous exceedances of the US ozone air quality standard have continued in the Lake Michigan region, especially during the very hot summers of 1987 and 1988. Analyses revealed that exceedances of the 120 PPB hourly standard were 400% more likely at monitors located within 20 km of the lakeshore. While the role of Lake Michigan in exacerbating regional air quality problems has been investigated for almost 20 years, the relative impacts of various phenomena upon regional photochemical air quality have yet to be quantified. In order to design a defensible regional emission control policy, LMOS sponsored the development of a comprehensive regional photochemical modeling system. This is comprised of an emission model, an advanced regional photochemical model, and a prognostic meteorological model.

  16. Variabilities in Ozone and Precursors over the Central Himalayas: Relation with Photochemical and Dynamical Processes

    NASA Astrophysics Data System (ADS)

    Sarangi, T.; Naja, M. K.; Ojha, N.; Kumar, R.; Venkataramani, S.; Lal, S.

    2013-12-01

    Trace gases play vital roles in the tropospheric chemistry, air quality degradation and climate change. Despite this, measurements of the key trace gases are sparse over the Indian region, particularly over the Northern India including Indo-Gangetic Plain (IGP), where elevated levels of pollution loadings has been observed in different satellite based studies. In view of this, measurements of ozone and related trace gases along with various weather parameters have been made at a high altitude site (Nainital; 29.37oN, 79.45oE, 1958 m amsl) in the central Himalayas. This site is located just north of the IGP region and topography is complex around the site. Diurnal variations in ozone do not show a daytime build up, indicating that photochemistry plays only a minor role in ozone variations at Nainital. While, in contrast, CO and NOy generally show higher levels during daytime and lower levels during nighttime. WRF model has been used to simulate the variability in vertical wind component and boundary layer height. It is shown that the diurnal variations in trace gases are mainly governed by the dynamical processes including upslope downslope mountain winds and boundary layer evolution and associated convective mixing. Seasonal variations in ozone, CO and NOy at Nainital are characterized by spring maxima and summer-monsoon minima. This seasonality is found in good agreement with the variability of weather parameters. Seasonality in CH4 and light (C2-C5) NMHCs shows a late autumn and early winter maxima and summer monsoon minima. Regional pollution supplemented with northern Indian biomass burning is suggested to play key roles in the variations of trace gases over Nainital. The classification based on the air-mass residence time and boundary layer height shows levels of ozone, CO and NOy, 57×14 ppbv, 206×125 ppbv, and 1856×1596 pptv in continental and 25×11 ppbv, 120×50 ppbv, and 336.6×211 pptv in marine air-mass respectively. Ozone-CO slope values are lower as

  17. 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. PMID:21155074

  18. Residence time analysis of photochemical buildup of ozone in central eastern China from surface observation at Mt. Tai, Mt. Hua, and Mt. Huang in 2004.

    PubMed

    Pochanart, Pakpong

    2015-09-01

    Using data from surface observation, backward trajectories, and residence time analysis, the amounts of regional photochemical ozone buildup due to the large-scale anthropogenic sources in central eastern China (CEC, 30.5-40.5 N, 112.5-122.5 E) at Mt. Tai, Mt. Hua, and Mt. Huang in 2004 were quantified. It was found that the CEC anthropogenic sources influenced the air masses and the associated ozone production most at Mt. Tai, located at the center of CEC domain. At Mt. Hua to the west of CEC domain and at Mt. Huang to the south of CEC domain, the air masses and the associated ozone production showed less CEC anthropogenic influences on a regional scale. At Mt. Tai and Mt. Huang, the ozone mixing ratios in the air masses that passed over polluted source regions in CEC increased during the first 40-70 h after arrival and showed the highest production rate of 31.2 and 12.2 ppb/day, respectively, in May and June. It was estimated that the CEC anthropogenic sources contributed 34-42% of ozone at Mt. Tai and 8-14% at Mt. Huang during this ozone peak season. The large contributions from CEC sources during fall season (Sep-Nov) were also estimated as 31-44 and 17-23% but with the lower ozone production rate of 22.6 and 8.4 ppb/day, respectively, for Mt. Tai and Mt. Huang.

  19. Role of ozone precursors in tropospheric ozone formation and control: A report to Congress

    SciTech Connect

    Not Available

    1993-07-01

    Tropospheric ozone pollution, which occurs at ground level and is the major component of ground-level summertime smog, remains an important environmental and health concern despite nearly 20 years of regulatory efforts. Ozone is a secondary pollutant formed in the atmosphere by reactions of volatile organic compounds (VOCs) and oxides of nitrogen (NOx) in the presence of sunlight. Carbon monoxide (CO) also plays a role in the formation of ozone. Major sources of VOCs include exhaust and evaporative emissions from motor vehicles, emissions from solvent use and emissions from the chemical and petroleum industries. The following EPA perspectives identify two key components (strategy selection; modeling and data bases) which must be addressed in resolving the tropospheric ozone problem.

  20. [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.

  1. 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.

  2. 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.

  3. 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

  4. [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

  5. [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

  6. 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.

  7. 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.

  8. 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.

  9. 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

  10. 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...

  11. Modeling Ozone Formation and Transport in the Cascadia Region of the Pacific Northwest.

    NASA Astrophysics Data System (ADS)

    Barna, Mike; Lamb, Brian; O'Neill, Susan; Westberg, Hal; Figueroa-Kaminsky, Cris; Otterson, Sally; Bowman, Clint; Demay, Jennifer

    2000-03-01

    The rapidly growing Cascadia region of the Pacific Northwest, consisting of western Washington, Oregon, and southwestern British Columbia, has experienced surface ozone concentrations that exceed federally mandated standards. A modeling system consisting of the prognostic meteorological model known as the Fifth-Generation Pennsylvania State University-National Center for Atmospheric Research Mesosale Model (MM5), the diagnostic meteorological model CALMET, and the photochemical air quality model CALGRID was developed to investigate ozone formation and transport in this region. To address both the complex topography within the model domain and the relatively sparse network of surface and upper-air meteorological observations, MM5 simulations were performed using 4D data assimilation and a relatively high-resolution inner domain (5-km grid). The MM5 results, however, failed to reproduce the observed wind patterns in some portions of the domain. As a result, it was necessary to employ the MM5 solution as the initial-guess wind field for CALMET (also with a 5-km grid). Objective analysis was applied within CALMET to interpolate the predicted winds with available surface observations. This method involved an iterative approach to find the optimal set of weighting factors within CALMET to merge the MM5 solution with the available meteorological observations.The predicted ozone concentration patterns for a July 1996 event were very complex but generally showed areas of maximum ozone (130 ppb) occurring to the south and east of Puget Sound and within and to the south of the Portland area (170 ppb). Widespread ozone buildup does not occur over the course of the episode; rather, the maximum ozone concentration occurs each day downwind of each urban center. There was no evidence for recirculation of pollutants from one day to the next within an urban area. It also does not appear that emissions from one urban center influence the neighboring downwind urban area. The predicted

  12. Characterizing the impacts of vertical transport and photochemical ozone production on an exceedance area

    NASA Astrophysics Data System (ADS)

    Yates, Emma L.; Iraci, Laura T.; Austerberry, David; Pierce, R. Bradley; Roby, Matthew C.; Tadić, Jovan M.; Loewenstein, Max; Gore, Warren

    2015-05-01

    Offshore and inland vertical profiles of ozone (O3) were measured from an aircraft during 16 flights from January 2012 to January 2013 over the northern San Joaquin Valley (SJV) and over the Pacific Ocean. Analysis of in situ measurements presents an assessment of the seasonality and magnitude of net O3 production and transport within the lower troposphere above the SJV. During the high O3 season (May-October), the Dobson Unit sum of O3 in the 0-2 km above sea level (km.a.s.l.) layer above the SJV exceeds that above the offshore profile by up to 20.5%, implying net O3 production over the SJV or vertical transport from above. During extreme events (e.g. Stratosphere-to-troposphere transport) vertical features (areas of enhanced or depleted O3 or water vapor) are observed in the offshore and SJV profiles at different altitudes, demonstrating the scale of vertical mixing during transport. Correlation analysis between offshore O3 profiles and O3 surface sites in the SJV lends further support the hypothesis of vertical mixing. Correlation analysis indicates that O3 mixing ratios at surface sites in the northern and middle SJV show significant correlations to the 1.5-2 km.a.s.l. offshore altitude range. Southern SJV O3 surface sites show a shift towards maximum correlations at increased time-offsets, and O3 surface sites at elevated altitudes show significant correlations with higher offshore altitudes (2.5-4 km.a.s.l.).

  13. 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.

  14. 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

  15. 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

  16. A Real-Time Eulerian Photochemical Model Forecast System: Overview and Initial Ozone Forecast Performance in the Northeast U.S. Corridor.

    NASA Astrophysics Data System (ADS)

    McHenry, John N.; Ryan, William F.; Seaman, Nelson L.; Coats, Carlie J., Jr.; Pudykiewicz, Janusz; Arunachalam, Sarav; Vukovich, Jeffery M.

    2004-04-01

    This article reports on the first implementation of a real-time Eulerian photochemical model forecast system in the United States. The forecast system consists of a tripartite set of one-way coupled models that run routinely on a parallel microprocessor supercomputer. The component models are the fifth-generation Pennsylvania State University (PSU) NCAR Mesoscale Model (MM5), the Sparse-Matrix Operator Kernel for Emissions (SMOKE) model, and the Multiscale Air Quality Simulation Platform—Real Time (MAQSIP-RT) photochemical model. Though the system has been run in real time since the summer of 1998, forecast results obtained during August of 2001 at 15-km grid spacing over New England and the northern mid-Atlantic—conducted as part of an “early start” NOAA air quality forecasting initiative—are described in this article.The development and deployment of a real-time numerical air quality prediction (NAQP) system is technically challenging. MAQSIP-RT contains a full pho-tochemical oxidant gas-phase chemical mechanism together with transport, dry deposition, and sophisticated cloud treatment. To enable the NAQP system to run fast enough to meet operational forecast deadlines, significant work was devoted to data flow design and software engineering of the models and control codes. The result is a turnkey system now in use by a number of agencies concerned with operational ozone forecasting.Results of the chosen episode are compared against three other models/modeling techniques: a traditional statistical model used routinely in the metropolitan Philadelphia, Pennsylvania, area, a set of publicly issued forecasts in the northeastern United States, and the operational Canadian Hemispheric and Regional Ozone and NOx System (CHRONOS) model. For the test period it is shown that the NAQP system performs as well or better than all of these operational approaches. Implications for the impending development of an operational U.S. ozone forecasting capability are

  17. An investigation of the meteorological and photochemical factors influencing the background rural and marine surface ozone levels in the Central and Eastern Mediterranean

    NASA Astrophysics Data System (ADS)

    Kalabokas, P. D.; Mihalopoulos, N.; Ellul, R.; Kleanthous, S.; Repapis, C. C.

    A study on the spatial distribution as well as an investigation of the possible factors influencing the observed variations of summer (JJA) rural and marine surface ozone background in the Central and Eastern Mediterranean is performed, following observations showing that the 60 ppb EU Air Quality Standard for Human Health Protection is frequently exceeded in the area. For this purpose the measurements of the following four Eastern Mediterranean stations are analyzed: Giordan Lighthouse-Gozo, Malta; Aliartos-Central Greece; Finokalia-Crete, Greece and Ag. Marina, Cyprus. The measured summer afternoon rural and marine ozone levels in Central Greece and on Crete Island are quite comparable, but are found to be significantly higher (by about 15-20%) than the corresponding levels in Malta and Cyprus. After investigating the characteristic meteorological conditions associated with high and low rural and marine surface ozone concentrations, it appears that an important factor leading to high tropospheric ozone values in the Eastern Mediterranean area is the anticyclonic influence of the high-pressure domination over the Central Mediterranean and the Balkans. The rural and marine surface ozone stations located across the Aegean Channel are also influenced by the long-range transport of polluted air masses from the European continent in the boundary layer during summer and the subsequent photochemical ozone production. This characteristic northern flow during summer is created by the combination of the Central Mediterranean anticyclone with the Middle-East low-pressure system. On the other hand, the lowest ozone levels, particularly in the Crete and Cyprus stations, are associated with an extension to the west of the Middle-East low and weak pressure gradients over the Eastern Mediterranean and an upper air trough in the North Eastern Europe.

  18. Design considerations for ozone and acid-aerosol exposure and health investigations: the Fairview Lake Summer Camp - photochemical smog case study

    SciTech Connect

    Lioy, P.J.; Spektor, D.; Thurston, G.; Citak, K.; Lippmann, M.

    1987-01-01

    The health effects associated with ozone and acidic particulate sulfate exposures to active children have been and are being addressed in field epidemiological studies at summer camps in rural areas of the Northeastern U.S. The rationale and study design for studies, which have been conducted in Pennsylvania and New Jersey, are developed and reviewed. As background, results are summarized for human clinical and epidemiological studies and animal studies. These provided the basis for selection of health outcomes. Measured results from chemical characterization and transport studies are reviewed to define the criteria used for selection of a site affected by high ozone and acid species during photochemical smog episodes. The integration of the study design is discussed in detail by reviewing its application to the 1984 - Fairview Lake Camp Study (July 8 to August 4). The features of the camp study are reviewed, including the study population, pulmonary function procedures and analyses, air pollution monitoring instrumentation, and the site characteristics.

  19. Impact of model resolution on chemical ozone formation in Mexico City: application of the WRF-Chem model

    NASA Astrophysics Data System (ADS)

    Tie, X.; Brasseur, G.; Ying, Z.

    2010-09-01

    resolution of the surface emissions has important effects on the calculated concentration fields, but the effects are smaller than those resulting from the model resolution. This study also suggests that the effect of model resolution on O3 precursors leads to important impacts on the photochemical formation of ozone. This results directly from the non-linear relationship between O3 formation and O3 precursor concentrations. Finally, this study suggests that, considering the balance between model performance and required computation time on current computers, the 6 km resolution is an optimal resolution for the calculation of ozone and its precursors in urban areas like Mexico City.

  20. 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.

  1. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

    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, 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 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 can

  3. 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.

  4. 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.

  5. Ozone production in urban plumes transported over water: Photochemical model and case studies in the northeastern and midwestern United States

    NASA Astrophysics Data System (ADS)

    Sillman, Sanford; Samson, Perry J.; Masters, Jeffrey M.

    1993-07-01

    Abnormally high concentrations of O3 have been observed in rural locations on the shore of Lake Michigan and on the Atlantic coast in Maine, at a distance of 300 km or more from major anthropogenic sources. We hypothesize that this O3 is associated with transport from major urban centers and with the suppression of vertical mixing as urban plumes are transported over water. A dynamical/photochemical model is developed that represents formation of O3 in shoreline environments and is used to simulate case studies for Lake Michigan and the northeastern United States. Results suggest that a broad region with elevated O3, NOx and volatile organic carbon (VOC) forms as the Chicago plume travels over Lake Michigan, a pattern consistent with observed O3 at surface monitoring sites. Near-total suppression of dry deposition of O3 and NOx over the lake is needed to produce high O3. Results for the east coast suggest that the observed peak O3 can only be reproduced by a model that includes suppressed vertical mixing and deposition over water, 2-day transport of a plume from New York, and superposition of the New York and Boston plumes. An investigation of the sensitivity of O3 to emissions of NOx and VOC suggests that results vary greatly between cities, even when the composition of urban emissions is similar. An index for VOC versus NOx sensitivity is shown to correlate with total reactive nitrogen (NOy) at the time of peak O3.

  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. PMID:27363129

  7. [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.

  8. Organic aerosol formation from photochemical oxidation of diesel exhaust in a smog chamber.

    PubMed

    Weitkamp, Emily A; Sage, Amy M; Pierce, Jeffrey R; Donahue, Neil M; Robinson, Allen L

    2007-10-15

    Diluted exhaust from a diesel engine was photo-oxidized in a smog chamber to investigate secondary organic aerosol (SOA) production. Photochemical aging rapidly produces significant SOA, almost doubling the organic aerosol contribution of primary emissions after several hours of processing at atmospherically relevant hydroxyl radical concentrations. Less than 10% of the SOA mass can be explained using a SOA model and the measured oxidation of known precursors such as light aromatics. However, the ultimate yield of SOA is uncertain because it is sensitive to treatment of particle and vapor losses to the chamber walls. Mass spectra from an aerosol mass spectrometer (AMS) reveal that the organic aerosol becomes progressively more oxidized throughout the experiments, consistent with sustained, multi-generational production. The data provide strong evidence that the oxidation of a wide array of precursors that are currently not accounted for in existing models contributes to ambient SOA formation.

  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.

    2014-09-01

    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.

  10. 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.

  11. Heterogeneous photocatalytic effect of zinc oxide on photochemical smog formation reaction of C 4H 8-NO 2-air

    NASA Astrophysics Data System (ADS)

    Takeuchi, Koji; Yazawa, Takenori; Ibusuki, Takashi

    As a model of heterogeneous photochemical smog formation reaction, butene-NO 2-air systems in the presence of zinc oxide were experimentally studied using a flowing reaction system. Zinc oxide revealed a remarkable photocatalytic action which involved the production of hitherto unreported species such as cyano-compounds (HCN and CH 3CN) as well as a striking change in the distribution of the reaction products (aldehydes, ketones, epoxides, alkyl nitrates, HNO 3, CO, CO 2, etc.). It is confirmed that ZnO little affected the initial process of gas-phase photochemical reactions but interacted photocatalytically with the gas-phase reaction products.

  12. Photochemical formation of polybrominated dibenzo-p-dioxins from environmentally abundant hydroxylated polybrominated diphenyl ethers.

    PubMed

    Arnoldsson, Kristina; Andersson, Patrik L; Haglund, Peter

    2012-07-17

    High levels of polybrominated dibenzo-p-dioxins (PBDDs) have been found in Baltic Sea biota, where the toxic load owing to, for example, polychlorinated dibenzo-p-dioxins and other organic pollutants is already high. The levels and geographic pattern of PBDDs suggest biogenic rather than anthropogenic origin, and both biotic and abiotic formation pathways have been proposed. Photochemical formation from hydroxylated polybrominated diphenyl ethers (OH-PBDE) is a proposed pathway for PBDDs in marine environments. Ultraviolet radiation-initiated transformations of OH-BDEs 47, 68, 85, 90, 99, and 123, which all are abundant in the environment, were investigated. It was shown that the most abundant PBDDs in the environment (1,3,7-triBDD and 1,3,8-triBDD) can be formed from the most abundant OH-BDEs (OH-BDE 47 and OH-BDE 68) at high rates and with percentage yields. In fact, most of the PBDDs that have been identified in the Baltic Sea environment were formed with high yield from the six studied OH-PBDE, through initial cyclization and subsequent debromination reactions. The high formation yields point to this route as an important source of PBDDs in biota. However, congeners showing relatively high retention in fish, specifically 1,3,6,8- and 1,3,7,9-tetraBDD, were not formed. These are likely formed by enzymatic coupling of brominated phenols.

  13. Study on the formation and transport of ozone in relation to the air quality management and vegetation protection in Tenerife (Canary Islands).

    PubMed

    Guerra, Juan-Carlos; Rodríguez, Sergio; Arencibia, M-Teresa; García, M-Dolores

    2004-09-01

    An experimental study on the formation and transport of ozone in ambient air was performed in Tenerife (Canary Islands) in order to investigate the processes affecting ozone levels and air quality. The special features of Tenerife (prevalence of the trade wind pattern (NE), orography and the specific location of the local ozone sources) permit to quantify the role of the 'long-range transport from northern latitudes' versus the 'formation and transport of ozone downwind of the main urban areas' of Tenerife. Levels of O(3), NO(2) and O(X) were monitored in different types of environments to achieve this purpose. The results showed that: (1) upwind of the urban areas ozone is mainly transported from the ocean by trade winds, (2) local ozone titration (by NO) and ozone replenishment from the ocean are the main causes of ozone variations in urban and suburban areas, and (3) photochemical ozone production occurs downwind of the urban areas. Photochemical production causes daylight O(3) and O(X) levels downwind of urban areas to be frequently (60% and 35% days/year, respectively) higher than upwind of the urban sites (O(3) and O(X) excess frequently in the range 5-20 ppbv). Due to the above processes, different daily ozone cycles occur in short distances (<30 km), with maximum O(3) levels during daylight or night depending on the site. Ozone phytotoxicity was assessed by calculating the AOT40 index upwind and downwind of the main urban areas. The critical value for the 5-day-AOT40 index was simultaneously exceeded at the two sites (few times/year) during long-range transport events. During the additional exceedances of the critical value downwind of the urban area, relatively high 5-day-AOT40 values were recorded upwind of the urban site. Thus, long-range transport from northern latitudes may produce relatively high 5-days-AOT40 levels in the oceanic boundary layer. These results are important for the protection of the large number of endemic plants in the Canaries. The

  14. Estimating the contribution of photochemical particle formation to ultrafine particle number averages in an urban atmosphere.

    PubMed

    Ma, N; Birmili, W

    2015-04-15

    Ultrafine particles (UFPs, diameter<100 nm) have gained major attention in the environmental health discussion due to a number of suspected health effects. Observations of UFPs in urban air reveal the presence of several, time-dependent particle sources. In order to attribute measured UFP number concentrations to different source type contributions, we analyzed observations collected at a triplet of observation sites (roadside, urban background, rural) in the city of Leipzig, Germany. Photochemical new particle formation (NPF) events can be the overwhelming source of UFP particles on particular days, and were identified on the basis of characteristic patterns in the particle number size distribution data. A subsequent segmentation of the diurnal cycles of UFP concentration yielded a quantitative contribution of NPF events to daily, monthly, and annual mean values. At roadside, we obtained source contributions to the annual mean UFP number concentration (diameter range 5-100 nm) for photochemical NPF events (7%), local traffic (52%), diffuse urban sources (20%), and regional background (21%). The relative contribution of NPF events rises when moving away from roadside to the urban background and rural sites (14 and 30%, respectively). Their contribution also increases when considering only fresh UFPs (5-20 nm) (21% at the urban background site), and conversely decreases when considering UFPs at bigger sizes (20-100 nm) (8%). A seasonal analysis showed that NPF events have their greatest importance on UFP number concentration in the months May-August, accounting for roughly half of the fresh UFPs (5-20 nm) at the urban background location. The simplistic source apportionment presented here might serve to better characterize exposure to ambient UFPs in future epidemiological studies.

  15. 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.

  16. 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.

  17. 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...

  18. 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.

  19. 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

  20. 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

  1. 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.; 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,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

  2. 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

  3. 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.

  4. 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.

  5. 13C and 15N fractionation of CH4/N2 mixtures during photochemical aerosol formation: Relevance to Titan

    NASA Astrophysics Data System (ADS)

    Sebree, Joshua A.; Stern, Jennifer C.; Mandt, Kathleen E.; Domagal-Goldman, Shawn D.; Trainer, Melissa G.

    2016-05-01

    The ratios of the stable isotopes that comprise each chemical species in Titan's atmosphere provide critical information towards understanding the processes taking place within its modern and ancient atmosphere. Several stable isotope pairs, including 12C/13C and 14N/15N, have been measured in situ or probed spectroscopically by Cassini-borne instruments, space telescopes, or through ground-based observations. Current attempts to model the observed isotope ratios incorporate fractionation resulting from atmospheric diffusion, hydrodynamic escape, and primary photochemical processes. However, the effect of a potentially critical pathway for isotopic fractionation - organic aerosol formation and subsequent deposition onto the surface of Titan - has not been considered due to insufficient data regarding fractionation during aerosol formation. To better understand the nature of this process, we have conducted a laboratory study to measure the isotopic fractionation associated with the formation of Titan aerosol analogs, commonly referred to as 'tholins', via far-UV irradiation of several methane (CH4) and dinitrogen (N2) mixtures. Analysis of the δ13C and δ15N isotopic signatures of the photochemical aerosol products using an isotope ratio mass spectrometer (IRMS) show that fractionation direction and magnitude are dependent on the initial bulk composition of the gas mixture. In general, the aerosols showed enrichment in 13C and 14N, and the observed fractionation trends can provide insight into the chemical mechanisms controlling photochemical aerosol formation.

  6. 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. PMID:26517390

  7. 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.

  8. (CF3)2CFCH=CHF (HFO-1438ezy): OH Radical Rate Coefficient, Infrared Spectrum Measurements and Estimated Global Warming Potentials and Photochemical Ozone Creation Potential

    NASA Astrophysics Data System (ADS)

    Papadimitriou, V.; Burkholder, J. B.

    2015-12-01

    Short-lived hydrofluoroolefins (HFOs) are proposed replacement compounds for ozone depleting substances (ODSs) and longer-lived greenhouse gases that are used in various industrial and technological applications. HFOs are not ODSs and the presence of the highly reactive unsaturated bond toward the common atmospheric oxidants (OH, Cl, NO3 and O3) is expected to lead to shorter tropospheric lifetimes relative to those of saturated hydrofluorocarbons. The shorter lifetime reduces their direct contribution to Climate Change. In this study, rate coefficients for the gas-phase reaction of the OH radical with (CF3)2CFCH=CHF (HFO-1438ezy), between 214 and 380 K and 50-450 Torr (He, N2), were measured using pulsed laser photolysis-laser induced fluorescence (PLP/LIF) and relative rate methods. No pressure dependence was observed within this measurement range. The reaction displays a non-Arrhenius temperature dependence over this temperature range with a slightly positive temperature dependence above 280 K and near temperature independence at lower temperatures. The infrared spectrum of HFO-1438ezy was measured as part of this work. On the basis of the present measurements, the atmospheric lifetime of HFO-1438ezy as well as its radiative efficiency, global warming potential and photochemical ozone creation potential were estimated.

  9. 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.

  10. 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

  11. 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

  12. 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. PMID:12676233

  13. 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.

  14. 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 ...

  15. Multi-year evaluation of ambient volatile organic compounds: temporal variation, ozone formation, meteorological parameters, and sources.

    PubMed

    Kim, Ku H; Chun, Ho-Hwan; Jo, Wan K

    2015-02-01

    The multi-year characteristics of ambient volatile organic compounds (VOCs) and their source contribution in a selected metropolitan (Seoul) and rural (Seokmolee) areas in Korea were investigated to provide the framework for development and implementation of ambient VOC control strategies. For Seoul, none of the three VOC groups exhibited any significant trend in their ambient concentrations, whereas for Seokmolee, they all showed a generally decreasing trend between 2005 and 2008 and an increasing trend after 2008. Two paraffinic (ethane and propane) and two olefin (ethylene and propylene) hydrocarbons displayed higher concentrations during the cold season than warm season, while the other target VOCs did not exhibit any significant trends. Ethylene and toluene were the first and second largest contributors to ozone formation, respectively, whereas several other VOCs displayed photochemical ozone formation potential values less than 0.01 ppb. For both areas, there was a significant negative correlation between ambient temperature and the selected VOC group concentrations. In contrast, a significant positive correlation was observed between relative humidity and the three VOC group concentrations, while no significant correlation was observed between wind speed and VOC group concentrations. For Seoul, the combination of vehicle exhaust and gasoline/solvent evaporation was the greatest source of VOCs, followed by liquid natural gas (LNG) and liquid petroleum gas (LPG). However, combination of LNG and LPG was the greatest source of VOCs at Seokmolee, followed by the combination of vehicle exhaust and gasoline evaporation, and then biogenic sources. PMID:25632908

  16. 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 ...

  17. Effect of pre-ozonation on the formation and speciation of DBPs.

    PubMed

    Hua, Guanghui; Reckhow, David A

    2013-09-01

    The objective of this study was to quantitatively evaluate the effect of pre-ozonation on the formation and speciation of disinfection byproducts (DBPs) from subsequent chlorination and chloramination. Laboratory experiments were conducted on six diverse natural waters with low to medium bromide concentrations. Four groups of DBPs were investigated in this study: trihalomethanes (THMs), trihaloacetic acids (THAAs), dihaloacetic acids (DHAAs), and dihaloacetonitriles (DHANs). The results showed that the relative destructions of chlorination DBP precursors by ozone generally follow the order of DHANs > THMs & THAAs > DHAAs. Pre-ozonation substantially increased the DHAA precursors in the waters with low specific ultraviolet absorbance values. Pre-ozonation shifted the formation of DBPs to more brominated species. The bromine substitution factors (BSF) of different chlorination DBPs typically increased by 1-8 percentage points after ozonation. Pre-ozonation reduced the yields of chloramination DHAAs and THMs and increased the BSFs of chloramination DHAAs by 1-6 percentage points.

  18. 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.

  19. 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.

  20. 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.

  1. Ozone-initiated particle formation, particle aging, and precursors in a laser printer.

    PubMed

    Wang, Hao; He, Congrong; Morawska, Lidia; McGarry, Peter; Johnson, Graham

    2012-01-17

    An increasing number of researchers have hypothesized that ozone may be involved in the particle formation processes that occur during printing, however no studies have investigated this further. In the current study, this hypothesis was tested in a chamber study by adding supplemental ozone to the chamber after a print job without measurable ozone emissions. Subsequent particle number concentration and size distribution measurements showed that new particles were formed minutes after the addition of ozone. The results demonstrated that ozone did react with printer-generated volatile organic compounds (VOCs) to form secondary organic aerosols (SOAs). The hypothesis was further confirmed by the observation of correlations among VOCs, ozone, and particles concentrations during a print job with measurable ozone emissions. The potential particle precursors were identified by a number of furnace tests, which suggested that squalene and styrene were the most likely SOA precursors with respect to ozone. Overall, this study significantly improved scientific understanding of the formation mechanisms of printer-generated particles, and highlighted the possible SOA formation potential of unsaturated nonterpene organic compounds by ozone-initiated reactions in the indoor environment.

  2. [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. PMID:27506038

  3. 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) ...

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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. PMID:19785277

  10. 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.

  11. 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. PMID:26624229

  12. 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.

  13. Ambient Ozone Control in a Photochemically Active Region: Short-Term Despiking or Long-Term Attainment?

    PubMed

    Ou, Jiamin; Yuan, Zibing; Zheng, Junyu; Huang, Zhijiong; Shao, Min; Li, Zekun; Huang, Xiaobo; Guo, Hai; Louie, Peter K K

    2016-06-01

    China has made significant progress decreasing the ambient concentrations of most air pollutants, but ozone (O3) is an exception. O3 mixing ratios during pollution episodes are far higher than the national standard in the Pearl River Delta (PRD), thus greater evidence-based control efforts are needed for O3 attainment. By using a validated O3 modeling system and the latest regional emission inventory, this study illustrates that control strategies for short-term O3 despiking and long-term attainment in the PRD may be contradictory. VOC-focused controls are more efficient for O3 despiking in urban and industrial areas, but significant NOx emission reductions and a subsequent transition to a NOx-limited regime are required for O3 attainment. By tracking O3 changes along the entire path toward long-term attainment, this study recommends to put a greater focus on NOx emission controls region-wide. Parallel VOC reductions around the Nansha port are necessary in summertime and should be extended to the urban and industrial areas in fall with a flexibility to be strengthened on days forecasted to have elevated O3. Contingent VOC-focused controls on top of regular NOx-focused controls would lay the groundwork for striking a balance between short-term despiking and long-term attainment of O3 concentrations in the PRD. PMID:27135547

  14. Effect of light intensity on the formation of the photochemical apparatus in the green bacterium Chloropseudomonas ethylicum.

    PubMed

    Holt, S C; Conti, S F; Fuller, R C

    1966-01-01

    Holt, Stanley C. (Dartmouth Medical School, Hanover, N.H.), S. F. Conti, and R. C. Fuller. Effect of light intensity on the formation of the photochemical apparatus in the green bacterium Chloropseudomonas ethylicum. J. Bacteriol. 91:349-355. 1966.-When the green bacterium Chloropseudomonas ethylicum was grown at various light intensities, the formation of the photosynthetic vesicles was found to be an inverse function of the light intensity at which the cells were grown. The specific chlorophyll content of isolated vesicles varied as the light intensity was changed over a wide range. Thus, the regulation of chlorophyll content in C. ethylicum in response to a change in light intensity is achieved both by a change in the number of vesicles that are formed and by a change in the specific chlorophyll content of these vesicles.

  15. 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.

  16. 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.

  17. 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.

  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. Reducing the formation of disinfection by-products by pre-ozonation.

    PubMed

    Chang, Cheng-Nan; Ma, Ying-Shih; Zing, Fang-Fong

    2002-01-01

    The objective of this study is to apply the pre-ozonation process to reduce the formation of disinfection by-products (DBPs). The raw water sample, collected from the Te-Chi Reservoir in central Taiwan, has been polluted by fertilizer. Three types of resins were used to isolate the natural organic matter into seven types of organic fractions. The pre-ozonation was used to oxidize each organic fraction to study the reduction of DBPs of each fraction. Experimental results indicated that the pre-ozonation could reduce the concentration of dissolved organic carbon resulting in the reduction of DBP formation. With the pre-ozonation, 9-54% of DOC and more than 40% of DBPs were reduced. With the analysis of UV adsorption and Fourier transform infrared spectrometer (FTIR), the reduction of A254 and unsaturated functional groups such as aromatic ring and C=C bond containing in the water sample is the major reaction mechanism.

  20. 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.

  1. Simulations of aerosols and their effects on photolysis and ozone formation in Mexico City

    NASA Astrophysics Data System (ADS)

    Li, G.; Zavala, M.; Lei, W.; Karydis, V. A.; Tsimpidi, A. P.; Pandis, S.; Molina, L. T.

    2009-04-01

    Atmospheric aerosols, formed from natural and anthropogenic sources, are believed to be associated with adverse human effects at high levels in polluted urban areas. They also play a key role in climate through direct and indirect effects. Therefore, accurate simulations of aerosol composition and distribution in the atmospheric models are important in evaluating their impact on environment and climate. In the present study, a flexible gas phase chemical module with SAPRC mechanism and the CMAQ/models3 aerosol module developed by EPA have been implemented into the WRF-CHEM model. Additionally, to further improve the aerosol, especially the secondary organic aerosol (SOA) simulations, an advanced SOA module [Tsimpidi et al., 2009] has been incorporated into the WRF-CHEM model. The new SOA module is based on the volatility basis-set approach in which both primary and secondary organic components are assumed to be semivolatile and photochemically reactive [Lane et al., 2008]. Gas phase species and aerosol simulation results are compared with the available measurements obtained during the MILAGRO 2006 campaign. When the advanced SOA mechanism is employed, the SOA simulations are significantly improved. Furthermore, the aerosol impacts on the photochemistry in Mexico City have been evaluated using the FTUV [Tie et al., 2005]. Aerosol optical properties are calculated using the Mie theory and compared with available observations in Mexico City [Paredes-Miranda et al., 2008]. Aerosols, principally black carbon, reduce the photolysis frequencies of J[O3(1D)] and J[NO2] in the planetary boundary layer and hence decrease the ground-level ozone concentration. Our study demonstrates that the impact of aerosols on photochemistry is significant in polluted urban atmosphere. References: Lane, T. E., N. M. Donahue, and S. N. Pandis (2008), Simulating secondary organic aerosol formation using the volatility basis-set approach in a chemical transport model, PMCAMx, Atmos. Environ

  2. Photochemical Formaldehyde Production in Anthropogenic Plumes during SENEX 2013

    NASA Astrophysics Data System (ADS)

    Kaiser, J.; Wolfe, G. M.; Hanisco, T. F.; Keutsch, F. N.; Aikin, K.; Brown, S. S.; De Gouw, J. A.; Gilman, J.; Graus, M.; Hatch, C. D.; Holloway, J.; Lee, B.; Lerner, B. M.; Liao, J.; Lopez-Hilfiker, F.; Middlebrook, A. M.; Min, K.; Peischl, J.; Pollack, I. B.; Roberts, J. M.; Ryerson, T. B.; Thornton, J. A.; Veres, P. R.; Warneke, C.

    2013-12-01

    In the Southeast United States, high emissions of biogenic volatile organic compounds (VOCs) coupled with hotspots of anthropogenic activity create ideal conditions for the formation of climate forcing agents and air pollutants. Formaldehyde (HCHO) is a ubiquitous photochemical product of VOC oxidation and thus a valuable tracer of integrated photochemical evolution within a plume. Using HCHO measurements acquired by laser-induced fluorescence aboard the NOAA WP-3D aircraft during the SENEX 2013 field campaign, we explore the magnitude and timescale of VOC oxidation in urban outflow and coal-fired power plant plumes. Comparison of photochemical HCHO production in and outside of a plume, as well as comparison between plumes of various origins, highlights the influence of anthropogenic emissions on the oxidation of VOCs, particularly isoprene. Preliminary results are used to track the linkage between VOC oxidation and production of secondary pollutants, particularly ozone and organic aerosol, throughout the lifetime of various plumes.

  3. [Effects of photochemical smog from a flow reactor on bacteria. I. Determination of the effects of photochemical smog on bacteria].

    PubMed

    Nover, H; Botzenhart, K

    1983-04-01

    To measure the damage to bacteria from photochemical smog Serratia marcescens, Staphylococcus epidermidis, Micrococcus luteus and spores of Bacillus cereus have been exposed to defined gas-mixtures. A smog-simulation-chamber has been used which allowed adjustment of reproducible and longterm constant smog formations due to the flow system. Two methods have been applied to examine the bactericidal effects of the photo-chemical smog: adsorption of bacteria to membrane filters and spraying on silk threads. Smog mixtures formed by olefines (propene 4200 ppb, isobutene 3000 ppb, trans-2-butene 1600 ppb) and nitrogene oxides (500-700 ppb) showed bactericidal effects at ozone levels of 500 ppb. The survival of exposed bacteria is influenced less by gasing with 500 ppb ozone than with the smog mixture.

  4. 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.

  5. 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.

  6. Photochirogenesis: Photochemical models on the absolute asymmetric formation of amino acids in interstellar space

    NASA Astrophysics Data System (ADS)

    Meinert, Cornelia; de Marcellus, Pierre; Le Sergeant D'Hendecourt, Louis; Nahon, Laurent; Jones, Nykola C.; Hoffmann, Søren V.; Bredehöft, Jan Hendrik; Meierhenrich, Uwe J.

    2011-10-01

    Proteins of all living organisms including plants, animals, and humans are made up of amino acid monomers that show identical stereochemical L-configuration. Hypotheses for the origin of this symmetry breaking in biomolecules include the absolute asymmetric photochemistry model by which interstellar ultraviolet (UV) circularly polarized light (CPL) induces an enantiomeric excess in chiral organic molecules in the interstellar/circumstellar media. This scenario is supported by a) the detection of amino acids in the organic residues of UV-photo-processed interstellar ice analogues, b) the occurrence of L-enantiomer-enriched amino acids in carbonaceous meteorites, and c) the observation of CPL of the same helicity over large distance scales in the massive star-forming region of Orion. These topics are of high importance in topical biophysical research and will be discussed in this review. Further evidence that amino acids and other molecules of prebiotic interest are asymmetrically formed in space comes from studies on the enantioselective photolysis of amino acids by UV-CPL. Also, experiments have been performed on the absolute asymmetric photochemical synthesis of enantiomer-enriched amino acids from mixtures of astrophysically relevant achiral precursor molecules using UV-circularly polarized photons. Both approaches are based on circular dichroic transitions of amino acids that will be highlighted here as well. These results have strong implications on our current understanding of how life's precursor molecules were possibly built and how life selected the left-handed form of proteinogenic amino acids.

  7. Formation of secondary ozonides from the reaction of an unsaturated phosphatidylcholine with ozone

    SciTech Connect

    Lai, C.C.; Finlayson-Pitts, B.J.; Willis, W.V. )

    1990-11-01

    Phosphatidylcholines are significant components of pulmonary surfactant in the alveolar region of the lung, where they play a major role in lung function due to their surface tension reducing properties. However, separation and the direct identification of many of the primary products of reaction of phosphatidylcholines with inhaled pollutant gases has not been possible until recently due to the lack of suitable analytical techniques, so that compounds such as fatty acid methyl esters generally have been used as analogues for the phospholipids. The authors report here the first isolation and identification of the products of reaction of ozone with one of the unsaturated components of lung surfactant, beta-oleoyl-gamma-palmitoyl-L-alpha-phosphatidylcholine (OPPC), using a combination of high-performance liquid chromatography, fast atom bombardment mass spectrometry, and Fourier transform infrared, ultraviolet absorption, and nuclear magnetic resonance spectrometry as well as gas chromatography. The products are shown to be the cis and trans secondary ozonides of the parent phosphatidylcholine, analogous to those previously observed by other researchers in the reactions of the simple fatty acid methyl esters with ozone. This also appears to be the first report of fast atom bombardment mass spectra of these phospholipid secondary ozonides. The implications of this work for the inhalation of ozone, formed in photochemical smog, are discussed.

  8. MTBE oxidation by conventional ozonation and the combination ozone/hydrogen peroxide: efficiency of the processes and bromate formation.

    PubMed

    Acero, J L; Haderlein, S B; Schmidt, T C; Suter, M J; von Gunten, U

    2001-11-01

    The present study investigates the oxidation of methyl tert-butyl ether (MTBE) by conventional ozonation and the advanced oxidation process (AOP) ozone/hydrogen peroxide under drinking water treatment conditions. The major degradation products identified were tert-butyl formate (TBF), tert-butyl alcohol (TBA), 2-methoxy-2-methyl propionaldehyde (MMP), acetone (AC), methyl acetate (MA), hydroxyisobutyraldehyde (HiBA), and formaldehyde (FA). The rate constants of the reaction of ozone and OH radicals with MTBE were found to be 0.14 and 1.9 x 10(9) M(-1) s(-1), respectively. The rate constants for the same oxidation processes were also measured for the degradation products TBF, MMP, MA, and HiBA (k(O3-TBF) = 0.78 M(-1) s(-1); k(OH-TBF) = 7.0 x 10(8) M(-1) s(-1); k(O3-MMP) = 5 M(-1) s(-1); k(OH-MMP) = 3 x 10(9) M(-1) s(-1), k(O3-MA) = 0.09 M(-1) s(-1), k(O3-HiBA) = 5 M(-1) s(-1); k(OH-HiBA) = 3 x 10(9) M(-1) s(-1)). Since all compounds reacted slowly with molecular ozone, only the degradation pathway of MTBE with OH radicals has been determined, including the formation of primary degradation products. In experiments performed with several natural waters, the efficiency of MTBE elimination and the formation of bromate as disinfection byproduct have been measured. With a bromide level of 50 microg/L, only 35-50% of MTBE could be eliminated by the AOP O3/H2O2 without exceeding the current drinking water standard of bromate (10 microg/L). The transient concentrations of MTBE and its primary degradation products were modeled using a combination of kinetic parameters (degradation product distribution and rate constants) together with the ozone and OH radical concentration and were in good agreement with the experimental results.

  9. 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. PMID:23009791

  10. 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.

  11. Empirical evidence for the low- and high-NO x photochemical regimes of sulfate and nitrate formation

    NASA Astrophysics Data System (ADS)

    Stein, Ariel F.; Lamb, Dennis

    The formation of sulfate and nitrate in eastern North America is chemically linked to the abundance of oxidants and therefore to the emissions of nitrogen oxides (NO x). Depending on conditions, NO x reacts under either of two distinct photochemical regimes, defined by the types and levels of radical production. In the low-NO x regime (typical of summer), nitrogen dioxide (NO 2) is readily consumed during nitric acid formation, leaving an excess of radicals that recombine to form peroxides and a highly oxidizing state favorable to sulfate formation. On the other hand, under high-NO x conditions (as in winter), the oxidizing capacity of the atmosphere is reduced because the NO 2 rapidly combines with and thereby depletes hydroxyl radicals, producing nitric acid, but few peroxides. The distinction between these two chemical regimes is crucial for interpreting atmospheric deposition data because it determines whether sulfate or nitrate is the dominant acidifying component. Evidence for these regimes is gained from seasonal observations of sulfate and nitrate in rain samples collected at several sites of the National Atmospheric Deposition Program (NADP). A simple modeling exercise elucidates the processes by which sulfate and nitrate are formed under the high- and low-NO x states.

  12. 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.

  13. 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.

  14. 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.

  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. Evaluating and elucidating the formation of nitrogen-contained disinfection by-products during pre-ozonation and chlorination.

    PubMed

    Chiang, Pen-Chi; Chang, E-E; Chuang, Chao-Chin; Liang, Chung-Huei; Huang, Chin-Pao

    2010-06-01

    The effects of pre-ozonation on the formation of haloacetonitriles (HANs), trichloronitromethane (TCNM), and haloketones (HKs) during chlorination were evaluated. Ozone dose used in this study was 8.0, 10.0 and 25.0 mg O(3)/min. Results showed high UV(254) reduction (>80%) and relatively low dissolved organic carbon removal (40-70%) after ozonation, indicating that ozone might change significantly the chemical properties of natural organic matter presented in the raw water. Undesired ozonation by-products such as aldehydes and ketones were also formed during ozonation. At high ozone dose of 25.0 mg O(3)/min, the formation of dichloroacetonitrile and bromochloroacetonitrile were reduced significantly. Chlorination of the ozonated water formed high concentration of TCNM and HKs were 8-10 and 31-48 microg/L, respectively. It was also found that continuous hydrolysis at longer reaction time rapidly decreased the formation of HKs. Ozonation prior to chlorination practice exhibited a negative effect on TCNM and HKs reduction. A model based on the dissolved organic carbon and chlorine decay was developed not only for determining the reaction rate constants, e.g. formation and hydrolysis of HANs, HKs and TCNM, but also for interpreting the mechanisms of formation and hydrolysis for HANs, HKs and TCNM during the chlorination of natural organic matter.

  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. [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.

  19. 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.

  20. Combined effects of organic reactivity and NMHC/NOx ratio on photochemical-oxidant formation - a modeling study

    SciTech Connect

    Dodge, M.C.

    1984-01-01

    A modeling study was undertaken to assess the effect of organic reactivity on photochemical-oxidant formation. A six-component hydrocarbon model was developed and tested against data collected in a smog chamber study of irradiated auto exhaust and oxides of nitrogen NOx mixtures. The model was then adjusted to conditions that closely approximated those of the urban environment and used to assess the relative reactivity of various organic constituents present in an urban-like air mass. Twelve organics were investigated in the study: ethane, propane, n-butane, ethylene, propylene, trans-2-butene, toluene, m-xylene, methanol, ethanol, formalehyde, and acetaldehyde. The findings of this study indicate that the reactivity of organics depends strongly on the hydrocarbon-to-NOx ratio of the mix in which they are reacting. At low hydrocarbon-to-NOx ratios, the organics investigated in this study displayed significantly different O/sub 3/-forming potentials. At high hydrocarbon-to-NOx ratios, however, all organics exhibited comparable O to 3-forming potential.

  1. 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

  2. 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.

  3. 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

  4. Transformation efficiency and formation of transformation products during photochemical degradation of TCE and PCE at micromolar concentrations

    PubMed Central

    2014-01-01

    Background Trichloroethene and tetrachloroethene are the most common pollutants in groundwater and two of the priority pollutants listed by the U.S. Environmental Protection Agency. In previous studies on TCE and PCE photolysis and photochemical degradation, concentration ranges exceeding environmental levels by far with millimolar concentrations of TCE and PCE have been used, and it is not clear if the obtained results can be used to explain the degradation of these contaminants at more realistic environmental concentration levels. Methods Experiments with micromolar concentrations of TCE and PCE in aqueous solution using direct photolysis and UV/H2O2 have been conducted and product formation as well as transformation efficiency have been investigated. SPME/GC/MS, HPLC/UV and ion chromatography with conductivity detection have been used to determine intermediates of degradation. Results The results showed that chloride was a major end product in both TCE and PCE photodegradation. Several intermediates such as formic acid, dichloroacetic acid, dichloroacetaldehyede, chloroform, formaldehyde and glyoxylic acid were formed during both, UV and UV/H2O2 treatment of TCE. However chloroacetaldehyde and chloroacetic acid were only detected during direct UV photolysis of TCE and oxalic acid was only formed during the UV/H2O2 process. For PCE photodegradation, formic acid, di- and trichloroacetic acids were detected in both UV and UV/H2O2 systems, but formaldehyde and glyoxylic acid were only detected during direct UV photolysis. Conclusions For water treatment UV/H2O2 seems to be favorable over direct UV photolysis because of its higher degradation efficiency and lower risk for the formation of harmful intermediates. PMID:24401763

  5. Formation of environmentally persistent free radicals from the heterogeneous reaction of ozone and polycyclic aromatic compounds.

    PubMed

    Borrowman, Cuyler K; Zhou, Shouming; Burrow, Timothy E; Abbatt, Jonathan P D

    2016-01-01

    In the 1980s long-lived radical species were identified in cigarette tar. Since then, environmentally persistent free radicals (EPFRs) have been observed in ambient particulate matter, and have been generated in particulate matter generated from internal combustion engines. For the first time, we measure in situ the formation and decay of EPFRs through the heterogeneous reaction of ozone and several polycyclic aromatic compounds (PAC). Solid anthracene (ANT), pyrene (PY), benzo[a]pyrene (BAP), benzo[ghi]perylene (BGHIP), 1,4-naphthoquinone (1,4NQ), and 9,10-anthraquinone (AQ) were reacted with gas-phase ozone in a flow system placed in the active cavity of an electron paramagnetic resonance (EPR) spectrometer, and the formation of radicals was measured on the timescale of tens of minutes at ambient levels of ozone down to 30 ppb. For most substrates the net radical production is initially rapid, slows at intermediate times, and is followed by a slow decay. For oxidized solid BAP, radical signal persists for many days in the absence of ozone. To evaluate the effect of substrate phase, the solid PAHs were also dissolved in squalane, an organic oil inert to ozone, which yielded a much higher maximum radical concentration and faster radical decay when exposed to ozone. With higher mobility, reactants were apparently able to more easily diffuse and react with each other, yielding the higher radical concentrations. The EPR spectra exhibit three radicals types, two of which have been assigned to semiquinone species and one to a PAH-derived, carbon-centered radical. Although our system uses levels of PAC not typically found in the environment it is worth noting that the amounts of radical formed, on the order of 10(18) radicals per g, are comparable to those observed in ambient particulate matter.

  6. Formation of environmentally persistent free radicals from the heterogeneous reaction of ozone and polycyclic aromatic compounds.

    PubMed

    Borrowman, Cuyler K; Zhou, Shouming; Burrow, Timothy E; Abbatt, Jonathan P D

    2016-01-01

    In the 1980s long-lived radical species were identified in cigarette tar. Since then, environmentally persistent free radicals (EPFRs) have been observed in ambient particulate matter, and have been generated in particulate matter generated from internal combustion engines. For the first time, we measure in situ the formation and decay of EPFRs through the heterogeneous reaction of ozone and several polycyclic aromatic compounds (PAC). Solid anthracene (ANT), pyrene (PY), benzo[a]pyrene (BAP), benzo[ghi]perylene (BGHIP), 1,4-naphthoquinone (1,4NQ), and 9,10-anthraquinone (AQ) were reacted with gas-phase ozone in a flow system placed in the active cavity of an electron paramagnetic resonance (EPR) spectrometer, and the formation of radicals was measured on the timescale of tens of minutes at ambient levels of ozone down to 30 ppb. For most substrates the net radical production is initially rapid, slows at intermediate times, and is followed by a slow decay. For oxidized solid BAP, radical signal persists for many days in the absence of ozone. To evaluate the effect of substrate phase, the solid PAHs were also dissolved in squalane, an organic oil inert to ozone, which yielded a much higher maximum radical concentration and faster radical decay when exposed to ozone. With higher mobility, reactants were apparently able to more easily diffuse and react with each other, yielding the higher radical concentrations. The EPR spectra exhibit three radicals types, two of which have been assigned to semiquinone species and one to a PAH-derived, carbon-centered radical. Although our system uses levels of PAC not typically found in the environment it is worth noting that the amounts of radical formed, on the order of 10(18) radicals per g, are comparable to those observed in ambient particulate matter. PMID:26603953

  7. Mechanism of Formation of the Ozone Valley over the Tibetan Plateau in Summer— Transport and Chemical Process of Ozone

    NASA Astrophysics Data System (ADS)

    Liu, Yu; Li, Weiliang; Zhou, Xiuji; He, Jiahai

    2003-01-01

    With the 3D chemical transport model OSLO CTM2, the valley of total column ozone over the Tibetan Plateau in summer is reproduced. The results show that when the ozone valley occurs and develops, the transport process plays the main part in the ozone reduction, but the chemical process partly compensates for the transport process. In the dynamic transport process of ozone, the horizontal transport process plays the main part in the ozone reduction in May, but brings about the ozone increase in June and July. The vertical advective process gradually takes the main role in the ozone reduction in June and July. The effect of convective activities rises gradually so that this effect cannot be overlooked in July, as its magnitude is comparable to that of the net changes. The effect of the gaseous chemical process brings about ozone increases which are more than the net changes sometimes, so the chemical effect is also important.

  8. 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.

  9. 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.

  10. 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.

  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. PMID:27080853

  13. Intense secondary aerosol formation due to strong atmospheric photochemical reactions in summer: observations at a rural site in eastern Yangtze River Delta of China.

    PubMed

    Wang, Dongfang; Zhou, Bin; Fu, Qingyan; Zhao, Qianbiao; Zhang, Qi; Chen, Jianmin; Yang, Xin; Duan, Yusen; Li, Juan

    2016-11-15

    High pollution episodes of PM2.5 and O3 were frequently observed at a rural site (N31.0935º, E120.978°) in eastern Yangtze River Delta (YRD) in summer. To study the impacts of photochemical reactions on secondary aerosol formation in this region, we performed real-time measurements of the mass concentration and composition of PM2.5, particle size distribution (13.6~736.5 nm), concentrations of gas pollutants including O3, SO2, NO2, CO, non-methane hydrocarbons (NMHC)), and nitrate radical in 2013. During the sampling period, the average concentration of PM2.5 was 76.1 (± 16.5) μg/m(3), in which secondary aerosol species including sulfate, nitrate, ammonium, and secondary organic aerosol (SOA) accounted for ~ 62%. Gas-phase oxidation of SO2 was mainly responsible for a fast increase of sulfate (at 1.70 μg/m(3)/h) in the morning. Photochemical production of nitric acid was intense during daytime, but particulate nitrate concentration was low in the afternoon due to high temperature. At night, nitrate was mainly formed through the hydrolysis of NO3 and/or N2O5. The correlations among NMHC, Ox (= O3 + NO2), and SOA suggested that a combination of high emission of hydrocarbons and active photochemical reactions led to the rapid formation of SOA. In addition, several new particle formation and fast growth events were observed despite high ambient aerosol loading. Since the onset of new particle events was accompanied by a rapid increase of H2SO4 and SOA, enhanced formation of sulfate and SOA driven by photochemical oxidation likely promoted the formation and growth of new particles. Together, our results demonstrated that strong atmospheric photochemical reactions enhanced secondary aerosols formation and led to the synchronous occurrence of high concentrations of PM2.5 and O3 in a regional scale. These findings are important for better understanding the air pollution in summer in YRD. PMID:27418517

  14. Effects of temperature and chemical addition on the formation of bromoorganic DBPs during ozonation.

    PubMed

    Zhang, Xiangru; Echigo, Shinya; Lei, Hongxia; Smith, Michael E; Minear, Roger A; Talley, Jeffrey W

    2005-01-01

    The effects of temperature and addition of OH radical scavengers/enhancers or HOBr scavenger on the formation of bromoorganic disinfection byproducts (DBPs) from ozonation of six raw waters were studied in true batch reactors. The formation of bromoorganic DBPs during ozonation generally increased with the increase of temperature, but might also decrease for the waters with somewhat higher values of specific UV absorbance (SUVA). The addition of hydrogen peroxide, ethanol, or ammonium dramatically decreased the formation of bromoorganic DBPs; t-butanol addition significantly increased the formation of bromoorganic DBPs; bicarbonate addition might increase or decrease bromoorganic DBP formation depending on the water source. For all the waters treated with the chemical addition, the level of total organic bromine (TOBr) varied with the same pace as that of ozone exposure (CT), which suggests that TOBr formed during ozonation may be used to estimate the CT, a measure for the achieved degree of disinfection. The results demonstrate that for each water, the correlation between TOBr and CT was less affected by the change of chemical composition of the water than that between BrO(3)(-) and CT; for a given chemical composition and temperature of a water, there generally were well-defined relationships between TOBr and CT, and bromoform and CT just as that between BrO(3)(-) and CT. The possible mechanisms behind the linear functions of TOBr or BrO(3)(-) versus CT were given. Further study is needed to examine whether the trends found in this research can be applicable for the high SUVA waters.

  15. The determination and role of peroxyacetil nitrate in photochemical processes in atmosphere

    PubMed Central

    2012-01-01

    Peroxyacetilnitrates (PAN) is the most characteristic photoxidant of a range of secondary pollutants formed by the photochemical reaction of hydrocarbons with nitrogen oxides in the atmosphere: it is phytotoxic and shows an increasing role in human health effects due to ambient air exposure, especially in presence of high ozone concentrations. Because of the similarity of the conditions required for their photochemical production PAN is observed in conjunction with elevated ozone concentrations. PAN has very low natural background concentrations so it is the very specific indicator of anthropogenic photochemical air pollution. In this paper we report PAN concentrations determined in Rome urban area during winter- and summer-period. PAN measurements were carried out by means of a gas-chromatograph equipped with an Electron Capture Detector (ECD) detector. For identifying the acute episodes of atmospheric photochemical pollutants the relationship between PAN and the variable Ox (=NO2+O3) which describes the oxidation process evolution is investigated. The role of Volatile Organic Compounds and PAN in the ozone formation is investigated as well the issue of taking in account the autovehicular emissions for checking the NOx fraction in fuel. PMID:22594443

  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. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. Photochemical formation of brominated dioxins and other products of concern from hydroxylated polybrominated diphenyl ethers (OH-PBDEs).

    PubMed

    Erickson, Paul R; Grandbois, Matthew; Arnold, William A; McNeill, Kristopher

    2012-08-01

    The photochemical conversion of selected hydroxylated polybrominated diphenyl ethers (OH-PBDEs) to dioxins and other products was investigated. OH-PBDEs, which are both transformation products of polybrominated diphenyl ethers and naturally occurring compounds, undergo direct photolysis to yield a number of products that may have a higher toxicity than their parent. The compounds investigated were 6-OH-PBDE 99, 6'-OH-PBDE 100, and 6'-OH-PBDE 118. Of special interest was 6'-OH-PBDE 118, a potential transformation product of PBDE 153 that is capable of photochemically generating 2,3,7,8-tetrabromodibenzo-p-dioxin, the most toxic brominated dioxin congener. Photolysis experiments were conducted at two different pH values to assess the photochemical behavior of both the phenol and phenolate form of the compounds. The percent conversion to dioxin and other photoproducts was determined and the natural product, 6-OH-PBDE 99, was found to have the highest conversion to dioxin (7%). The reaction quantum yields ranged from 0.027 to 0.16 across all photolysis conditions. In addition, it is shown that all three compounds are capable of photochemically generating other compounds of concern, including brominated phenols and a dibenzofuran.

  3. 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.

  4. 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.

  5. 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. PMID:25601614

  6. 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.

  7. Ozone-induced formation of O,O'-dityrosine cross-linked in proteins.

    PubMed

    Verweij, H; Christianse, K; Van Steveninck, J

    1982-02-18

    Treatment of spectrin, insulin, glucagon and ribonuclease with ozone results in covalent cross-linking of these proteins. This cross-linking is not reversed by treatment with dithiothreitol and thus can not be ascribed to -S-S- bond formation. A concomitant O,O'-dityrosine formation is observed by spectrofluorometric analysis of the protein and by amino acid analysis and thin-layer chromatography of hydrolyzed protein samples. It is highly probable that the observed protein cross-linking should be attributed to interpeptide O,O'-dityrosine bonds. Several authors have shown before that oxidation of proteins with horseradish peroxidase and H2O2 also leads to O,O'-dityrosine formation. Peroxidase-induced O,O'-dityrosine formation in galactose oxidase (d-galactose:oxygen 6-oxidoreductase, EC 1.1.3.9) causes a strong increase of enzyme activity. In accordance with these observations ozone treatment of galactose oxidase also leads to O,O'-dityrosine formation with a concomitant 8-fold increase of enzyme activity.

  8. 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 (...

  9. A general circulation model simulation of the springtime Antarctic ozone decrease and its impact on mid-latitudes

    SciTech Connect

    Cariolle, D.; Lasserre-Bigorry, A.; Royer, J.F. ); Geleyn, J.F. )

    1990-02-20

    Ozone is treated as an interactive variable calculated by means of a continuity equation which takes account of advection and photochemical production and loss. The ozone concentration is also used to compute the heating and cooling rates due to the absorption of solar ultraviolet radiation, and the infrared emission in the stratosphere. The daytime ozone decrease due to the perturbed chlorine chemistry found at high southern latitudes is introduced as an extra loss in the ozone continuity equation. Results of the perturbed simulation show a very good agreement with the ozone measurements made during spring 1987. The simulation also shows the development of a high-latitude anomalous circulation, with a warming of the upper stratosphere resulting mainly from dynamical heating. In addition, a substantial ozone decrease is found at mid-latitudes in a thin stratospheric layer located between the 390 and the 470 K {theta} surfaces. A significant residual ozone decrease is found at the end of the model integration, 7 months after the final warming and the vortex breakdown. If there is a significant residual ozone decrease in the atmosphere, the ozone trends predicted by photochemical models which do not take into account the high-latitude perturbed chemistry are clearly inadequate. Finally, it is concluded that further model simulations at higher horizontal resolution, possibly with a better representation of the heterogeneous chemistry, will be needed to evaluate with more confidence the magnitude of the mid-latitudinal ozone depletion induced by the ozone hole formation.

  10. High atmospheric NO(x) levels and multiple photochemical steady states

    NASA Technical Reports Server (NTRS)

    Kasting, J. F.; Ackerman, T. P.

    1985-01-01

    The rate of removal of atmospheric NO(x) compounds at different NO(x) levels is estimated using a one-dimensional photochemical model. NO(x) removal by wet deposition, surface deposition, and thermochemical processes is examined. NO(x) removal rates at different surface NO mixing ratios are calculated and the data are analyzed. It is revealed that at low NO(x) levels NO(x) is photochemically converted to HNO3 by either wet or dry deposition; however, at high NO(x) levels formation of HNO3 is inhibited due to the disappearance of tropospheric ozone and OH, and the NO(x) is removed by rainout of N2O4 and N2O5, surface deposition of NO and NO2, and direct dissolution of NO and NO2 in rainwater. The effects of NO(x) mixing ratios greater than 10 to the -7th on the ozone and climate are investigated.

  11. 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.

  12. 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.

  13. 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

    2014-09-01

    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.

  14. 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.

  15. The effects of increasing atmospheric ozone on biogenic monoterpene profiles and the formation of secondary aerosols

    NASA Astrophysics Data System (ADS)

    Pinto, Delia M.; Tiiva, Päivi; Miettinen, Pasi; Joutsensaari, Jorma; Kokkola, Harri; Nerg, Anne-Marja; Laaksonen, Ari; Holopainen, Jarmo K.

    Monoterpenes are biogenic volatile organic compounds (BVOCs) which play an important role in plant adaptation to stresses, atmospheric chemistry, plant-plant and plant-insect interactions. In this study, we determined whether ozonolysis can influence the monoterpenes in the headspace of cabbage. The monoterpenes were mixed with an air-flow enriched with 100, 200 or 400 ppbv of ozone (O 3) in a Teflon chamber. The changes in the monoterpene and O 3 concentrations, and the formation of secondary organic aerosols (SOA) were determined during ozonolysis. Furthermore, the monoterpene reactions with O 3 and OH were modelled using reaction kinetics equations. The results showed that all of the monoterpenes were unequally affected: α-thujene, sabinene and D-limonene were affected to the greatest extend, whereas the 1,8-cineole concentration did not change. In addition, plant monoterpene emissions reduced the O 3 concentration by 12-24%. The SOA formation was dependent on O 3 concentration. At 100 ppbv of O 3, virtually no new particles were formed but clear SOA formation was observed at the higher ozone concentrations. The modelled results showed rather good agreements for α-pinene and 1,8-cineole, whereas the measured concentrations were clearly lower compared to modelled values for sabinene and limonene. In summary, O 3-quenching by monoterpenes occurs beyond the boundary layer of leaves and results in a decreased O 3 concentration, altered monoterpene profiles and SOA formation.

  16. 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. PMID:25730285

  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. Nitrogen dioxide measurement by cavity attenuated phase shift spectroscopy (CAPS) and implications in ozone production efficiency and nitrate formation in Beijing, China

    NASA Astrophysics Data System (ADS)

    Ge, Baozhu; Sun, Yele; Liu, Ying; Dong, Huabin; Ji, Dongsheng; Jiang, Qi; Li, Jie; Wang, Zifa

    2013-08-01

    dioxide (NO2) is a key species in studying photochemical smog and formation mechanisms of nitrate in fine particles. However, the conventional commercially available chemiluminescence (CL)-based method often has uncertainties in measuring NO2 because of interferences with other reactive nitrogen species. In this study, an Aerodyne Cavity Attenuated Phase Shift Spectroscopy (CAPS) NO2 monitor that essentially has no interferences with nitrogen containing species was deployed in Beijing for the first time during August 2012. The CAPS NO2 monitor is highly sensitive with a detection limit (3σ) of 46.6 ppt for 1 min integration. The NO2 measured by CAPS shows overall agreement with that from CL, yet large differences up to 20% were also observed in the afternoon. Further, the discrepancies of NO2 measurements between CAPS and CL appear to be NOz dependent with larger differences at higher NOz concentrations (e.g., > 14 ppb). As a result, the ozone production efficiency of NOx (OPEx) derived from the correlations of Ox-NOz with the CL NO2 can be overestimated by 19-37% in Beijing. The daily OPEx calculated with the CAPS NO2 ranges from 1.0 to 6.8 ppb/ppb with an average (±1σ) of 2.6 (±1.3) for the entire study. The relatively low OPEx and the relationship between OPEx and NOx suggest that ozone production chemistry is VOC sensitive during summer in Beijing. Two case studies further show that high concentrations of NOx can significantly enhance the formation of nitrate in fine particles in the presence of high O3 and favorable meteorological conditions.

  19. 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. PMID:27387808

  20. Changes in stratospheric ozone.

    PubMed

    Cicerone, R J

    1987-07-01

    The ozone layer in the upper atmosphere is a natural feature of the earth's environment. It performs several important functions, including shielding the earth from damaging solar ultraviolet radiation. Far from being static, ozone concentrations rise and fall under the forces of photochemical production, catalytic chemical destruction, and fluid dynamical transport. Human activities are projected to deplete substantially stratospheric ozone through anthropogenic increases in the global concentrations of key atmospheric chemicals. Human-induced perturbations may be occurring already.

  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. 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.

  3. 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

  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. Ozone production in four major cities of China: sensitivity to ozone precursors and heterogeneous processes

    NASA Astrophysics Data System (ADS)

    Xue, L. K.; Wang, T.; Gao, J.; Ding, A. J.; Zhou, X. H.; Blake, D. R.; Wang, X. F.; Saunders, S. M.; Fan, S. J.; Zuo, H. C.; Zhang, Q. Z.; Wang, W. X.

    2013-10-01

    Despite a large volume of research over a number of years, our understandings of the key precursors that control tropospheric ozone production and the impacts of heterogeneous processes remain incomplete. In this study, we analyze measurements of ozone and its precursors made at rural/suburban sites downwind of four large Chinese cities - Beijing, Shanghai, Guangzhou and Lanzhou. At each site the same measurement techniques were utilized and a photochemical box model based on the Master Chemical Mechanism (v3.2) was applied, to minimize uncertainties in comparison of the results due to differences in methodology. All four cities suffered from severe ozone pollution. At the rural site of Beijing, export of the well-processed urban plumes contributed to the extremely high ozone levels (up to an hourly value of 286 ppbv), while the pollution observed at the suburban sites of Shanghai, Guangzhou and Lanzhou was characterized by intense in-situ ozone production. The major anthropogenic hydrocarbons were alkenes and aromatics in Beijing and Shanghai, aromatics in Guangzhou, and alkenes in Lanzhou. The ozone production was found to be in a VOCs-limited regime in both Shanghai and Guangzhou, and a mixed regime in Lanzhou. In Shanghai, the ozone formation was most sensitive to aromatics and alkenes, while in Guangzhou aromatics were the predominant ozone precursors. In Lanzhou, either controlling NOx or reducing emissions of olefins from the petrochemical industry would mitigate the local ozone production. The potential impacts of several heterogeneous processes on the ozone formation were assessed. The hydrolysis of dinitrogen pentoxide (N2O5), uptake of the hydroperoxyl radical (HO2) on particles, and surface reactions of NO2 forming nitrous acid (HONO) present considerable sources of uncertainty in the current studies of ozone chemistry. Further efforts are urgently required to better understand these processes and refine atmospheric models.

  6. Research on Efficiency of Ozonation and Bromate Formation in Low Temperature and Low Turbidity Water

    NASA Astrophysics Data System (ADS)

    Zhu, Qi; Liu, Dongmei; Cui, Fuyi; Fang, Lei; Zhao, Zhiwei; Liu, Tongmian

    2010-11-01

    The efficiency of ozonation and the influence factor of bromate formation were studied in filtered water at low temperature and low turbidity in Harbin Shaohe water treatment plant, of which source water was from Songhua river. The results showed that when adding 3 mg/L O3 to the filtered water, the average removal rate of UV254 were 22.31%, the removal rate of TOC in filtered water were 6.33%. When adding 2 mg/L O3 and 4 mg/L O3 to the filtered water, the CODMn decreased by 21.53% and 24.68%, respectively. Ozonation had no obvious effect on reducing turbidity and the content of ammonia nitrogen of filtered water in Shaohe water treatment plant. It could be found that the formation amount of BrO3- would increase with the concentration of Br- increasing in low temperature and low turbidity water. When Ct value of filtered water in Shaohe water treatment plant was less than 30 mgṡL-1ṡmin, the formation amount of BrO3- could be controlled under 10 μg/L.

  7. 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.

  8. 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

  9. 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...

  10. 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

  11. 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)

  12. Understanding ozone formation and the radical budget during oil sands plume transport in the Athabasca region of Alberta

    NASA Astrophysics Data System (ADS)

    Moussa, S. G.; Leithead, A.; Li, S. M.; Wang, D. K.; O'brien, J.; Mittermeier, R. L.; Gordon, M.; Staebler, R. M.; Liu, P.; Liggio, J.

    2015-12-01

    The sources of ozone and hydroxyl radicals (OH) in the Alberta oil sands (OS) region have not previously been well characterized. In the summer of 2013, airborne measurements of various volatile organic compounds (VOCs), nitrogen oxides (NOx = NO2+NO) and ozone were made in the Athabasca OS region between August 13 and September 7, 2013. Proton Transfer Reaction-Time of Flight-Mass Spectrometry (PTR-ToF-MS) and whole air samples were used to measure VOCs. A box model incorporating the Master Chemical Mechanism (MCM v3.3), was constrained by measured chemical species and meteorological parameters and used to simulate the evolution of an OS plume. In doing so, an improved understanding of the chemical factors controlling the radical budget and the evolution of ozone in oil sands plumes is achieved. Our results indicate that approximately 20% of the in-plume generated OH radicals are derived from primary sources (HCHO, O3 and HONO photolysis). The remaining OH is derived from the recycling of hydroperoxyl radical (HO2). The HO2 and alkyl peroxyl radical (RO2) chemistry leads to 35% of the ozone formation in the plume, while the main sink for ozone in the plume was via reactions with alkenes (anthropogenic and biogenic). The results of this work will help to characterize ozone formation and the factors influencing its atmospheric fate in the oil sands region.

  13. Convective Signatures in Ozone Profiles: Guidance for Cloud Models

    NASA Astrophysics Data System (ADS)

    Stone, J. B.; Thompson, A. M.; Miller, S. K.; Witte, J. C.; Pickering, K. E.; Tao, W. K.

    2006-05-01

    Ozone throughout the free troposphere is a tracer for convection, stratospheric exchange and pollution. Convective influences are typically manifested in two ways: (1) redistribution of ozone from the boundary-layer to free troposphere. In unpolluted regions, this usually means decreasing ozone in the upper troposphere (UT) or UT/LS (upper troposphere-lower stratosphere). Over polluted regions, the opposite may occur. (2) enhancing O3 precursors (NO, CO, hydrocarbons) in the free troposphere, through redistribution, or in the case of lightning, through direct production of NO, adds to photochemical ozone formation. Since about 1990 we have studied ozone dynamics and photochemistry with cloud-resolving (CRM) and larger-scale models. Aircraft profiles of O3, ozone precursors (NO, CO, hydrocarbons) and photochemically related constituents guide model input and are used to evaluate model output. Recently, we have used a semi-empirical approach ("lamina-layering," after Pierce and Grant [1998]) to identifying convective impacts on ozone profiles taken with soundings. The latter are measured by ozonesondes that are flown with radiosondes, to collect PTU data. The advantage of ozonesondes is consistent vertical sampling of ozone into the UT/LS with 5- 25 m resolution, and regular frequency at stations where they are launched. Examples of convective influence in ozone profiles - case studies and climatology at selected locations - will be shown for mid-latitudes and tropics. In mid-latitudes convective ozone budgets are compared to influences of stratospheric exchange and pollution. In the tropics, convective impacts reflect El Nino, the MJO and possible trends in a cooling UT/LS.

  14. 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

  15. 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.

  16. 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.

  17. Sensitivity of ozone to precursor emissions in urban Beijing with a Monte Carlo scheme

    NASA Astrophysics Data System (ADS)

    Tang, Xiao; Wang, Zifa; Zhu, Jiang; Gbaguidi, Alex E.; Wu, Qizhong; Li, Jie; Zhu, Tong

    2010-10-01

    In order to understand the formation mechanisms of high surface ozone and identify the main contributor sources in Beijing, this study investigates the sensitivity of surface ozone to NO, NO 2 and nine types of NMVOC emissions during a photochemical smog episode. Monte Carlo sensitivity analysis scheme with fifty simulations is established based on the Nested Air Quality Prediction Model System (NAQPMS). At every simulation, each of the eleven precursor emissions is perturbed with a distinct set of perturbations. The sensitivities of ozone to emissions are identified by multiple linear regressions. The stability of sensitivity results is validated by two experiments with standard deviations of log-normal perturbations set as 30% and 50% respectively. The sensitivity results suggest that the current high surface ozone is strongly stimulated by NMVOC emissions. Among NMVOC emissions, formaldehyde, ethylene and olefins emissions present the greatest impacts on ozone. On the other hand, NOx emissions have a strong inhibitory effect on ozone formation, even after 50% NOx emission reduction. This indicates that the current ozone formation in Beijing is under NOx-saturated conditions. A transition of ozone formation is observed from NOx-saturated to NOx-limited sensitivity behavior with a 75% reduction of NOx emissions. This study gives the implication that abatement of the four NMVOC types mentioned above could be efficient on reducing the high levels of surface ozone in central urban Beijing, while inadequate abatement in NOx emissions probably induces reverse effects.

  18. 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.

  19. 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. PMID:27525579

  20. 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.; Sachse, G. W.

    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.

  1. 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.

  2. 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.

  3. 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. PMID:26287571

  4. 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.

  5. 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.

  6. 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...

  7. 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.

  8. [Pollution characteristics and ozone formation potential of ambient VOCs in winter and spring in Xiamen].

    PubMed

    Xu, Hui; Zhang, Han; Xing, Zhen-yu; Deng, Jun-jun

    2015-01-01

    Air samples were collected at urban and rural sites in Xiamen from January to April 2014. The concentrations of 48 ambient volatile organic compounds (VOC) species were measured by the method of cryogenic pre-concentrator and gas chromatography-mass spectrometry (GC/MS). The ozone formation potential (OFP) of VOCs was also calculated with the method of maximum incremental reactivity (MIR). The results showed that the average mixing ratios of VOCs in winter were 11.13 x 10(-9) and 7.17 x 10(-9) at urban and rural sites, respectively, and those in spring were 24.88 x 10(-9) and 11.27 x 10(-9) at urban and rural sites, respectively. At both sites, alkanes contributed the most to VOCs, followed by aromatics and alkenes. The ratios of B/T showed that vehicle and solvent evaporation were the main sources of VOCs at urban site. While at rural site, transport of anthropogenic sources was another important source of VOCs besides local biomass emissions. Ten main components including propene, n-butane, i-butane, n-pentane, i-pentane, n-hexane, benzene, toluene, ethylbenzene and m/p-xylene accounted for 61.57% and 45.83% of total VOCs at urban and rural sites in winter, respectively, and 62.83% and 53.74% at urban and rural sites in spring, respectively. Aromatics contributed the most to total OFP, followed by alkenes. Alkanes contributed the least to OFP with the highest concentration. C3, C4 alkenes and aromatics were found to be the more reactive species with relatively high contributions to ozone formation in Xiamen. Comparing the average MIR of VOCs at the two sites, it was found that the reactivity of VOCs at rural site was higher than that at urban site. PMID:25898641

  9. 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).

  10. 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.

  11. 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.

  12. 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.

  13. Semiclassical wave packet study of anomalous isotope effect in ozone formation.

    PubMed

    Vetoshkin, Evgeny; Babikov, Dmitri

    2007-10-21

    We applied the semiclassical initial value representation method to calculate energies, lifetimes, and wave functions of scattering resonances in a two-dimensional potential for O+O2 collision. Such scattering states represent the metastable O3* species and play a central role in the process of ozone formation. Autocorrelation functions for scattering states were computed and then analyzed using the Prony method, which permits one to extract accurate energies and widths of the resonances. We found that the results of the semiclassical wave packet propagation agree well with fully quantum results. The focus was on the 16O16O18O isotopomer and the anomalous isotope effect associated with formation of this molecule, either through the 16O16O+18O or the 16O+16O18O channels. An interesting correlation between the local vibration mode character of the metastable states and their lifetimes was observed and explained. New insight is obtained into the mechanism by which the long-lived resonances in the delta zero-point energy part of spectrum produce the anomalously large isotope effect.

  14. 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.

  15. Interactions of fire emissions and urban pollution over California: Ozone formation and air quality simulations

    NASA Astrophysics Data System (ADS)

    Singh, H. B.; Cai, C.; Kaduwela, A.; Weinheimer, A.; Wisthaler, A.

    2012-09-01

    An instrumented DC-8 aircraft was employed to perform airborne observations in rural and urban environs of California during the summer 2008 NASA ARCTAS-CARB campaign. The fortuitous occurrence of large wildfire episodes in Northern California allowed for studies of fire emissions, their composition, and their interactions with rural and urban air. Relative to CO, emissions of HCN were shown to vary non-linearly with fire characteristics while those of CH3CN were nearly unchanged, making the latter a superior quantitative tracer of biomass combustion. Although some fire plumes over California contained little NOx and virtually no O3 enhancement, others contained ample VOCs and sufficient NOx, largely from urban influences, to result in significant ozone formation. The highest observed O3 mixing ratios (170 ppb) were also in fire-influenced urban air masses. Attempts to simulate these interactions using CMAQ, a high-resolution state of the art air quality model, were only minimally successful and indicated several shortcomings in simulating fire emission influences on urban smog formation. A variety of secondary oxidation products (e.g. O3, PAN, HCHO) were substantially underestimated in fire-influenced air masses. Available data involving fire plumes and anthropogenic pollution interactions are presently quite sparse and additional observational and mechanistic studies are needed.

  16. [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.

  17. 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. PMID:27396671

  18. 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.

  19. 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.

  20. 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.

  1. 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

  2. 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)

  3. 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

  4. 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 ...

  5. 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.

  6. 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

  7. 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

  8. 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

  9. 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

  10. Quantum-mechanical calculations on termolecular association reactions XY+Z+M-->XYZ+M: Application to ozone formation

    NASA Astrophysics Data System (ADS)

    Charlo, David; Clary, David C.

    2002-07-01

    We present a quantum-mechanical model for termolecular association reactions XY+Z+M→XYZ+M involving the formation of a long-lived complex XYZ*. The rotation of the molecule XYZ is treated in the infinite order sudden approximation (IOS) and its vibrations are treated by the coupled-channel method (VCC). Resonances featuring the XYZ* long-lived complex formation are first computed by means of the stabilization method and are then included in the vibrational basis functions used for the inelastic VCC-IOS scattering calculation. The method yields rate constants for the association process selected in resonance and bound states of XYZ. We apply the method to the formation of ozone and investigate isotope effects. Calculations of energy transfer and collision-induced recombination of O+O2 in collision with Ar are reported for a range of ozone isotopomers. The bending mode of O3 is not treated explicitly in these computations. The results establish a strong selectivity in vibrational state-to-state cross sections for the deactivation of O3 during the collisional energy transfer process with Ar. The present calculations also account for the high sensitivity of rate constants with respect to the isotopic composition of ozone molecules but not in the same proportion as experiments. The energy transfer from selected initial vibrational states is also calculated as a function of the initial relative kinetic energy.

  11. 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). PMID:9072953

  12. 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).

  13. 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.

  14. 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.

  15. 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. PMID:15093111

  16. 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.

  17. 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

  18. Photochemical products in urban mixtures enhance inflammatory responses in lung cells.

    PubMed

    Sexton, Kenneth G; Jeffries, Harvey E; Jang, Myoseon; Kamens, Richard M; Doyle, Melanie; Voicu, Iuliana; Jaspers, Ilona

    2004-01-01

    Complex urban air mixtures that realistically mimic urban smog can be generated for investigating adverse health effects. "Smog chambers" have been used for over 30 yr to conduct experiments for developing and testing photochemical models that predict ambient ozone (O(3)) concentrations and aerosol chemistry. These chambers were used to generate photochemical and nonirradiated systems, which were interfaced with an in vitro exposure system to compare the inflammatory effects of complex air pollutant mixtures with and without sunlight-driven chemistry. These are preliminary experiments in a new project to study the health effects of particulate matter and associated gaseous copollutants. Briefly, two matched outdoor chambers capable of using real sunlight were utilized to generate two test atmospheres for simultaneous exposures to cultured lung cells. One chamber was used to produce a photochemically active system, which ran from sunrise to sunset, producing O(3) and the associated secondary products. A few hours after sunset, NO was added to titrate and remove completely the O(3), forming NO(2). In the second chamber, an equal amount of NO(2) and the same amount of the 55-component hydrocarbon mixture used to setup the photochemical system in the first side were injected. A549 cells, from an alveolar type II-like cell line grown on membranous support, were exposed to the photochemical mixture or the "original" NO(2)/hydrocarbon mixture for 5 h and analyzed for inflammatory response (IL-8 mRNA levels) 4 h postexposure. In addition, a variation of this experiment was conducted to compare the photochemical system producing O(3) and NO(2), with a simple mixture of only the O(3) and NO(2). Our data suggest that the photochemically altered mixtures that produced secondary products induced about two- to threefold more IL-8 mRNA than the mixture of NO(2) and hydrocarbons or O(3). These results indicate that secondary products generated through the photochemical reactions

  19. 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

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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

  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. A Status Report on the SHADOZ (Southern Hemisphere Additional Ozonesondes) Project and Some Issues Affecting Ozone Climatology

    NASA Technical Reports Server (NTRS)

    Thompson, Anne M.; Witte, J. C.; McPeters, R. D.; Einaudi, Franco (Technical Monitor)

    2000-01-01

    SHADOZ aims to support the study of local and global patterns in stratospheric and tropospheric ozone and to provide a data set for the validation for satellite products and model calculations of ozone. Southern hemispheric tropical ozone is of particular interest because this region appears to have complex interplay among photochemical ozone formation (from biomass burning and lightning), stratospheric dynamics, convection and possibly cross-hemispheric transport. Balloon-borne ozone instrumentation (ozonesondes), joined with standard radiosondes for measurement of pressure, temperature and relative humidity, is used to collect profiles throughout the troposphere and lower- to mid-stratosphere. A network of 10 southern hemisphere tropical and subtropical stations, called the Southern Hemisphere ADditional OZonesondes (SHADOZ) project, has been established from operational sites to assemble sonde data for 1998-2000. A status report on the archive, with station operating characteristics, will be given, along with some operational issues that may affect data analysis and interpretation.

  7. 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.

  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. 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.

  10. 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

  11. Isoprene and terpene gas-phase mechanisms and their effect on ozone formation over the regional scale

    SciTech Connect

    Stockwell, W.R.; Kuhn, M.; Seefeld, S.; Kirchner, F.

    1997-12-31

    Ozone is produced through the photo-oxidation of nitrogen oxides and volatile organic compounds. Biogenic emissions are an important source of reactive organic compounds such as isoprene and terpenes. Their reactions contribute to the production of ozone and aerosol particles. The photo-oxidation of isoprene and terpene affect the atmosphere`s nitrogen budget through the formation of nitrates and peroxyacetyl nitrates (PAN). Biogenic compounds also affect hydroperoxide formation rates. The authors have developed new oxidation mechanisms for isoprene, a-pinene and d-limonene based upon recent laboratory results. However, many unknowns remain in the experimental data and it was necessary to complete the a-pinene and d-limonene mechanism by using reactions that were analogous to known reactions for alkenes of lower carbon number. The new mechanism for isoprene, a-pinene and d-limonene was successfully tested against smog chamber runs. The authors will present the new biogenic mechanisms, compare simulations with environmental chamber runs and show results of simulations for typical urban, rural and remote conditions. They will show evaluations of the influence of biogenic emissions on the concentrations of ozone, nitrates, hydroperoxides and peroxynitrates over the regional scale.

  12. 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.

  13. 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. PMID:26746418

  14. 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 ...

  15. 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.

  16. 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.

  17. 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...

  18. 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.

  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. 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.

  20. 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.

  1. The role of chlorine chemistry in Antarctic ozone loss - Implications of new kinetic data

    NASA Technical Reports Server (NTRS)

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

    1990-01-01

    New kinetic data yielding a slower formation rate and larger absorption cross sections of Cl2O2 are incorporated into a photochemical model to reassess the role of chlorine chemistry in accounting for the ozone reductions derived from TOMS observations in different regions of the Antarctic polar vortex during 1987. The model is further constrained by existing measurements from the Airborne Antarctic Ozone Experiment and the National Ozone Expedition II. Calculated concentrations of ClO based on the new kinetic data increase by almost a factor of two between the collar and core regions of the vortex during the second half of September. The calculated ozone reductions in the vortex core appear to be consistent with the TOMS observations in spite of the slower rate for the self-reaction of ClO.

  2. 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

  3. 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.

  4. 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. PMID:26971810

  5. 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.

  6. 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.

  7. Rapid formation of molecular bromine from deliquesced NaBr aerosol in the presence of ozone and UV light

    NASA Astrophysics Data System (ADS)

    Nissenson, Paul; Wingen, Lisa M.; Hunt, Sherri W.; Finlayson-Pitts, Barbara J.; Dabdub, Donald

    2014-06-01

    The formation of gas-phase bromine from aqueous sodium bromide aerosols is investigated through a combination of chamber experiments and chemical kinetics modeling. Experiments show that Br2(g) is produced rapidly from deliquesced NaBr aerosols in the presence of OH radicals produced by ozone irradiated by UV light. The mechanisms responsible for the “bromine explosion” are examined using a comprehensive chemical kinetics Model of Aqueous, Gaseous, and Interfacial Chemistry (MAGIC). A sensitivity analysis on the model confirms that a complex mechanism involving gas-phase chemistry, aqueous-phase chemistry, and mass transfer is responsible for most of the observed bromine. However, the rate-limiting steps in the bromine explosion pathway vary, depending on the availability of ozone and bromide in the system. Interface reactions, an important source of bromine production under dark conditions, account for only a small fraction of total bromine under irradiation. Simulations performed with gaseous ozone and aerosol bromide concentrations typical of the marine boundary layer also show Br2(g) production, with BrO(g) and HOBr(g) as the dominant Br-containing products through this mechanism. Aerosol bromide is depleted after several hours of daylight, with photolysis of BrO(g) and HOBr(g) becoming major sources of Br atoms that continue generating Br2(g) after aerosol bromide is depleted.

  8. 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. PMID:26776458

  9. 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.

  10. Transformation of ranitidine during water chlorination and ozonation: Moiety-specific reaction kinetics and elimination efficiency of NDMA formation potential.

    PubMed

    Jeon, Dahee; Kim, Jisoo; Shin, Jaedon; Hidayat, Zahra Ramadhany; Na, Soyoung; Lee, Yunho

    2016-11-15

    Ranitidine can produce high yields of N-nitrosodimethylamine (NDMA) upon chloramination and its presence in water resources is a concern for water utilities using chloramine disinfection. This study assessed the efficiency of water chlorination and ozonation in transforming ranitidine and eliminating its NDMA formation potential (NDMA-FP) by determining moiety-specific reaction kinetics, stoichiometric factors, and elimination levels in real water matrices. Despite the fact that chlorine reacts rapidly with the acetamidine and thioether moieties of ranitidine (k>10(8)M(-1)s(-1) at pH 7), the NDMA-FP decreases significantly only when chlorine reacts with the less reactive tertiary amine (k=3×10(3)M(-1)s(-1) at pH 7) or furan moiety (k=81M(-1)s(-1) at pH 7). Ozone reacts rapidly with all four moieties of ranitidine (k=1.5×10(5)-1.6×10(6)M(-1)s(-1) at pH 7) and its reaction with the tertiary amine or furan moiety leads to complete elimination of the NDMA-FP. Treatments of ranitidine-spiked real water samples have shown that ozonation can efficiently deactivate ranitidine in water and wastewater treatment, while chlorination can be efficient for water containing low concentration of ammonia. This result can be applied to the other structurally similar, potent NDMA precursors. PMID:27381234

  11. 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

  12. Formation of molecular chlorine from the photolysis of ozone and aqueous sea-salt particles

    PubMed

    Oum; Lakin; DeHaan; Brauers; Finlayson-Pitts

    1998-01-01

    Halogen atoms from the reactions of sea-salt particles may play a significant role in the marine boundary layer. Reactions of sodium chloride, the major component of sea-salt particles, with nitrogen oxides generate chlorine atom precursors. However, recent studies suggest there is an additional source of chlorine in the marine troposphere. This study shows that molecular chlorine is generated from the photolysis of ozone in the presence of sea-salt particles above their deliquescence point; this process may also occur in the ocean surface layer. Given the global distribution of ozone, this process may provide a global source of chlorine.

  13. Photochemical Synthesis of Nepetanudone.

    PubMed

    Jayan, Swapna; Jones, Paul B

    2015-06-26

    Nepetanudone and nepetaparnone have been suspected of being the products of a photochemical dimerization of nepetapyrone. Both are natural products found in a variety of Nepeta species. The synthesis of (±)-nepetapyrone and subsequent photochemical experiments are described. (±)-Nepetanudone was produced upon irradiation of (±)-nepetapyrone, while (±)-nepetaparnone, a diastereomer of nepetanudone, was not observed. PMID:25978278

  14. Nitrogen origins and the role of ozonation in the formation of haloacetonitriles and halonitromethanes in chlorine water treatment.

    PubMed

    Yang, Xin; Shang, Chii; Shen, Qianqian; Chen, Baiyang; Westerhoff, Paul; Peng, Jinfeng; Guo, Wanhong

    2012-12-01

    Nitrogenous disinfection byproducts (N-DBPs) such as haloacetonitriles (HANs) and halonitromethanes (HNMs) are formed during water chlorination. Preozonation is sometimes applied to control trihalomethane (THM) formation, but this may risk promoting the formation of HNMs and HANs. The role of ozone in the formation of HANs and HNMs in natural waters remains unclear. The nitrogen sources involved in HAN and HNM formation during the chloramination of dissolved organic matter (DOM) with and without preozonation were evaluated using (15)N-labeled monochloramine. The origin of the nitrogen involved in HAN formation was found to depend on the ratio of dissolved organic carbon to nitrogen. In nitrogen-rich solutions HAN nitrogen was mainly from DOM constituents. The formation of (15)N-labeled dichloroacetontrile (DCAN) accounted for approximately 30% of the DCAN produced from all hydrophilic acidic and neutral isolates, which have low carbon to nitrogen ratios, while it reached over 50% for the hydrophobic acidic, basic, and neutral isolates with high carbon to nitrogen ratios. Unlabeled trichloronitromethane (TCNM) accounted for over 90% of the total TCNM produced from most of the isolates. The remaining less than 10% of the TCNM was probably generated through an aldehyde pathway. Preozonation reduced DCAN but enhanced the yield of TCNM. The destruction of amino acids and amine structures and subsequent formation of nitro groups by preozonation may help explain the reduced DCAN and increased TCNM formation. PMID:23153098

  15. 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. PMID:22916444

  16. 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...

  17. 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...

  18. 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.

  19. 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. PMID:21086985

  20. 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.

  1. 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.

  2. 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

  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. Formation of ozone and growth of aerosols in young smoke plumes from biomass burning: 1. Lagrangian parcel studies

    NASA Astrophysics Data System (ADS)

    Alvarado, Matthew James; Prinn, Ronald G.

    2009-05-01

    We have developed a new model of the gas- and aerosol-phase chemistry of biomass burning smoke plumes called Aerosol Simulation Program (ASP). Here we use ASP combined with a Lagrangian parcel model to simulate the chemistry in smoke plumes from three fires: the Otavi savannah fire in Namibia, an Alaska boreal forest fire, and the Timbavati savannah fire. Our model explained the observations of ozone in the Otavi and Alaska plumes fairly well, but our initial model simulation of the Timbavati plume underestimated the concentrations of ozone, OH, and secondary aerosol matter. The Timbavati simulation agrees with observations if we increase OH to equal its observed levels. Heterogeneous reactions of NO2 and SO2 could explain the needed higher concentrations of OH and the rapid formation of ozone, nitrate, and sulfate in the smoke plume if the uptake coefficients on smoke aerosols are large (O(10-3) and O(10-4), respectively). Uncharacterized organic species in the smoke plume were likely responsible for the rapid formation of aerosol organic carbon. The changes in the aerosol size distribution were dominated by plume dilution and condensational growth. The single scattering albedo of the modeled smoke increases from 0.866 to 0.902 over 1 h of aging. The change in aerosol scattering with relative humidity for the modeled fresh smoke matches observations up to 66% RH, but the model greatly overestimates the humidification factor at 80% RH (2.88 versus an observed value of 1.70-1.79). For the aged smoke, the modeled humidification factor is 1.22, slightly below the observed value of 1.40.

  5. 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

    2015-08-01

    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.

  6. 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

    2015-08-01

    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. PMID:26151227

  7. Combination of UV absorbance and electron donating capacity to assess degradation of micropollutants and formation of bromate during ozonation of wastewater effluents.

    PubMed

    Chon, Kangmin; Salhi, Elisabeth; von Gunten, Urs

    2015-09-15

    In this study, the changes in UV absorbance at 254 nm (UVA254) and electron donating capacity (EDC) were investigated as surrogate indicators for assessing removal of micropollutants and bromate formation during ozonation of wastewater effluents. To measure the EDC, a novel method based on size exclusion chromatography followed by a post-column reaction was developed and calibrated against an existing electrochemical method. Low specific ozone doses led to a more efficient abatement of EDC than of UVA254. This was attributed to the abatement of phenolic moieties in the dissolved organic matter (DOM), which lose their EDC upon oxidation, but are partially transformed into quinones, which still absorb in the measured UV range. For higher specific ozone doses, the relative EDC abatement was lower than the relative UVA abatement, which can be explained by the oxidation of UV absorbing moieties (e.g. non-activated aromatic compounds), which contribute less to EDC. The abatement of the selected micropollutants (i.e., 17α-ethinylestradiol (EE2), carbamazepine (CBZ), atenolol (ATE), bezafibrate (BZF), ibuprofen (IBU), and p-chlorobenzoic acid (pCBA)) varied significantly depending on their reactivity with ozone in the examined specific ozone dose range of 0-1.45 mgO3/mgDOC. The decrease of EE2 and CBZ with high ozone reactivity was linearly proportional to the reduction of the relative residuals of UVA254 and EDC. The abatement of ATE, BZF, IBU, and pCBA with intermediate to low ozone reactivities was not significant in a first phase (UVA254/UVA254,0 = 1.00-0.70; EDC/EDC0 = 1.00-0.56) while their abatement was more efficient than the degradation of the relative residual UVA254 and much more noticeable than the degradation of the relative residual EDC in a second phase (UVA254/UVA254,0 = 0.70-0.25; EDC/EDC0 = 0.56-0.25) because the partially destroyed UV absorbing and electron donating DOM moieties become recalcitrant to ozone attack. Bromate formation was

  8. Combination of UV absorbance and electron donating capacity to assess degradation of micropollutants and formation of bromate during ozonation of wastewater effluents.

    PubMed

    Chon, Kangmin; Salhi, Elisabeth; von Gunten, Urs

    2015-09-15

    In this study, the changes in UV absorbance at 254 nm (UVA254) and electron donating capacity (EDC) were investigated as surrogate indicators for assessing removal of micropollutants and bromate formation during ozonation of wastewater effluents. To measure the EDC, a novel method based on size exclusion chromatography followed by a post-column reaction was developed and calibrated against an existing electrochemical method. Low specific ozone doses led to a more efficient abatement of EDC than of UVA254. This was attributed to the abatement of phenolic moieties in the dissolved organic matter (DOM), which lose their EDC upon oxidation, but are partially transformed into quinones, which still absorb in the measured UV range. For higher specific ozone doses, the relative EDC abatement was lower than the relative UVA abatement, which can be explained by the oxidation of UV absorbing moieties (e.g. non-activated aromatic compounds), which contribute less to EDC. The abatement of the selected micropollutants (i.e., 17α-ethinylestradiol (EE2), carbamazepine (CBZ), atenolol (ATE), bezafibrate (BZF), ibuprofen (IBU), and p-chlorobenzoic acid (pCBA)) varied significantly depending on their reactivity with ozone in the examined specific ozone dose range of 0-1.45 mgO3/mgDOC. The decrease of EE2 and CBZ with high ozone reactivity was linearly proportional to the reduction of the relative residuals of UVA254 and EDC. The abatement of ATE, BZF, IBU, and pCBA with intermediate to low ozone reactivities was not significant in a first phase (UVA254/UVA254,0 = 1.00-0.70; EDC/EDC0 = 1.00-0.56) while their abatement was more efficient than the degradation of the relative residual UVA254 and much more noticeable than the degradation of the relative residual EDC in a second phase (UVA254/UVA254,0 = 0.70-0.25; EDC/EDC0 = 0.56-0.25) because the partially destroyed UV absorbing and electron donating DOM moieties become recalcitrant to ozone attack. Bromate formation was

  9. Prompt formation of organic acids in pulse ozonation of terpenes on aqueous surfaces

    NASA Astrophysics Data System (ADS)

    Hoffmann, M. R.; Colussi, A. J.; Enami, S.

    2010-12-01

    A major atmospheric process, the gas-phase ozonation of terpenes yields suites of products via a cascade of chemically activated intermediates that ranges from primary ozonides to dioxiranes. If a similar mechanism operated in water, as it is generally assumed, such intermediates would be deactivated within picoseconds and, henceforth, unable to produce carboxylic acids in microseconds. Herein we report the online electrospray mass spectrometric detection of (M + 2O - H+) and (M + 3O - H+) carboxylates on the surface of aqueous β-caryophyllene (C15H24, M = 204 Da) microjets exposed to a few ppmv O3(g) for < 10 μs. Since neither species is formed on dry solvent microjets, and both incorporate deuterium from D2O, we infer that carboxylates ensue from the interaction of nascent intermediates with interfacial water via a heretofore unreported mechanism. These interfacial events proceed much faster than in bulk liquids saturated with ozone.

  10. 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.

  11. Photochemical Chlorine Activation From Artificial Saline Snowpacks

    NASA Astrophysics Data System (ADS)

    Wren, S. N.; Abbatt, J.; Donaldson, J.

    2012-12-01

    Halogen activation on snow and ice substrates has a profound influence on the oxidative capacity of the polar boundary layer. The release of reactive chlorine species is of particular interest since chlorine atoms can participate in both ozone depletion and organic oxidation. However, the mechanisms by which halides in sea ice substrates are converted into reactive halogen species are not well understood. In this study we investigated the photochemical activation of chlorine from artificial saline snow. Gas phase Cl2, BrCl and Br2 were detected using a chemical ionization mass spectrometer. We observe the dark release of Br2 in the presence of ozone; BrCl and Cl2 are only observed in the presence of both ozone and light. Interestingly, the release of reactive chlorine species persists when a 320 nm or a 380 nm long-pass filter is placed in the light path. Results suggest that smaller snow grains, which present a larger total snow surface area, enhance chlorine production to a greater extent than BrCl or Br2 production. Here we also present the effect of temperature (above and below the NaCl euctectic), acidity, chloride concentration, and ozone concentration on the production of Br2, BrCl and Cl2. Overall the results indicate that a mechanism involving UV-A light and ozone leads to chlorine activation, which may be particularly important in bromide-depleted snow.

  12. 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.

  13. Photochemical Energy Conversion.

    ERIC Educational Resources Information Center

    Batschelet, William H.; George, Arnold

    1986-01-01

    Describes procedures for two demonstrations: (1) photochemical energy conversion using ferric oxalate actinometry and (2) liquification of gases using Freon 114. Safety precautions are given for both demonstrations, as are procedures and material specifications. (JM)

  14. UV photolysis of ClOOCl and the ozone hole.

    PubMed

    Lin, Jim J; Chen, Andrew F; Lee, Yuan T

    2011-07-01

    The photochemistry of the ClO dimer (ClOOCl) plays a central role in the catalytic destruction of polar stratospheric ozone. In spite of decades of intense investigations, some of its laboratory photochemical data had not reached the desired accuracy to allow a reliable simulation of the stratospheric ozone loss until recently. Inevitable impurities in ClOOCl samples have obstructed conventional measurements. In particular, an absorption measurement of ClOOCl in 2007, which gave much lower cross sections than previous studies, implied that the formation of the ozone hole cannot be explained with current chemical models. Scientists have wondered whether the model is insufficient or the data is erroneous. Efforts aiming to resolve this controversy are reviewed in this paper, which emphasizes newly developed experiments to determine two critical photochemical properties of ClOOCl--its absorption cross section and product branching ratio--including the first reported product branching ratio at 351.8 nm photolysis. PMID:21538907

  15. Long wavelength photochemistry of ozone and n-butylferrocene: A matrix isolation study

    NASA Astrophysics Data System (ADS)

    Pinelo, Laura F.; Ault, Bruce S.

    2016-07-01

    The photochemical reaction of ozone and n-butylferrocene has been studied using a combination of argon-matrix isolation, infrared spectroscopy, and theoretical calculations. The dark deposition produced a vivid green matrix that, when irradiated with red light, turned a brownish-red color. This green matrix as well as slightly red-shifted O3 infrared absorptions are indicative of the formation an initial charge transfer complex between ozone and n-butylferrocene. The spectral results support the photodissociation of the complexed ozone with red light (λ ≥ 600 nm) producing an oxygen atom, O(3P), and a dioxygen molecule, O2(3Σ). The O(3P) then reacts with n-butylferrocene to form products consisting of an iron atom with a coordinated n-butylcyclopentadienyl or cyclopentadienyl ring and either: (1) a pyran, (2) an aldehyde, or (3) a bidentate cyclic aldehyde with a seven-membered ring including the iron atom. The photochemical products were characterized with FT-IR spectroscopy, 18O-labeled O3 experiments, and DFT calculations using the B3LYP functional with the 6-311++G(d, 2p) basis set. A possible mechanism for the photochemical reaction is discussed.

  16. 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.

  17. Large-scale variations in ozone and polar stratospheric clouds measured with airborne lidar during formation of the 1987 ozone hole over Antarctica

    NASA Technical Reports Server (NTRS)

    Browell, Edward V.; Poole, Lamont R.; Mccormick, M. Patrick; Ismail, Syed; Butler, Carolyn F.; Kooi, Susan A.; Szedlmayer, Margaret M.; Jones, Rod; Krueger, Arlin J.; Tuck, Adrian

    1988-01-01

    A joint field experiment between NASA and NOAA was conducted during August to September 1987 to obtain in situ and remote measurements of key gases and aerosols from aircraft platforms during the formation of the ozone (O3) hole over Antarctica. The ER-2 (advanced U-2) and DC-8 aircraft from the NASA Ames Research Center were used in this field experiment. The NASA Langley Research Center's airborne differential absorption lidar (DIAL) system was operated from the DC-8 to obtain profiles of O3 and polar stratospheric clouds in the lower stratosphere during long-range flights over Antarctica from August 28 to September 29, 1987. The airborne DIAL system was configured to transmit simultaneously four laser wavelengths (301, 311, 622, and 1064 nm) above the DC-8 for DIAL measurements of O3 profiles between 11 to 20 km ASL (geometric altitude above sea level) and multiple wavelength aerosol backscatter measurements between 11 to 24 km ASL. A total of 13 DC-8 flights were made over Antarctica with 2 flights reaching the South Pole. Polar stratospheric clouds (PSC's) were detected in multiple thin layers in the 11 to 21 km ASL altitude range with each layer having a typical thickness of less than 1 km. Two types of PSC's were found based on aerosol backscattering ratios: predominantly water ice clouds (type 2) and clouds with scattering characteristics consistent with binary solid nitric acid/water clouds (type 1). Large-scale cross sections of O3 distributions were obtained. The data provides additional information about a potentially important transport mechanism that may influence the O3 budget inside the vortex. There is also some evidence that strong low pressure systems in the troposphere are associated with regions of lower stratospheric O3. This paper discusses the spatial and temporal variations of O3 inside and outside the polar vortex region during the development of the O3 hole and relates these data to other measurements obtained during this field experiment.

  18. Effects of ozone and simulated acid rain on birch seedling growth and formation of ectomycorrhizae.

    PubMed

    Keane, K D; Manning, W J

    1988-01-01

    Four-week-old paper birch (Betula papyrifera Marsh.) seedlings, inoculated or non-inoculated with the ectomycorrhizal fungus Pisolithus tinctorius (Pers.) Coker & Couch and grown in steamed or non-steamed soil, were exposed to ozone (O(3)) and/or simulated acid rain (SAR). Plants were exposed to O(3) for 7 h per day on 5 days per week for 12 weeks. O(3) concentrations were maintained between 0.06 and 0.08 ppm. SAR was applied 10 min per day on 2 days per week. O(3), SAR, soil regime and mycorrhizal treatment did not significantly affect any of the measured variables. Interactions between O(3) and SAR, SAR and mycorrhizal treatment, soil regime and mycorrhizal treatment and ozone and soil regime had significant effects. Treatment of seedlings with pH 3.5 SAR caused increases in growth which were more apparent in birch exposed to O(3). Mucorrhizal treatment caused increased growth in non-steamed soil, while growth appeared to decrease in steamed soil. Birch seedlings grew much better in steamed soil. The implications of increased growth in steamed soil may demonstrate the importance of looking at the secondary effects of pollutants on soil-borne organisms.

  19. 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.

  20. 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 the ozone layer recovery here because of the greenhouse gases growth. On the contrary, the mechanism of the impact of the greenhouse gases on the ozone through PSC modification begins to be more effective in Arctic in comparison with the gas phase mechanism in springs after about 2020, which leads to retard the expected recovery of the

  1. Engineering photochemical smog through convection towers

    SciTech Connect

    Elliott, S.; Prueitt, M.L.; Bossert, J.E.; Mroz, E.J.; Krakowski, R.A.; Miller, R.L.; Jacobson, M.Z.; Turco, R.P. |

    1995-02-01

    Reverse convection towers have attracted attention as a medium for cleansing modern cities. Evaporation of an aqueous mist injected at the tower opening could generate electrical power by creating descent, and simultaneously scavenge unsightly and unhealthful particulates. The study offered here assesses the influence to tower water droplets on the photochemical component of Los Angeles type smog. The primary radical chain initiator OH is likely removed into aqueous phases well within the residence time of air in the tower, and then reacts away rapidly. Organics do not dissolve, but nighttime hydrolysis of N{sub 2}O{sub 5} depletes the nitrogen oxides. A lack of HOx would slow hydrocarbon oxidation and so also ozone production. Lowering of NOx would also alter ozone production rates, but the direction is uncertain. SO{sub 2} is available in sufficient quantities in some urban areas to react with stable oxidants, and if seawater were the source of the mist, the high pH would lead to fast sulfur oxidation kinetics. With an accommodation coefficient of 10{sup {minus}3}, however, ozone may not enter the aqueous phase efficiently. Even if ozone is destroyed or its production suppressed, photochemical recovery times are on the order of hours, so that tower processing must be centered on a narrow midday time window. The cost of building the number of structures necessary for this brief turnover could be prohibitive. The increase in humidity accompanying mist evaporation could be controlled with condensers, but might otherwise counteract visibility enhancements by recreating aqueous aerosols. Quantification of the divergent forcings convection towers must exert upon the cityscape would call for coupled three dimensional modeling of transport, microphysics, and photochemistry. 112 refs.

  2. Inhibition of trihalomethane formation in city water by radiation-ozone treatment and rapid composting of radiation disinfected sewage sludge

    NASA Astrophysics Data System (ADS)

    Takehisa, M.; Arai, H.; Arai, M.; Miyata, T.; Sakumoto, A.; Hashimoto, S.; Nishimura, K.; Watanabe, H.; Kawakami, W.; Kuriyama, I.

    Humic acid and Fulvic acid in natural water are precursors of carcinogenic THM which is formed during chlorine disinfection in city water processing. The radiation-oxidation process in the presence of ozone is effective to remove the precursors. The THM formation was reduced more than the decrease in TOC by the combination treatment. This is mainly due to a change in the chemical structure of the oxidation products. A composting of radiation disinfected sludge cake for agricultural reuse could be achieved within 3 days primary fermentation in a sewage plant. The rapid fermentation with use of radiation is effective to scale down of a fermentor of composting plant and the process reduces a health risk from the workers as well as final users.

  3. Product analyses of ozone mediated nitration of benzimidazole derivatives with nitrogen dioxide: formation of 1-nitrobenzimidazoles and conversion to benzotriazoles.

    PubMed

    Kaiya, Toyo; Nakamura, Kei; Tanaka, Masaru; Miyata, Naoki; Kohda, Kohfuku

    2004-05-01

    Several benzimidazole derivatives having electron-withdrawing or -donating substituent(s) at the benzene moiety were used as models of the imidazole moiety of purine bases and their nitration with nitrogen dioxide and ozone (so-called Kyodai nitration) were examined. Products were extracted from the reaction mixture with AcOEt and their structures were analyzed. 1-Nitrobenzimidazole derivatives and unexpected 1-nitrobenzotriazole derivatives were identified. Although the yields of 1-nitrobenzimidazole derivatives were quite low, these were all new compounds that could be obtained only by Kyodai nitration. It was speculated that benzotriazoles were formed via 1-nitrobenzimidazoles and subsequent nitration toward benzotriazoles resulted in the formation of 1-nitrobenzotriazoles. PMID:15133210

  4. The photochemistry of synoptic-scale ozone synthesis Implications for the global tropospheric ozone budget

    NASA Technical Reports Server (NTRS)

    Fishman, J.; Browell, E. V.; Vukovich, F. M.

    1985-01-01

    The oxidation of nonmethane hydrocarbons represents a source of tropospheric ozone that is primarily confined to the boundary layers of several highly industrialized regions. (Each region has an area greater than one million km/sq cm). Using a photochemical model, the global tropospheric ozone budget is reexamined by including the in-situ production from these localized regimes. The results from these calculations suggest that the net source due to this photochemistry, which takes place on the synoptic scale, is approximately as large as the amount calculated for global scale photochemical processes which consider only the oxidation of methane and carbon monoxide. Such a finding may have a considerable impact on our understanding of the tropospheric ozone budget. The model results for ozone show reasonable agreement with the climatological summer distribution of ozone and the oxides of nitrogen at the surface and with the vertical distribution of ozone and nonmethane hydrocarbons obtained during a 1980 field program.

  5. Sensitivity of ozone concentrations to VOC and NO x emissions in the Canadian Lower Fraser Valley

    NASA Astrophysics Data System (ADS)

    Jiang, Weimin; Singleton, Donald L.; Hedley, Mark; McLaren, Robert

    The SAPRC90 chemical mechanism module implemented in CALGRID is updated for the specific emissions and applications of the Lower Fraser Valley (LFV) of British Columbia, Canada. The kinetic and mechanistic parameters of lumped VOC reactions recalculated using the LFV emissions profiles are noticeably different from those based on default emissions profiles, indicating the importance of tailoring the parameters to specific regions. The sensitivities of ozone concentrations to total and speciated VOC and NO x emissions as well as to the NO2/NOx ratios are determined. Significant VOC model species are identified based on the impact of their emissions on ozone formation in the LFV. Of note is the importance of the emissions of a lumped class of aromatics, ARO2, which contains mostly isomers of xylene and trimethylbenzene and is derived chiefly from the use and distribution of gasoline fuels. The ARO2 emissions make the largest contribution of all model VOC species to the ozone levels in the urban plume. The results indicate that reduction of AR02 emissions alone could achieve significant reduction of ozone levels in the LFV. Base case emissions of NO x(NO or NO 2) in the LFV contribute negatively to the ozone formation. Any overestimation of NO x or underestimation of VOC in the emissions inventory could cause underestimations of ozone levels by photochemical models.

  6. On-road emission characteristics of VOCs from rural vehicles and their ozone formation potential in Beijing, China

    NASA Astrophysics Data System (ADS)

    Yao, Zhiliang; Wu, Bobo; Shen, Xianbao; Cao, Xinyue; Jiang, Xi; Ye, Yu; He, Kebin

    2015-03-01

    This paper is the second in a series of papers aimed at understanding volatile organic compound (VOC) emissions from motor vehicles in Beijing using on-board emission measurements, focusing specifically on rural vehicles (RVs). In this work, 13 RVs, including 6 different 3-wheel (3-W) RVs and 7 different 4-wheel (4-W) RVs, were examined using a portable emissions measurement system (PEMS) as the vehicles were driven on predesigned fixed test routes in rural areas of Beijing. Overall, 50 VOC species were quantified in this study, including 18 alkanes, 5 alkenes, 11 aromatics, 13 carbonyls and 3 other compounds. The average emission factor (EF) of the total VOCs for the 4-W RVs based on the distance traveled was 326.2 ± 129.3 mg/km, which is 2.5 times greater than that of the 3-W RVs. However, the VOC emissions for the 3-W RVs had higher EFs based on their CO2 emissions due to the different fuel economies of the two types of RVs. Formaldehyde, toluene, acetaldehyde, m-xylene, p-xylene, isopentane, benzene, ethylbenzene, n-pentane, 2-methoxy-2-methylpropane and butenal were the dominant VOC species from the RVs, accounting for an average of 68.6% of the total VOC emissions. Overall, the RVs had high proportions of aromatics and carbonyls. The ozone formation potentials (OFPs) were 670.6 ± 227.2 and 1454.1 ± 643.0 mg O3/km for the 3-W and 4-W RVs, respectively, and approximately 60%-70% of the OFP resulted from carbonyls. We estimated that the 3-W and 4-W RVs accounted for approximately 50% and 10%, respectively, of the total OFP caused by diesel vehicles (including diesel trucks and RVs) in Beijing in 2012. Thus, more attention should be given to VOC emissions and their impact on ozone formation.

  7. Using measured and modeled indicators to assess ozone-NO x-VOC sensitivity in a western Mediterranean coastal environment

    NASA Astrophysics Data System (ADS)

    Stein, Ariel F.; Mantilla, Enrique; Millán, Millán M.

    It is widely known that the formation of ozone (O 3) is chemically linked to the emissions of nitrogen oxides (NO x) and volatile organic compounds (VOC). This chemical interdependence is highly complex and gives rise to non-linear and coupled pollutant formation processes. In the present study, airborne measurements of sulfur dioxide (SO 2), total reactive oxides of nitrogen (NO y), and O 3 taken from an instrumented aircraft within MECAPIP-1989 project have been reexamined to asses the governing photochemical processes of ozone formation. This experiment was carried out in the Castellón urban-industrial area, located on the Mediterranean coast of the Iberian Peninsula. Noon near field (within a 25-km radius from the coast line) transects show a strong ozone titration effect downwind of the main source area. Moreover, while afternoon measurements still depict ozone consumption near the emissions area, ozone net formation is observed in the mid-field (within a 75-km radius) of the Castellón urban-industrial complex. Ozone yields have been derived from these aircraft measurements. This analysis shows that there is almost no O 3 production for the noon period. Conversely, the O 3 yield reaches a maximum downwind of the emissions complex for the afternoon hours. Furthermore, measured values for the O 3/NO y ratio have been used as photochemical indicators to determine the effectiveness of VOC or NO x controls in decreasing O 3 abundance. The concentrations of these indicator species have been calculated from a series of simulations using a lagrangian photochemical model and good agreement has been observed between modeled and measured data. The sensitivity of ozone to changes in its primary sources has been examined by simulating scenarios with varying rates of NO x and VOC emissions. The results presented here show that for this particular case the measured and modeled O 3/NO y ratios seem to identify a photochemical regime in which reductions in upwind NO x

  8. Efficient quantum-classical method for computing thermal rate constant of recombination: application to ozone formation.

    PubMed

    Ivanov, Mikhail V; Babikov, Dmitri

    2012-05-14

    Efficient method is proposed for computing thermal rate constant of recombination reaction that proceeds according to the energy transfer mechanism, when an energized molecule is formed from reactants first, and is stabilized later by collision with quencher. The mixed quantum-classical theory for the collisional energy transfer and the ro-vibrational energy flow [M. Ivanov and D. Babikov, J. Chem. Phys. 134, 144107 (2011)] is employed to treat the dynamics of molecule + quencher collision. Efficiency is achieved by sampling simultaneously (i) the thermal collision energy, (ii) the impact parameter, and (iii) the incident direction of quencher, as well as (iv) the rotational state of energized molecule. This approach is applied to calculate third-order rate constant of the recombination reaction that forms the (16)O(18)O(16)O isotopomer of ozone. Comparison of the predicted rate vs. experimental result is presented.

  9. ON THE FORMATION OF OZONE IN SOLAR SYSTEM OXYGEN ICES EXPOSED TO HEAVY IONS

    SciTech Connect

    Ennis, Courtney; Kaiser, Ralf I.

    2012-02-01

    Mimicking the bombardment of icy surfaces with heavy ions from solar system radiation fields, solid-phase molecular oxygen ({sup 32}O{sub 2}) and its isotope labeled analogue ({sup 36}O{sub 2}) were irradiated with monoenergetic carbon (C{sup +}), nitrogen (N{sup +}), and oxygen (O{sup +}) ions in laboratory experiments simulating the interaction of ions from the solar wind and those abundant in planetary magnetospheres. Online Fourier-transform infrared spectroscopy of the irradiated oxygen ices (12 K) showed that the yields of molecular ozone monomer (O{sub 3} {approx} 2 Multiplication-Sign 10{sup -3} molecules eV{sup -1} in {sup 32}O{sub 2}) were independent of the mass of the implanted C{sup +}, N{sup +}, and O{sup +} ions ({Phi}{sub max} = 4.0 Multiplication-Sign 10{sup 14} ions cm{sup -2}). The production of oxygen atoms in the solid was observed in the mid-IR stabilized via the [O{sub 3}...O] van der Waals complex. We expand on this inference by comparing the ozone yields induced by light particles (e{sup -}, H{sup +}, and He{sup +}) to the heavy ions (C{sup +}, N{sup +}, and O{sup +}) to provide compelling evidence that the abundance of radiolytic products in an oxygen-bearing solid is primarily dependent on electronic stopping regimes, which supersedes the contribution of nuclear stopping processes irrespective of the mass of the particle irradiation in the kinetic energy regime of solar wind and magnetospheric particles.

  10. Constraining ozone-precursor responsiveness using ambient measurements

    EPA Science Inventory

    This study develops probabilistic estimates of ozone (O3) sensitivities to precursoremissions by incorporating uncertainties in photochemical modeling and evaluating modelperformance based on ground-level observations of O3 and oxides of nitrogen (NOx).Uncertainties in model form...

  11. A study of aerosol optical properties during ozone pollution episodes in 2013 over Shanghai, China

    NASA Astrophysics Data System (ADS)

    Shi, Chanzhen; Wang, Shanshan; Liu, Rui; Zhou, Rui; Li, Donghui; Wang, Wenxin; Li, Zhengqiang; Cheng, Tiantao; Zhou, Bin

    2015-02-01

    Aerosol optical property is essential to the tropospheric ozone formation mechanism while it was rarely measured in ozone-rich environment for a specific study. With the retrieved products of the sun-photometer, a comparative investigation was conducted on aerosol optical depth (AOD), single scattering albedo (SSA) and size distribution during ozone-polluted episodes and clean background. Contrary to expectations, aerosol loading was found to be positively-correlated with ozone concentration: daily averaged AOD at 500 nm in ozone episodes (~ 0.78) displayed 2.4 times higher than that in clean days (~ 0.32). Large Ångström exponent (~ 1.51) along with heavy aerosol loading indicated a considerable impact of fine particles on optical extinction. The dynamic diurnal fluctuation of these parameters also implied a complex interaction between aerosols and photo-chemical reactions. The bimodal lognormal distribution pattern for aerosol size spectra exhibited in both ozone-polluted and clean days. The occurrence of maximum volume concentration (~ 0.28) in fine mode (radius < 0.6 μm) was observed at 3 p.m. (local time), when ozone was substantially generated. Pronounced scattering feature of aerosol was reproduced in high-concentration ozone environment. SSA tended to increase continuously from morning (~ 0.91 at 440 nm) to afternoon (~ 0.99), which may be associated with secondary aerosol formation. The scattering aerosol (with moderately high aerosol loading) may favor the ozone formation through increasing solar flux in boundary layer. Utilizing the micro-pulse lidar (MPL), a more developed planet boundary layer (PBL, top height ~ 1.96 km) was discovered during ozone-polluted days than clean condition (~ 1.4 km). In episodes, the maximum extinction ratio (~ 0.5 km- 1) was presented at a height of 1.2 km in the late afternoon. The humidity profile by sounding also showed the extreme value at this altitude. It suggested that optical extinction was mainly attributed to

  12. Photochemical Aging of α-pinene and β-pinene Secondary Organic Aerosol formed from Nitrate Radical Oxidation: New Insights into the Formation and Fates of Highly Oxygenated Gas- and Particle-phase Organic Nitrates

    NASA Astrophysics Data System (ADS)

    Nah, T.; Sanchez, J.; Boyd, C.; Ng, N. L.

    2015-12-01

    The nitrate radical (NO3), one of the most important oxidants in the nocturnal atmosphere, can react rapidly with a variety of biogenic volatile organic compounds (BVOCs) to form high mass concentrations of secondary organic aerosol (SOA) and organic nitrates (ON). Despite its critical importance in aerosol formation, the mechanisms and products from the NO3 oxidation of BVOCs have been largely unexplored, and the fates of their SOA and ON after formation are not well characterized. In this work, we studied the formation of SOA and ON from the NO3 oxidation of α-pinene and β-pinene and investigated for the first time how they evolve during dark and photochemical aging through a series of chamber experiments performed at the Georgia Tech Environmental Chamber (GTEC) facility. The α-pinene and β-pinene SOA are characterized using real-time gas- and particle-phase measurements, which are used to propose mechanisms for SOA and organic nitrate formation and aging. Highly oxygenated gas- and particle-phase ON (containing as many as 9 oxygen atoms) are detected during the NO3 reaction. In addition, the β-pinene SOA and α-pinene SOA exhibited drastically different behavior during photochemical aging. Our results indicate that nighttime ON formed by NO3+monoterpene chemistry can serve as either NOx reservoirs or sinks depending on the monoterpene precursor. Results from this study provide fundamental data for evaluating the contributions of NO3+monoterpene reactions to ambient OA measured in the Southeastern U.S.

  13. How Tropospheric is Tropospheric Ozone?

    NASA Astrophysics Data System (ADS)

    Trickl, Thomas; Scheel, Hans-Eckhart; Sprenger, Michael; Vogelmann, Hannes

    2010-05-01

    There has been a long debate on the reasons of the increase in tropospheric ozone during the past century. Mostly the photochemical ozone formation combined with the growing level of air pollution has been stressed. However, with decreasing European precursor emissions in the 1990s and the ongoing positive trend of O3 at the high-lying Alpine station Zugspitze (2962 m a.s.l.) until about 2000 this view has started to change. Data filtering of the Zugspitze data based on relative humidity (RH), 7Be and CO measurements have revealed that the only positive ozone trend could be found for descending air masses of dominating stratospheric origin whereas the trend for polluted air masses is around zero. The 7Be data, recorded since 1970, showed a positive trend since the mid-seventies. Based on daily model forecasts by ETH of stratospheric air intrusions co-ordinated lidar measurements of ozone and, more recently, water vapour (Vogelmann and Trickl, 2008) have been carried out. It could be shown that there is an excellent agreement between the intrusion forecasts, the lidar measurements and low-RH events at the Zugspitze summit (Trickl et al., 2010). The forecasts also allowed us to define intrusion types as well as to review and to revise the data-filtering criteria used for the in-situ data. This study, carried out for the period 2001-2005, yields a significantly higher number of intrusions reaching 3000 m than obtained in previous investigations, with even about 20 per cent more cases (mostly overpasses) predicted by the forecasts. Seasonal cycles of the intrusion frequency were derived and, in all but one intrusion type, peaked during the cold season. Recent measurements with the water-vapour lidar (see parallel contribution) have revealed RH values of 0-2 per cent even in very thin layers of stratospheric origin reaching the lower troposphere. This indicates that significant mixing with tropospheric air can only occur during the early phase of an intrusion, if not

  14. On the temporal and spatial variation of ozone in Cyprus.

    PubMed

    Kleanthous, Savvas; Vrekoussis, Mihalis; Mihalopoulos, Nikolaos; Kalabokas, Pavlos; Lelieveld, Jos

    2014-04-01

    More than sixteen years (1997-2013) of continuous ozone concentrations at the rural Agia Marina (EMEP, 532 ma.s.l.) station in Cyprus, together with a number of ancillary chemical and meteorological parameters have been analyzed on a multiannual, annual and diurnal basis. The observations reveal a) the presence of a prominent seasonality with maxima observed during summer (54±5 ppbv) and the minima in winter (39±3 ppbv) b) a relatively small diurnal variability with the noon levels (50±9 ppbv) being higher by ~4 pbbv compared to nighttime (46±9 ppbv) and c) a non-significant upward trend over the 16 years of 0.11±0.12 ppbv y(-1). To assess the spatial variability over Cyprus, simultaneous measurements in 2011-2012 have been performed at Inia, Stavrovouni and Cavo Greco, three remote marine monitoring sites located to the west, central and the east of the Island, respectively. Our results show that ambient ozone levels over Cyprus are mostly influenced by regional/transported ozone while the local precursor emissions play a minor role in ozone formation. On an annual basis a net ozone reduction of 1.5 and 1.0 ppbv occurs when the air masses originate from northerly and westerly directions, respectively, while this is 2.4 ppbv during southerly wind. This suggests continuous net ozone loss controlled by surface deposition and photochemical destruction, and highlights the importance of long-range transport in controlling ozone levels in Cyprus. PMID:24508856

  15. Assessing spatial occurrence of ground level ozone around coal mining areas of Chandrapur District, Maharashtra, India.

    PubMed

    Salve, Pradeep R; Satapathy, Deepty Ranjan; Katpatal, Yashwant B; Wate, Satish R

    2007-10-01

    Stratospheric input and photochemical ozone formation in the troposphere are the two main sources determining the ozone levels in the surface layer of the atmosphere. Because of the importance of ozone in controlling the atmospheric chemistry and its decisive role in the heat balance of atmosphere, leading to climate change, the examination of its formation and destruction are of great interest. This study characterized the distribution of Ground level Ozone (GLO) in Chandrapur district is lying between 19 degrees 25'N to 20 degrees 45'N and 78 degrees 50'E to 80 degrees 10'E. Continuous ozone analyzer was used to quantify GLO at thirteen locations fixed by Global Positioning System (GPS) during the winter of 2005-2006. The daily GLO at all the locations ranged between 6.4 and 24.8 ppbv with an average and standard deviation of 14.9 +/- 6.5 ppbv. The maximum and minimum concentration occurs during 1300-1600 h and 0300-0500 h may be due to high solar radiation facilitating photochemical production of O(3) and downward mixing from the overlying air mass and in situ destruction of ozone by deposition and/or the reaction between O(3) and NO. GIS based spatial distribution of GLO in Chandrapur district is indicates that the central core of the district and southern sites experienced elevated levels of GLO relative to the northern and western areas. The sites near by Chandrapur city are particularly affected by elevated GLO. The average variation of GLO with temperature shows a significant correlation of r = 0.55 indicating a direct relationship between GLO and temperature. Similarly an attempt has been made to compare the GLO monitored data in Chandrapur district with the reported values for other locations in Indian cities. This generated database helps regulatory agencies to identify locations where the natural resources and human health could be at risk.

  16. Airborne measurements of tropospheric ozone destruction and particulate bromide formation in the Arctic

    NASA Technical Reports Server (NTRS)

    Schnell, Russell C.; Sheridan, Patrick J.; Peterson, Richard E.; Oltmans, S. J.

    1988-01-01

    Aircraft profiles of O3 concentrations over the Arctic ice pack in spring exhibit a depletion of O3 beneath the surface temperature inversion. One such profile from the NOAA WP-3D Arctic Gas and Aerosol Sampling Program (AGASP) flights in April, 1986 north of Alert, NWT (YLT, 82.5 N) is shown. The gradient of O3 across the temperature inversion, which is essentially a step function from tropospheric values (35 to 40 ppbv) to 0, is somewhat masked by a 1-min running mean applied to the data. Evidence is presented that O3 destruction beneath the Arctic temperature inversion is the result of a photochemical reaction between gaseous Br compounds and O3 to produce particulate Br aerosol. It is noted that in springtime, O3 at the Alert Baseline Station regularly decreases from 30 to 40 ppbv to near 0 over the period of a few hours to a day. At the same time, there is a production of particulate Br with a near 1.0 anti-correlation to O3 concentration. Surface concentrations of bromoform in the Arctic exhibit a rapid decrease following polar sunrise. AGASP aircraft measurements of filterable bromine particulates in the Arctic (March-April, 1983 and 1986) are shown. The greatest concentrations of Br aerosol (shown as enrichment factors relative to to Na in seawater, EFBR (Na)) were observed in samples collected beneath the surface temperature inversion over ice. Samples collected at the same altitude over open ocean (off Spitzbergen) labeled Marine did not exhibit similar Br enrichments. A second region of particulate Br enrichment was observed in the lower stratosphere, which regularly descends to below 500 mb (5.5 km) in the high Arctic. The NOAA WP-3D flew in the stratosphere on all AGASP flights and occasionally measured O3 concentrations in excess of 300 ppbv.

  17. Photodegradation of antibiotics on soil surfaces: laboratory studies on sulfadiazine in an ozone-controlled environment.

    PubMed

    Wolters, André; Steffens, Markus

    2005-08-15

    Among the processes affecting transport and degradation of antibiotics released to the environment during application of manure and slurry to agricultural land, photochemical transformations are of particular interest. Drying-out of the top soil layer under field conditions enables sorption of surface-applied antibiotics to soil dust, thus facilitating direct, indirect, and sensitized photodegradation at the soil/atmosphere interface. For studying various photochemical transformation processes of sulfadiazine, a photovolatility chamber designed in accordance with the requirements of the USEPA Guideline and 161-3 was used. Application of 14C-labeled sulfadiazine enabled complete mass balances and allowed for investigating the impact of various surfaces (glass and soil dust) and environmental factors, i.e., irradiation and atmospheric ozone, on photodegradation and volatilization. Volatilization was shown to be a negligible process. Even after increasing the air temperature up to 35 degrees C only minor amounts of sulfadiazine and transformation products (0.01-0.28% of applied radioactivity) volatilized. Due to direct and indirect photodegradation, the highest extent of mineralization to 14CO2 (3.9%), the formation of degradation products and of nonextractable soil residues was measured in irradiated soil dust experiments using ozone concentrations of 200 ppb. However, even in the dark significant mineralization was observed when ozone was present, indicating ozone-controlled transformation of sulfadiazine to occur at the soil surface.

  18. Comparison of formation of disinfection by-products by chlorination and ozonation of wastewater effluents and their toxicity to Daphnia magna.

    PubMed

    Park, Keun-Young; Choi, Su-Young; Lee, Seung-Hoon; Kweon, Ji-Hyang; Song, Ji-Hyeon

    2016-08-01

    This study compared the two most frequently used disinfectants (i.e., chlorine and ozone) to understand their efficiency in wastewater effluents and the ecotoxicity of disinfection by-products created during chlorination and ozonation. Four trihalomethanes (THMs) and nine haloacetic acids (HAAs) were measured from a chlorine-disinfected sample and two aldehydes (i.e., formaldehydes and acetaldehydes) were analyzed after ozonation. Chlorination was effective for total coliform removal with Ct value in the range of 30-60 mg-min/L. Over 1.6 mg/L of ozone dose and 0.5 min of the contact time presented sufficient disinfection efficiency. The concentration of THMs increased with longer contact time (24 h), but that of HAAs showed little change with contact time. The measured concentration of formaldehyde at the ozone dose of 1.6 mg/L and the contact time of 9 min showed the greatest value in this study, approximately 330 μg L(-1), from which the corresponding ecotoxicity was determined using an indicator species, Daphnia magna. The ecotoxicity results were consistent with the toxicological features judged by occurrence, genotoxicity, and carcinogenicity. Both the disinfection efficiency as well as the DBP formation potential should therefore be considered to avoid harmful impacts on aquatic environments when a disinfection method is used for wastewater effluents. PMID:27213572

  19. Effect of photochemical models on calculated equilibria and cooling rates in the stratosphere

    NASA Technical Reports Server (NTRS)

    Blake, D.; Lindzen, R. S.

    1973-01-01

    The determination of the relaxation time of a temperature perturbation in the stratosphere must take into account the effects of the absorption of solar energy by ozone, while the ozone density itself is dependent on temperature. A photochemical model, consisting of continuity equations for each of 29 constituents with reaction rates and adjustment times, is used to obtain the vertical distribution of ozone. The altitude range from 35 to 60 km in non-Arctic regions is shown to be in approximate joint radiative-photochemical equilibrium. The temperature and ozone distributions are thus well buffered. Modest changes in ozone and temperature were calculated on the basis of this model from large changes in cooling rates and reaction rates, and the results are shown to be more in line with actual observations. The importance of estimating the mixing ratios for NO and H2O is emphasized.

  20. Photochemical tissue bonding

    DOEpatents

    Redmond, Robert W.; Kochevar, Irene E.

    2012-01-10

    Photochemical tissue bonding methods include the application of a photosensitizer to a tissue and/or tissue graft, followed by irradiation with electromagnetic energy to produce a tissue seal. The methods are useful for tissue adhesion, such as in wound closure, tissue grafting, skin grafting, musculoskeletal tissue repair, ligament or tendon repair and corneal repair.

  1. Effects of Relative Humidity on Ozone and Secondary Organic Aerosol Formation from the Photooxidation of Benzene and Ethylbenzene

    NASA Astrophysics Data System (ADS)

    Jia, L.; Xu, Y.

    2012-12-01

    The formation of ozone and secondary organic aerosol from benzene-NOx and ethylbenzene-NOx irradiations was investigated under different levels of relative humidity (RH) in a smog chamber. The results show that the increase in RH can greatly reduce the maximum O3 by the transformation of -NO2 and -ONO2-containing products into the particle phase. In benzene irradiations, the SOA number concentration increases over 26 times as RH rises from <5% to 80%, and the intensity of the bands of -OH, -C=O and C-OH from SOA samples also greatly increases with RH. In ethylbenzene irradiations, ethylglyoxal favors the formation of monohydrate, which limits the RH effects. During evaporating processes, the lost substances have similar structures for both benzene and ethylbenzene. This demonstrates that ethyl-containing substances are very stable and difficult to evaporate. For benzene some of glyoxal hydrates are left to form C-O-C and C=O-containing species like hemiacetal and acetal after evaporation, whereas for ethylbenzene, glyoxal favors cross reactions with ethylglyoxal during the evaporating process. It is concluded that the increase in RH can irreversibly enhance the yields of SOA from both benzene and ethylbenzene.

  2. Trends in total column ozone measurements

    NASA Technical Reports Server (NTRS)

    Rowland, F. S.; Angell, J.; Attmannspacher, W.; Bloomfield, P.; Bojkov, R. D.; Harris, N.; Komhyr, W.; Mcfarland, M.; Mcpeters, R.; Stolarski, R. S.

    1989-01-01

    It is important to ensure the best available data are used in any determination of possible trends in total ozone in order to have the most accurate estimates of any trends and the associated uncertainties. Accordingly, the existing total ozone records were examined in considerable detail. Once the best data set has been produced, the statistical analysis must examine the data for any effects that might indicate changes in the behavior of global total ozone. The changes at any individual measuring station could be local in nature, and herein, particular attention was paid to the seasonal and latitudinal variations of total ozone, because two dimensional photochemical models indicate that any changes in total ozone would be most pronounced at high latitudes during the winter months. The conclusions derived from this detailed examination of available total ozone can be split into two categories, one concerning the quality and the other the statistical analysis of the total ozone record.

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

    ERIC Educational Resources Information Center

    Christidou, Vasilia; Koulaidis, Vasilis

    1996-01-01

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

  4. Photochemical production of molecular bromine in Arctic surface snowpacks

    NASA Astrophysics Data System (ADS)

    Pratt, Kerri A.; Custard, Kyle D.; Shepson, Paul B.; Douglas, Thomas A.; Pöhler, Denis; Stephan, General; Zielcke, Johannes; Simpson, William R.; Platt, Ulrich; Tanner, David J.; Gregory Huey, L.; Carlsen, Mark; Stirm, Brian H.

    2013-05-01

    Following the springtime polar sunrise, ozone concentrations in the lower troposphere episodically decline to near-zero levels. These ozone depletion events are initiated by an increase in reactive bromine levels in the atmosphere. Under these conditions, the oxidative capacity of the Arctic troposphere is altered, leading to the removal of numerous transported trace gas pollutants, including mercury. However, the sources and mechanisms leading to increased atmospheric reactive bromine levels have remained uncertain, limiting simulations of Arctic atmospheric chemistry with the rapidly transforming sea-ice landscape. Here, we examine the potential for molecular bromine production in various samples of saline snow and sea ice, in the presence and absence of sunlight and ozone, in an outdoor snow chamber in Alaska. Molecular bromine was detected only on exposure of surface snow (collected above tundra and first-year sea ice) to sunlight. This suggests that the oxidation of bromide is facilitated by a photochemical mechanism, which was most efficient for more acidic samples characterized by enhanced bromide to chloride ratios. Molecular bromine concentrations increased significantly when the snow was exposed to ozone, consistent with an interstitial air amplification mechanism. Aircraft-based observations confirm that bromine oxide levels were enhanced near the snow surface. We suggest that the photochemical production of molecular bromine in surface snow serves as a major source of reactive bromine, which leads to the episodic depletion of tropospheric ozone in the Arctic springtime.

  5. A Process-Analysis Based Study of the Ozone Weekend Effect

    SciTech Connect

    Tonse, Shaheen R.; Brown, Nancy J.; Harley, Robert A.; Jin, Ling

    2008-05-09

    We have used the 3D photochemical model CMAQ to simulate the ozone weekend effect, a phenomenon in which urban areas can have higher ozone concentrations on weekends than on weekdays even though NO{sub x} emissions are usually lower on weekends. A simulation containing a weekend is compared to hypothetical simulations in which the anthropogenic emissions for the weekend have been replaced by weekday emissions. The simulations are identical in all other respects. Process analysis is used to explain the results. We find that the weekend effect can be decomposed into an ozone titration component and an odd oxygen component, each contributing about half of the excess weekend ozone. The titration component simply requires that there be lower weekend NO{sub x} emissions. The odd oxygen component additionally requires that on weekends there be a higher rate of OH + (VOC or CO) reactions, brought about by one or more of lower nitric acid formation, higher OH formation from O{sub 3} photolysis, and higher VOC emissions. This causes higher weekend peroxy radical formation. The odd oxygen component also requires sufficiently high NO concentration even on the lower-NO{sub x} weekends to propagate this higher rate of peroxy formation back to higher weekend OH formation.

  6. Introductory study of the chemical behavior of jet emissions in photochemical smog. [computerized simulation

    NASA Technical Reports Server (NTRS)

    Whitten, G. Z.; Hogo, H.

    1976-01-01

    Jet aircraft emissions data from the literature were used as initial conditions for a series of computer simulations of photochemical smog formation in static air. The chemical kinetics mechanism used in these simulations was an updated version which contains certain parameters designed to account for hydrocarbon reactivity. These parameters were varied to simulate the reaction rate constants and average carbon numbers associated with the jet emissions. The roles of surface effects, variable light sources, NO/NO2 ratio, continuous emissions, and untested mechanistic parameters were also assessed. The results of these calculations indicate that the present jet emissions are capable of producing oxidant by themselves. The hydrocarbon/nitrous oxides ratio of present jet aircraft emissions is much higher than that of automobiles. These two ratios appear to bracket the hydrocarbon/nitrous oxides ratio that maximizes ozone production. Hence an enhanced effect is seen in the simulation when jet exhaust emissions are mixed with automobile emissions.

  7. Methods for the photochemical utilization of solar energy

    NASA Technical Reports Server (NTRS)

    Schwerzel, R. E.

    1978-01-01

    The paper considers the 'ground rules' which govern the efficiency of photochemical solar energy conversion and then summarizes the most promising approaches in each of three categories: photochemically assisted thermal systems for the heating and/or cooling of structures; photogalvanic systems for the production of electrical power in applications, such as photorechargeable batteries or inexpensive 'solar cells'; and photochemical formation of fuels for combustion and for use as chemical feedstocks or foods. Three concepts for the photochemical utilization of solar energy in space are found to be particularly promising: (1) photochemical trans-cis isomerization of indigold dyes for photoassisted heating or cooling, (2) the redox stabilized photoelectrolysis cell for the production of hydrogen (and/or oxygen or other useful chemicals), and (3) the liquid-junction photovoltaic cell for the production of electrical power.

  8. Trace Tropospheric Species Sensing-Fabry-Perot Interferometer (TTSS-FPI): spaceborne sensor concept studies for measuring tropospheric ozone

    NASA Astrophysics Data System (ADS)

    Puschell, Jeffery J.; Hastings, C. T.; Chrien, Thomas; Larar, Allen M.; Cook, William B.; Mills, Carl S.; Flood, Michael A.; Skinner, Wilbert R.

    2005-01-01

    We present results of studies of instrument concepts for a spaceborne imaging Fabry-Perot interferometer to measure tropospheric ozone. Ozone is recognized as one of the most important trace constituents of the troposphere. Tropospheric ozone is responsible for acute and chronic human health problems and contributes toward destruction of plant and animal populations. Furthermore, it is a greenhouse gas and contributes toward radiative forcing and climate change. Tropospheric ozone levels have been increasing and will continue to do so as concentrations of precursor gases (oxides of nitrogen, methane, and other hydrocarbons) necessary for the photochemical formation of tropospheric ozone continue to rise. Space-based detection and monitoring of tropospheric ozone is critical for enhancing scientific understanding of creation and transport of this important trace gas and for providing data needed to help develop strategies for mitigating impacts of exposure to elevated concentrations of tropospheric ozone. Measurement concept details are discussed in a companion paper by Larar et al. Development of an airborne prototype instrument for this application is discussed by Cook et al. in another companion paper.

  9. Emissions of organic trace gases from savanna fires in southern Africa during the 1992 Southern African Fire Atmosphere Research Initiative and their impact on the formation of tropospheric ozone

    NASA Astrophysics Data System (ADS)

    Koppmann, R.; Khedim, A.; Rudolph, J.; Poppe, D.; Andreae, M. O.; Helas, G.; Welling, M.; Zenker, T.

    1997-08-01

    CO, CH4, and organic trace gases were measured in air samples collected during several flights with a DC-3 aircraft through the plumes from savanna fires and agricultural fires during the SAFARI 92 campaign in southern Africa in September and October 1992. In all samples a variety of higher molecular weight organic compounds was found, most of which are very reactive. More than 70 of the roughly 140 major components present could be identified. Typically, mixing ratios of several hundred parts per billion carbon of organic compounds were measured inside the plumes, corresponding to an emission ratio of total organic carbon relative to CO2 of up to 1%. About 50% of these emissions were in the form of oxygenated and unsaturated compounds. The contributions of still unknown compounds to the total emission of organic compounds add up to another 20-30%. The observed emission ratios relative to CO2 show a considerable variation depending on the fuel type and the burning stages of the fire. The lowest value of the emission ratio of the sum of all identified organic compounds relative to CO2 was found for a sugar cane fire with (1.7±0.7)×10-3 (ppb C/ppb CO2). For a large savanna fire in Kruger National Park the ratio was (7.4±1.6)×10-3 (ppb C/ppb CO2). The highest value was (13.7±0.9)×10-3 (ppb C/ppb CO2) for an uncontrolled fire of mainly wood and shrub in the Drakensberg region. Results of model calculations show that in biomass-burning plumes, reactive organic compounds contribute significantly to the formation of ozone, especially during the initial phase of photochemical processing.

  10. Photochemical isotope separation

    DOEpatents

    Robinson, C. Paul; Jensen, Reed J.; Cotter, Theodore P.; Greiner, Norman R.; Boyer, Keith

    1987-01-01

    A process for separating isotopes by selective excitation of isotopic species of a volatile compound by tuned laser light. A highly cooled gas of the volatile compound is produced in which the isotopic shift is sharpened and defined. Before substantial condensation occurs, the cooled gas is irradiated with laser light precisely tuned to a desired wavelength to selectively excite a particular isotopic species in the cooled gas. The laser light may impart sufficient energy to the excited species to cause it to undergo photochemical reaction or even to photoionize. Alternatively, a two-photon irradiation may be applied to the cooled gas to induce photochemical reaction or photoionization. The process is particularly applicable to the separation of isotopes of uranium and plutonium.

  11. Photochemical isotope separation

    DOEpatents

    Robinson, C.P.; Jensen, R.J.; Cotter, T.P.; Greiner, N.R.; Boyer, K.

    1987-04-28

    A process is described for separating isotopes by selective excitation of isotopic species of a volatile compound by tuned laser light. A highly cooled gas of the volatile compound is produced in which the isotopic shift is sharpened and defined. Before substantial condensation occurs, the cooled gas is irradiated with laser light precisely tuned to a desired wavelength to selectively excite a particular isotopic species in the cooled gas. The laser light may impart sufficient energy to the excited species to cause it to undergo photochemical reaction or even to photoionize. Alternatively, a two-photon irradiation may be applied to the cooled gas to induce photochemical reaction or photoionization. The process is particularly applicable to the separation of isotopes of uranium and plutonium. 8 figs.

  12. Materials Integrating Photochemical Upconversion.

    PubMed

    McCusker, Catherine E; Castellano, Felix N

    2016-04-01

    This review features recent experimental work focused on the preparation and characterization of materials that integrate photochemical upconversion derived from sensitized triplet-triplet annihilation, resulting in the conversion of low energy photons to higher energy light, thereby enabling numerous wavelength-shifting applications. Recent topical developments in upconversion include encapsulating or rigidifying fluid solutions to give them mechanical strength, adapting inert host materials to enable upconversion, and using photoactive materials that incorporate the sensitizer and/or the acceptor. The driving force behind translating photochemical upconversion from solution into hard and soft materials is the incorporation of upconversion into devices and other applications. At present, some of the most promising applications of upconversion materials include imaging and fluorescence microscopy, photoelectrochemical devices, water disinfection, and solar cell enhancement.

  13. Materials Integrating Photochemical Upconversion.

    PubMed

    McCusker, Catherine E; Castellano, Felix N

    2016-04-01

    This review features recent experimental work focused on the preparation and characterization of materials that integrate photochemical upconversion derived from sensitized triplet-triplet annihilation, resulting in the conversion of low energy photons to higher energy light, thereby enabling numerous wavelength-shifting applications. Recent topical developments in upconversion include encapsulating or rigidifying fluid solutions to give them mechanical strength, adapting inert host materials to enable upconversion, and using photoactive materials that incorporate the sensitizer and/or the acceptor. The driving force behind translating photochemical upconversion from solution into hard and soft materials is the incorporation of upconversion into devices and other applications. At present, some of the most promising applications of upconversion materials include imaging and fluorescence microscopy, photoelectrochemical devices, water disinfection, and solar cell enhancement. PMID:27573144

  14. Numerical photochemical modeling over Madrid (Spain) mesoscale urban area

    NASA Astrophysics Data System (ADS)

    San Jose, Roberto; Ramirez-Montesinos, Arturo; Marcelo, Luis M.; Sanz, Miguel A.; Rodriguez, Luis M.

    1995-09-01

    Photochemical air quality models provide the most defensible method for relating future air quality to changes in emission, and hence are the foundation for determining the effectiveness of proposed control strategies. In this contribution, we will show results from different photochemical schemes under typical emission conditions for a summer day in the Madrid mesocsale urban area. We will show that complex numerical integrated urban mesoscale models are a powerful tool to predict the ozone levels on this area. The comparison of model simulations at different grid points show an acceptable preliminary behavior. The results presented in this paper are prepared for August 15th, 1991 and the predicted ozone values are compared with those measured at two stations of the Madrid city monitoring network. Results show that the shape is successfully predicted by using the NUFOMO (numerical photochemical model) model. Because of the computer limitations, we have limited the results to this case study. Further investigations will provide additional information to produce a statistical analysis of the results. However, preliminary results show that the NUFOMO model is able to reproduce the measured ozone values.

  15. Chlorophyll fluorescence quenching during ozone exposure of leaves of Phaseolus vulgaris (pinto)

    SciTech Connect

    Guralnick, L.J. ); Miller, R.; Heath, R.L. )

    1990-05-01

    During ozone exposure, observations have noted an initial decrease in CO{sub 2} uptake followed by a decrease in stomatal conductance. We examined this response utilizing the technique of fluorescence quenching. Fourteen day old plants were exposed to 0.3 ul/l ozone for 1 hour. Fluorescence quenching was monitored using the Hanstech modulated fluorescence system. This enabled us to measure changes in photochemical quenching (qQ) and non-photochemical quenching (qE) in control and ozone treated plants. Results have indicated no differences in qQ and qE between ozone treated and control plants. We are initiating further studies utilizing different ozone levels.

  16. Secondary organic aerosol formation by limonene ozonolysis: Parameterizing multi-generational chemistry in ozone- and residence time-limited indoor environments

    NASA Astrophysics Data System (ADS)

    Waring, Michael S.

    2016-11-01

    Terpene ozonolysis reactions can be a strong source of secondary organic aerosol (SOA) indoors. SOA formation can be parameterized and predicted using the aerosol mass fraction (AMF), also known as the SOA yield, which quantifies the mass ratio of generated SOA to oxidized terpene. Limonene is a monoterpene that is at sufficient concentrations such that it reacts meaningfully with ozone indoors. It has two unsaturated bonds, and the magnitude of the limonene ozonolysis AMF varies by a factor of ∼4 depending on whether one or both of its unsaturated bonds are ozonated, which depends on whether ozone is in excess compared to limonene as well as the available time for reactions indoors. Hence, this study developed a framework to predict the limonene AMF as a function of the ozone [O3] and limonene [lim] concentrations and the air exchange rate (AER, h-1), which is the inverse of the residence time. Empirical AMF data were used to calculate a mixing coefficient, β, that would yield a 'resultant AMF' as the combination of the AMFs due to ozonolysis of one or both of limonene's unsaturated bonds, within the volatility basis set (VBS) organic aerosol framework. Then, β was regressed against predictors of log10([O3]/[lim]) and AER (R2 = 0.74). The β increased as the log10([O3]/[lim]) increased and as AER decreased, having the physical meaning of driving the resultant AMF to the upper AMF condition when both unsaturated bonds of limonene are ozonated. Modeling demonstrates that using the correct resultant AMF to simulate SOA formation owing to limonene ozonolysis is crucial for accurate indoor prediction.

  17. A model study of atmospheric temperatures and the concentrations of ozone, hydroxyl, and some other photochemically active gases during the glacial, the pre-industrial holocene and the present

    NASA Astrophysics Data System (ADS)

    Crutzen, Paul J.; Bruehl, Christoph

    1993-06-01

    Analysis of air trapped in ice cores shows that the atmospheric contents of the greenhouse gases CO2, CH4 and N2O have increased from the glacial to the preindustrial holocene. Further increases have been occurring during the industrial era, which may have contributed to the observed global warming. In addition, CH4 and N2O play large roles in ozone and hydroxyl chemistry. Here we present a model analysis of the changes in atmospheric temperatures and the concentration of O3, OH and related gases between the three epochs. Despite large changes in the atmospheric contents of CO2, CH4 and N2O, total ozone and tropospheric OH hardly changed between the glacial and preindustrial holocene. The global annual atmospheric CH4 sink increased from 90 to 210 Tg between the glacial and preindustrial, and since then to 510 Tg, largely following the changes in atmospheric concentrations. Our results indicate less than half as much CH4 production from tropical wetlands during the ice age than during the holocene.

  18. Peroxy radical observations over West Africa during the AMMA 2006 campaign: Photochemical activity in episodes of formation of convective systems on the basis of radical measurements

    NASA Astrophysics Data System (ADS)

    Andrés-Hernández, M. D.; Kartal, D.; Reichert, L.; Burrows, J. P.; Meyer Arnek, J.; Lichtenstern, M.; Stock, P.; Schlager, H.

    2009-01-01

    Peroxy radical measurements made on board the DLR-Falcon research aircraft over West Africa within the African Monsoon Multidisciplinary Analysis (AMMA) campaign during the 2006 wet monsoon are presented in this study. The analysis of data focuses on the photochemical activity of air masses sampled during episodes of intense convection and biomass burning. Generally, the total sum of peroxy radical mixing ratios, measured in the outflow of convective clouds, are quite variable but occasionally are coupled with the NO variations indicating the coexistence, or simultaneously emission of NOx, with a potential radical precursor (i.e., formaldehyde, acetone or peroxides) which has likely been transported to higher atmospheric layers. Based on the measurements, significant O3 production rates up to 2 ppb/h in the MCS outflow are estimated by using a box model with simplified chemistry. Peroxy radicals having mixing ratios around 20-25 pptv and with peak values of up to 60-70 pptv are measured within biomass burning plumes, detected at the coast in Ghana. Calculations of back-trajectory densities confirm the origin of these air masses being a biomass burning region at southern latitudes and close to the Gulf of Guinea, according to satellite pictures. Measured peroxy radical concentrations agree reasonably with modelled estimations taking into account simple local chemistry. Moreover the vertical profiles taken at the aircraft base in Ouagadougou, Burkina Faso, indicate the common feature of having maximum concentrations between 2 and 4 km, in agreement with other literature values obtained under similar conditions.

  19. Ozone and cardiovascular injury.

    PubMed

    Srebot, Vera; Gianicolo, Emilio A L; Rainaldi, Giuseppe; Trivella, Maria Giovanna; Sicari, Rosa

    2009-06-24

    evidence comes from studies of ambient particles concentrations. However, in Europe and elsewhere, the air pollution profile has gradually changed toward a more pronounced photochemical component. Ozone is one of the most toxic components of the photochemical air pollution mixture. Indeed, the biological basis for these observations has not been elucidated. In the present review, the role of ozone as chemical molecule will be firstly considered. Secondly, pathogenetic mechanisms connecting the atmospheric ozone level and cardiovascular pathology will be examined. Thirdly, the literature relating hospitalization frequency, morbidity and mortality due to cardiovascular causes and ozone concentration will be studied. The correlation between ozone level and occurrence of acute myocardial infarction will be eventually discussed.

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

    PubMed

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

    2004-02-01

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

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

    PubMed

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

    2004-02-01

    Metrics associated with ozone (O3) formation are investigated using the California Institute of Technology (CIT) three-dimensional air-quality model. Variables investigated include the O3 production rate (P(O3)), O3 production efficiency (OPE), and total reactivity (the sum of the reactivity of carbon monoxide (CO) and all organic gases that react with the hydroxyl radical). Calculations are spatially and temporally resolved; surface-level and vertically averaged results are shown for September 9, 1993 for three Southern California locations: Central Los Angeles, Azusa, and Riverside. Predictions indicate increasing surface-level O3 concentrations with distance downwind, in line with observations. Surface-level and vertically averaged P(O3) values peak during midday and are highest downwind; surface P(O3) values are greater than vertically averaged values. Surface OPEs generally are highest downwind and peak during midday in downwind locations. In contrast, peaks occur in early morning and late afternoon in the vertically averaged case. Vertically averaged OPEs tend to be greater than those for the surface. Total reactivities are highest in upwind surface locations and peak during rush hours; vertically averaged reactivities are smaller and tend to be more uniform temporally and spatially. Total reactivity has large contributions from CO, alkanes, alkenes, aldehydes, unsubstituted monoaromatics, and secondary organics. Calculations using estimated emissions for 2010 result in decreases in P(O3) values and reactivities but increases in OPEs. PMID:14968859

  2. Source profiles and ozone formation potentials of volatile organic compounds in three traffic tunnels in Kaohsiung, Taiwan.

    PubMed

    Chen, K S; Lai, C H; Ho, Y T

    2003-01-01

    Twenty-five volatile organic compounds (VOCs) up to C10 were measured using Carbotrap multibed thermal adsorption tubes during the morning and afternoon rush hours on four different days in all three traffic tunnels in Kaohsiung, Taiwan. A gas chromatograph (GC) equipped with a flame-ionization detector (FID) was then used to analyze the VOCs. The analytical results show that VOC concentrations increase with traffic flow rate, and emission profiles in the three tunnels are mostly in the range C2-C6. In addition to the traffic conditions and vehicle type, the pattern of emissions in each tunnel was also influenced by other factors, such as vehicle age, nearby pollution sources, and the spatial or temporal variation of VOCs in the urban atmosphere. The ozone formation potential (OFP) in each tunnel was assessed based on the maximum incremental reactivities of the organic species, demonstrating that OFP increases with traffic flow rate. Vehicle distribution influences the contributions of organic group to OFP in a tunnel. Meanwhile, when ranked in descending order of contribution to OFP in all tunnels, the organic groups followed the sequence olefins, aromatics, and paraffins.

  3. Numerical study on the impacts of heterogeneous reactions on ozone formation in the Beijing urban area

    NASA Astrophysics Data System (ADS)

    Xu, Jun; Zhang, Yuanhang; Wang, Wei

    2006-12-01

    The air quality model CMAQ-MADRID (Community Multiscale Air Quality-Model of Aerosol Dynamics, Reaction, Ionization and Dissolution) was employed to simulate summer O3 formation in Beijing China, in order to explore the impacts of four heterogeneous reactions on O3 formation in an urban area. The results showed that the impacts were obvious and exhibited the characteristics of a typical response of a VOC-limited regime in the urban area. For the four heterogeneous reactions considered, the NO2 and HO2 heterogeneous reactions have the most severe impacts on O3 formation. During the O3 formation period, the NO2 heterogeneous reaction increased new radical creation by 30%, raising the atmospheric activity as more NO→NO2 conversion occurred, thus causing the O3 to rise. The increase of O3 peak concentration reached a maximum value of 67 ppb in the urban area. In the morning hours, high NO titration reduced the effect of the photolysis of HONO, which was produced heterogeneously at night in the surface layer. The NO2 heterogeneous reaction in the daytime is likely one of the major reasons causing the O3 increase in the Beijing urban area. The HO2 heterogeneous reaction accelerated radical termination, resulting in a decrease of the radical concentration by 44% at the most. O3 peak concentration decreased by a maximum amount of 24 ppb in the urban area. The simulation results were improved when the heterogeneous reactions were included, with the O3 and HONO model results close to the observations.

  4. Measured and modeled HOCl profiles in the mid-latitude stratosphere : implication for ozone loss

    NASA Technical Reports Server (NTRS)

    Kovalenko, L. J.; Salawitch, R. J.; Blavier, J. -F.; Sen, B.; Toon, G. C.; Jucks, K. W.; Johnson, D. G.; Stachnik, R. A.; Margitan, J. J.

    2004-01-01

    The HOCl catalytic cycle is an efficient ozone loss mechanism in the lower mid-latitude stratosphere. We use a diurnal steady-state photochemical model to calculate profiles of HOCl for conditions encountered by a number of high-altitude balloon flights. To assess how well this model represents ozone loss by the HOCl cycle, we compare our calculations of HOCl and its precursors Cl0 and HO2 with measurements obtained by an FTIR solar absorption spectrometer (MkIV), a far-infrared emission spectrometer (FIRS-2), and a submillimetenvave limb sounder (SLS). We then evaluate these comparisons in light of a number of recent laboratory studies of the main formation mechanism of HOCl, the reaction of Cl0 + HO2. Those studies measured both the reaction rate constant and the quantum yield for a second product pathway, formation of HCl.

  5. Effect of particle water on ozone and secondary organic aerosol formation from benzene-NO2-NaCl irradiations

    NASA Astrophysics Data System (ADS)

    Wang, Yujie; Luo, Hao; Jia, Long; Ge, Shuangshuang

    2016-09-01

    Ozone (O3) and secondary organic aerosol (SOA) are important pollutants in the urban atmosphere. Benzene is one of the most important aromatic species in urban air, which could produce O3 and SOA in the presence of NOx (x = 1, 2) and UV light. A series of experiments was carried out to study the effect of particle water on O3 and SOA formation from benzene under various humid conditions in an indoor smog chamber. The results show that the peak O3 concentrations decreased with the increase of RH or the mass concentration of liquid NaCl particles. The peak O3 concentration reduced by 30% as RH increased from 9% to 87% with the similar initial concentrations of NaCl (about 46 μg m-3), and decreased by 10% as the initial NaCl concentrations increased from 36.0 μg m-3 to 152.1 μg m-3 at about 73% RH. The relationships between liquid water content (LWC) and O3 or SOA were investigated. The results show that LWC is the key factor that leads to an opposite effect on O3 and SOA formation from benzene. The peak O3 concentration exponentially decreased 37% as LWC0 increased from zero to 349.8 μg m-3. Heterogeneous reaction of dinitrogen pentoxide (N2O5) with particle water is the major reason for the decrease of O3. The yields of SOA increased from 5.2 to 10.5% as LWC0 increased from zero to 349.8 μg m-3. The relative intensities of bands Osbnd H, Cdbnd O, Csbnd OH and NO3- increased by 22.9, 6.8, 6.7 and 13.1 times respectively as compared with dry condition. Alcohols or hydrates are confirmed to be the major contributors to SOA with increasing LWC.

  6. CMAQ predictions of tropospheric ozone in the U.S. southwest: influence of lateral boundary and synoptic conditions.

    PubMed

    Shi, Chune; Fernando, H J S; Hyde, Peter

    2012-02-01

    Phoenix, Arizona, has been an ozone nonattainment area for the past several years and it remains so. Mitigation strategies call for improved modeling methodologies as well as understanding of ozone formation and destruction mechanisms during seasons of high ozone events. To this end, the efficacy of lateral boundary conditions (LBCs) based on satellite measurements (adjusted-LBCs) was investigated, vis-à-vis the default-LBCs, for improving the predictions of Models-3/CMAQ photochemical air quality modeling system. The model evaluations were conducted using hourly ground-level ozone and NO(2) concentrations as well as tropospheric NO(2) columns and ozone concentrations in the middle to upper troposphere, with the 'design' periods being June and July of 2006. Both included high ozone episodes, but the June (pre-monsoon) period was characterized by local thermal circulation whereas the July (monsoon) period by synoptic influence. Overall, improved simulations were noted for adjusted-LBC runs for ozone concentrations both at the ground-level and in the middle to upper troposphere, based on EPA-recommended model performance metrics. The probability of detection (POD) of ozone exceedances (>75ppb, 8-h averages) for the entire domain increased from 20.8% for the default-LBC run to 33.7% for the adjusted-LBC run. A process analysis of modeling results revealed that ozone within PBL during bulk of the pre-monsoon season is contributed by local photochemistry and vertical advection, while the contributions of horizontal and vertical advections are comparable in the monsoon season. The process analysis with adjusted-LBC runs confirms the contributions of vertical advection to episodic high ozone days, and hence elucidates the importance of improving predictability of upper levels with improved LBCs.

  7. Photochemistry of Dihydrido(hydrotris(3,5-dimethylpyrazolyl)borato)(Z-cyclooctene)iridium. Synthetic Intermediates and Mechanism of the Photochemical Formation of Hydridophenyl(hydrotris(3,5-dimethylpyrazolyl)borato)(trimethyl phosphite)iridium.

    PubMed

    Ferrari, Arlen; Polo, Eleonora; Rüegger, Heinz; Sostero, Silvana; Venanzi, Luigi M.

    1996-03-13

    The photolysis of a benzene solution of [Tp(Me2)IrH(2)(COE)], 1 (Tp(Me2) = hydrotris(3,5-dimethylpyrazolyl)borate, COE = Z-cyclooctene), in the presence of P(OMe)(3), gives the stable novel complex [Tp(Me2)IrH(C(6)H(5))(P(OMe)(3))], 3a. The photochemical syntheses of [Tp(Me2)IrH(2)(P(OMe)(3))], from 1 and P(OMe)(3) in diethyl ether, and [Tp(Me2)IrH(2)(CH(2)=CHCOO(t)Bu)], from 1 in tert-butyl acrylate, are also reported. The above reactions and several experiments using C(6)D(6) and P(OCD(3))(3) show that, in all cases, the primary photoproduct is the 16-electron, five-coordinate iridium(III) intermediate {Tp(Me2)IrH(2)}, 6a, produced by loss of COE from 1. The above experiments also allow the postulation of a mechanistic pathway for the formation of 3a which involves the oxidative addition of an aromatic C-H bond by 6a. Furthemore, the photochemical reaction of 1 in the presence of P(OCD(3))(3) shows that, under the reaction conditions used, oxidative addition of C-H bonds of P(OMe)(3) and of coordinated Tp(Me2)-ligands, presumably, to the intermediates 6a and {Tp(Me2)IrH(C(6)H(5))}, also occurs. Thus, coordinatively unsaturated iridium(III) species readily activate C-H bonds.

  8. Photochemical source of metals for sediments.

    PubMed

    Kopácek, Jirí; Maresová, Marie; Norton, Stephen A; Porcal, Petr; Veselý, Josef

    2006-07-15

    A mass budget study of major in-lake Al fluxes, palaeolimnological data on a >10,000 year old sediment record, and in situ photochemical experiments performed at Plesné Lake (Czech Republic) suggest that photochemical liberation of organically bound aluminum (Al) and iron (Fe) by solar radiation is a significant natural source of their ionic species for lakes and subsequent oxyhydroxides for sediments. The results show that photochemically induced transformation of dissolved Al and Fe to solid oxyhydroxides deposited to Plesné Lake sediment dominated (91 and 73%, respectively) their sedimentary flux throughout the preindustrial era, since soil formation initiated in the catchment. The following sequence of processes occurs: (i) soil organic acids dissolve and bind metals and export them from terrestrial to aquatic systems. (ii) Photochemical decomposition of organic-metal complexes liberates a significant portion (approximately 50% in Pleseé Lake) of organically bound Al and Fe as inorganic ions. (iii) The liberated ionic Al and Fe hydrolyze, precipitate as oxyhydroxide particles, and settle. We hypothesise that the same Al and Fe transporting process occurs in other lakes and coastal marine areas and is ecologically important because Al and Fe oxyhydroxides can bind trace metals and phosphorus.

  9. Influence of photochemical processes on traffic-related airborne pollutants in urban street canyon

    NASA Astrophysics Data System (ADS)

    Střižík, Michal; Zelinger, Zdeněk; Kubát, Pavel; Civiš, Svatopluk; Bestová, Iva; Nevrlý, Václav; Kadeřábek, Petr; Čadil, Jan; Berger, Pavel; Černý, Alexandr; Engst, Pavel

    2016-09-01

    The urban street canyon of Legerova Street is part of the north-south trunk road that passes through the centre of Prague and remains an unresolved environmental issue for the capital of the Czech Republic. As many as one hundred thousand cars move through this region per day, and mortality has increased as a result of dust, NOx and other exhaust pollutants. The spatial distribution of pollutants (i.e., NO2, NO, and O3) during a day was measured by combined DIAL/SODAR techniques and spot analyzers that were appropriately located near the bottom of the street canyon. The measurements were performed under different meteorological conditions (autumn versus summer period). A purely physical approach does not provide a true description of reality due to photochemical processes that take place in the street canyon atmosphere. Sunlight in the summer triggers the production of ozone and thereby influences the concentration of NO2. The formation of an inverse non-diffuse vertical concentration distribution of NO2 in the morning hours was found to be related to the direct emission of O3 in the street and its background concentration. Rapid changes of NO2 concentrations were observed over time and in the vertical profile. An approach using a photochemical reactor to describe processes in a street canyon atmosphere was developed and verified as a useful tool for prediction purposes.

  10. Development and testing of a chemical mechanism for atmospheric photochemical transformations of 1,3-butadiene.

    PubMed

    Sexton, Kenneth G; Doyle, Melanie L; Jeffries, Harvey E; Ebersviller, Seth

    2007-03-20

    1,3-Butadiene (BD) in the atmosphere is a highly reactive hazardous air pollutant, which has a short lifetime and is quickly transformed to reaction products, some of which are also toxic. The ability to predict exposure to BD and its' products requires models with chemical mechanisms which can simulate these transformations. The atmospheric photochemical reactions of BD have been studied in the University of North Carolina Outdoor smog chamber, which has been used for over 30 years to test photochemical mechanisms for air quality simulation models for ozone. Experiments have been conducted under conditions of real sunlight and realistic temperature and humidity to study the transformations of BD and to develop and test chemical mechanisms for the simulation of these processes. Experimental observation of time-concentration data of BD decay and the formation of many products is compared to simulation results. This chemical mechanism can be incorporated into air quality simulation models which can be used to estimate ambient concentrations needed for exposure estimates. PMID:17328875

  11. Photochemical ablation of organic solids

    NASA Astrophysics Data System (ADS)

    Yingling, Yaroslava G.; Garrison, Barbara J.

    2003-04-01

    We have investigated by molecular dynamics simulations the ablation of material that is onset by photochemical processes. We compare this system with only photochemical processes to a system containing photochemical and photothermal processes. The simulations reveal that ablation by purely photochemical processes is accompanied by the ejection of relatively cold massive molecular clusters from the surface of the sample. The top of the plume exhibits high temperatures whereas the residual part of the sample is cold. The removal of the damaged material through big molecular cluster ejection is consistent with experimental observations of low heat damage of material.

  12. Mechanisms of impact of greenhouse gases on the Earth's ozone layer in the Polar Regions

    NASA Astrophysics Data System (ADS)

    Zadorozhny, Alexander; Dyominov, Igor

    A numerical 2-D zonally averaged interactive dynamical radiative-photochemical model of the atmosphere including aerosol physics is used to examine the impact of the greenhouse gases CO2, CH4, and N2O on the future long-term changes of the Earth's ozone layer, in particular on its expected recovery after reduction of anthropogenic discharges of chlorine and bromine compounds into the atmosphere. The model allows calculating self-consistently diabatic circu-lation, temperature, gaseous composition of the troposphere and stratosphere at latitudes from the North to South Poles, as well as distribution of sulphate aerosol particles and polar strato-spheric clouds (PSCs) of types I and II. The scenarios of expected changes of the anthropogenic pollutants for the period from 1980 through 2050 are taken from Climate Change 2001. The processes, which determine the influence of anthropogenic growth of atmospheric abun-dance of the greenhouse gases on the long-term changes of the Earth's ozone layer in the Polar Regions, have been studied in details. Expected cooling of the stratosphere caused by increases of greenhouse gases, most importantly CO2, essentially influences the ozone layer by two ways: through temperature dependencies of the gas phase reaction rates and through enhancement of polar ozone depletion via increased PSC formation. The model calculations show that a weak-ness in efficiencies of all gas phase catalytic cycles of the ozone destruction due to cooling of the stratosphere is a dominant mechanism of the impact of the greenhouse gases on the ozone layer in Antarctic as well as at the lower latitudes. This mechanism leads to a significant acceleration of the ozone layer recovery here because of the greenhouse gases growth. On the contrary, the mechanism of the impact of the greenhouse gases on the ozone through PSC modification be-gins to be more effective in Arctic in comparison with the gas phase mechanism in springs after about 2020, which leads to retard

  13. Photochemical cutting of fabrics

    DOEpatents

    Piltch, Martin S.

    1994-01-01

    Apparatus for the cutting of garment patterns from one or more layers of fabric. A laser capable of producing laser light at an ultraviolet wavelength is utilized to shine light through a pattern, such as a holographic phase filter, and through a lens onto the one or more layers of fabric. The ultraviolet laser light causes rapid photochemical decomposition of the one or more layers of fabric, but only along the pattern. The balance of the fabric of the one or more layers of fabric is undamaged.

  14. Effects of ozone pretreatment on the formation of disinfection by-products and its associated bromine substitution factors upon chlorination/chloramination of Tai Lake water.

    PubMed

    Wang, Fangyuan; Ruan, Mengyong; Lin, Hongjun; Zhang, Yu; Hong, Huachang; Zhou, Xiaoling

    2014-03-15

    This study investigated the effects of preozonation on disinfection by-products (DBPs) formation during chlorination and chloramination of the water collected from Tai Lake. Results showed that the high ozone dose (0.6-1.0 mg O₃/mg DOC) pretreatment reduced the yields of trihaloacetic acids (reduced 62-63% in chlorination), dihaloacetonitriles (reduced 53-55% and 14-26% in chlorination and chloramination, respectively) and trihaomethanes (reduced 19% in chloramination), but markedly increased the formation of halonitromethanes (increased 4.7-5.6 times in chlorination and 2.1-2.7 times in chloramination), haloketones (increased 4.8-7.1 times in chlorination and 2.5-2.9 times in chloramination) and dihaloacetic acids (increased 1.5-2.4 times in chlorination and 0.3-0.6 times in chloramination). Thus the high ozone dose pretreatment should be avoided during chlorination/chloramination of Tai Lake water. Also, chloramination (with and without preozonation) produced much lower DBPs yields as compared with chlorination (with and without preozonation), indicating that chloramine was a better choice to control the DBPs yields. Further analysis also revealed that the bromine substitution factors (BSFs) of DBPs varied with disinfection mode. In chlorinamination, the BSFs generally showed a decrease trend with the ozone dose, yet in chlorination, the BSFs mostly exhibited first an increase and then a decrease trend. Moreover, the BSFs of DBPs in chloramination (with or without preozonation) were dominantly lower than those in chlorination (with or without preozonation).

  15. Characteristics of C-, N-DBPs formation from algal organic matter: role of molecular weight fractions and impacts of pre-ozonation.

    PubMed

    Zhou, Shiqing; Zhu, Shumin; Shao, Yisheng; Gao, Naiyun

    2015-04-01

    Extracellular organic matter (EOM) and intracellular organic matter (IOM) of Microcystis aeruginosa have been reported to contribute to the formation of carbonaceous disinfection by-products (C-DBPs) and nitrogenous disinfection by-products (N-DBPs). Little is known about DBPs formation from different molecular weight (MW) fractions, especially for N-nitrosodimethylamine (NDMA). This study fractionated EOM and IOM into several MW fractions using a series of ultrafiltration membranes and is the first to report on the C-DBPs and N-DBPs formation from chlorination and chloramination of different MW fractions. Results showed that EOM and IOM were mainly distributed in low-MW (<1 KDa) and high-MW (>100 KDa) fractions. Additionally, the low-MW and high-MW fractions of EOM and IOM generally took an important part in forming C-DBPs and N-DBPs, either in chlorination or in chloramination. Furthermore, the effects of pre-ozonation on the formation of DBPs in subsequent chlorination and chloramination were also investigated. It was found that ozone shifted the high-MW fractions of EOM and IOM into lower MW fractions and increased the C-DBPs and N-DBPs yields to different degrees. As low-MW fractions are more difficult to remove than high-MW fractions by conventional treatment processes, therefore, activated carbon adsorption, nanofiltration (NF) and biological treatment processes can be ideal to remove the low-MW fractions and minimize the formation potential of C-DBPs and N-DBPs. Moreover, the use of ozone should be carefully considered in the treatment of algal-rich water.

  16. Impact on surface ozone by fugitive emissons of ethylene and propylene from a petrochemical plant cluster

    NASA Astrophysics Data System (ADS)

    Hsieh, H.; Chang, J.; Chen, S.; Wang, J.

    2010-12-01

    Ethylene and propylene are two most produced organic compounds in the world which are mainly produced from the cracking process in the oil refinery industry. In a large petrochemical plant cluster a large variety of petrochemical products are derived from these two compounds used as starting reagents. Fugitive emissions of these two compounds from storage tanks and pipelines are often inevitable, which could pose a great burden on the formation of surface ozone and thus deteriorate air quality if leakage is significant. In this study, a photochemical assessment monitoring station (PAMS) was deployed 7 kilometers south of a large petrochemical plant cluster. Concentration spikes of ethylene and propylene were frequently observed by the on-line gas chromatographic system whenever northerly prevailed. The impact of ethylene and propylene’s leakage on ozone formation was simulated by an air quality model (i.e., PAMS-AQM), of which emission inventory of non-methane hydrocarbons (NMHCs) were speciated and calibrated by the PAMS measurements. Contribution to ozone formation by these two compounds in the downwind areas was able to be assessed by turning off the emissions of ethylene and propylene from this plant cluster while maintaining those of other precursors in the model. Scenarios of precursor (NMHC and NOx) reduction or increase were also simulated from the perspectives of ozone control strategies.

  17. Formation of hydrogen polyoxides as constituents of peroxy radical condensate upon low-temperature interaction of hydrogen atoms with liquid ozone.

    PubMed

    Levanov, Alexander V; Isaykina, Oksana Ya; Antipenko, Ewald E; Lunin, Valerii V

    2014-01-01

    The composition of low-temperature condensates obtained by the reaction of hydrogen atoms with liquid ozone has been determined from the Raman spectra and data on the molar ratio of O2 to H2O2 in the decomposition products. The main constituents are hydrogen tetroxide H2O4, trioxide H2O3, and peroxide H2O2 in comparable amounts and also water H2O. The mechanism and quantitative kinetic model of their formation have been proposed. H2O4, H2O3, and H2O2 are formed in the diffusion-controlled reactions between OH and HO2 in the liquid ozone layer and stabilized by transfer to the solid phase. OH and HO2 radicals are generated via a sequence of the reactions initiated by the interaction H + O3(liq). The model adequately reproduces the properties of the real condensates.

  18. Issues on urban ozone: Natural hydrocarbons, urbanization and ozone control strategies

    SciTech Connect

    Cardelino, C.A.

    1991-01-01

    Using the Atlanta metropolitan area as a case study, the author has examined the effects of urbanization and its associated heat island on urban ozone concentrations. As cities grow, two important effects take place: the amount of trees is reduced and there is an increase in ambient temperature due to the urban heat island effect. As the temperature increases, more ozone is photochemically produced, more anthropogenic hydrocarbons are released into the atmosphere, and more biogenic hydrocarbons are emitted from the remaining trees. This increase in hydrocarbons helps produce even more ozone. Numerical simulations using conditions of a typical summertime day in Atlanta suggest that these processes are able to offset the reductions in anthropogenic hydrocarbon emissions caused by emission controls. To study ozone control strategies, the author has developed a photochemical model that utilizes ozone and ozone precursors observations as input data, and is therefore independent of the highly uncertain processes of emission inventories and transport. In contrast with the operation of the current emission-based models, the observation-based model (OBM) is relatively easy to implement and very fast to operate. Using numerical simulations of different meteorological and chemical conditions in Atlanta, he has shown that the ozone sensitivities obtained with the observation-based model, are in very good agreement with similar ozone sensitivities derived using an emission-based model that includes transport. He also illustrated the potential utility of the OBM by applying it to the ozone non-attainment problem in Baton Rouge, Louisiana.

  19. Enhanced formation of fine particulate nitrate at a rural site on the North China Plain in summer: The important roles of ammonia and ozone

    NASA Astrophysics Data System (ADS)

    Wen, Liang; Chen, Jianmin; Yang, Lingxiao; Wang, Xinfeng; Xu, Caihong; Sui, Xiao; Yao, Lan; Zhu, Yanhong; Zhang, Junmei; Zhu, Tong; Wang, Wenxing

    2015-01-01

    Severe PM2.5 pollution was observed frequently on the North China Plain, and nitrate contributed a large fraction of the elevated PM2.5 concentrations. To obtain a comprehensive understanding of the formation pathways of these fine particulate nitrate and the key factors that affect these pathways, field measurements of fine particulate nitrate and related air pollutants were made at a rural site on the North China Plain in the summer of 2013. Extremely high concentrations of fine particulate nitrate were frequently observed at night and in the early morning. The maximum hourly concentration of fine particulate nitrate reached 87.2 μg m-3. This concentration accounted for 29.9% of the PM2.5. The very high NH3 concentration in the early morning significantly accelerated the formation of fine particulate nitrate, as indicated by the concurrent appearance of NH3 and NO3- concentration peaks and a rising neutralization ratio (the equivalent ratio of NH4+ to the sum of SO42- and NO3-). On a number of other episode days, strong photochemical activity during daytime led to high concentrations of O3 at night. The fast secondary formation of fine particulate nitrate was mainly attributed to the hydrolysis of N2O5, which was produced from O3 and NO2. Considering the important roles of NH3 and O3 in fine particulate nitrate formation, we suggest the control of NH3 emissions and photochemical pollution to address the high levels of fine particulate nitrate and the severe PM2.5 pollution on the North China Plain.

  20. Evaluating 2012 Ozone Impacts of Natural Gas Development in the Haynesville Shale with an Updated Emission Inventory

    NASA Astrophysics Data System (ADS)

    Kemball-Cook, S. R.; Bar-Ilan, A.; Yarwood, G.

    2013-12-01

    materials, equipment, and personnel to and from wells and the types and activity of non-road equipment operating at well sites. Well production data for 2009 through 2012 from Texas and Louisiana state regulatory agencies was used to update the well decline curve used to project formation-wide gas production. The updated emission inventory was used to quantify 2012 ozone impacts from the Haynesville with the CAMx photochemical grid model. The ozone contribution from truck traffic was determined. We evaluated the effect of the Haynesville on ozone design values in Northeast Texas and Northwest Louisiana as well as on regional ozone. The model projections for ozone were compared to recent trends in observed ozone.

  1. [Effects of photochemical smog from a flow reactor on bacteria. II. Determination of bactericidal components in photochemical smog].

    PubMed

    Nover, H; Botzenhart, K

    1983-04-01

    The mixture of substances in the photochemical smog could be detected by different reduction rates of exposed bacteria. Beside ozone other products of the ozone/olefine-reaction could reduce the survival of exposed bacteria. For Staph. epidermidis a toxic influence from the reaction products could be found only after UV-irradiation. The main components were aldehydes, hydrocarbons, radicals, peroxiradicals and radicaloxides. For peroxiacetylnitrate (PAN) no bactericidal effect could be found for bacteria adsorbed on membrane filters in concentrations of 300 ppb in the smog (UV-irradiation was put off for two hours) and even in concentrations of 1000 ppb prepared by gaschromatography. The influence on lipopolysaccharide (lps) defective mutants of Salmonella minnesota showed the protection of the lps-layer against e.g. relative humidity and ozone (500 ppb), but no specific protection against smog components.

  2. Photochemical properties of trans-1-chloro-3,3,3-trifluoropropene (trans-CHCl═CHCF3): OH reaction rate constant, UV and IR absorption spectra, global warming potential, and ozone depletion potential.

    PubMed

    Orkin, Vladimir L; Martynova, Larissa E; Kurylo, Michael J

    2014-07-17

    Measurements of the rate constant for the gas-phase reactions of OH radicals with trans-1-chloro-3,3,3-trifluoropropene (trans-CHCl═CHCF3) were performed using a flash photolysis resonance-fluorescence technique over the temperature range 220-370 K. The reaction rate constant exhibits a noticeable curvature of the temperature dependence in the Arrhenius plot, which can be represented by the following expression: kt-CFP (220-370 K) = 1.025 × 10(-13) × (T/298)(2.29) exp(+384/T) cm(3 )molecule(-1) s(-1). The room-temperature rate constant was determined to be kt-CFP (298 K) = (3.29 ± 0.10) × 10(-13) cm(3) molecule(-1) s(-1), where the uncertainty includes both two standard errors (statistical) and the estimated systematic error. For atmospheric modeling purposes, the rate constant below room temperature can be represented by the following expression: kt-CFP (220-298 K) = (7.20 ± 0.46) × 10(-13) exp[-(237 ± 16)/T] cm(3) molecule(-1) s(-1). There was no difference observed between the rate constants determined at 4 kPa (30 Torr) and 40 kPa (300 Torr) at both 298 and 370 K. The UV and IR absorption cross sections of this compound were measured at room temperature. The atmospheric lifetime, global warming potential, and ozone depletion potential of trans-CHCl═CHCF3 were estimated. PMID:24955760

  3. Large Scale Atmospheric Chemistry Simulations for 2001: An Analysis of Ozone and Other Species in Central Arizona

    SciTech Connect

    Atherton, C; Bergmann, D; Cameron-Smith, P; Connell, P; Molenkamp, C; Rotman, D; Tannahil, J

    2002-10-08

    A key atmospheric gas is ozone. Ozone in the stratosphere is beneficial to the biosphere because it absorbs a significant fraction of the sun's shorter wavelength ultraviolet radiation. Ozone in the troposphere is a pollutant (respiratory irritant in humans and acts to damage crops, vegetation, and many materials). It affects the Earths energy balance by absorbing both incoming solar radiation and outgoing long wave radiation. An important part of the oxidizing capacity of the atmosphere involves ozone, through a photolysis pathway that leads to the hydroxyl radical (OH). Since reaction with OH is a major sink of many atmospheric species, its concentration controls the distributions of many radiatively important species. Ozone in the troposphere arises from both in-situ photochemical production and transport from the stratosphere. Within the troposphere, ozone is formed in-situ when carbon monoxide (CO), methane (CH4), and non-methane hydrocarbons (NMHCs) react in the presence of nitrogen oxides (NO, = NO + NO2) and sunlight. The photochemistry of the stratosphere differs significantly from that in the troposphere. Within the stratosphere, ozone formation is initiated by the photolysis of 02. Stratospheric ozone may be destroyed via catalytic reactions with NO, H (hydrogen), OH, CI (chlorine) and Br (bromine), or photolysis. In the past, attempts to simulate the observed distributions of ozone (and other important gases) have focused on either the stratosphere or the troposphere. Stratospheric models either employed simplified parameterizations to represent tropospheric chemical and physical processes, or assumed the troposphere behaved as a boundary condition. Likewise, tropospheric models used simplified stratospheric chemistry and transport.

  4. Photochemical oxidation: A solution for the mixed waste dilemma

    SciTech Connect

    Prellberg, J.W.; Thornton, L.M.; Cheuvront, D.A.

    1995-12-31

    Numerous technologies are available to remove organic contamination from water or wastewater. A variety of techniques also exist that are used to neutralize radioactive waste. However, few technologies can satisfactorily address the treatment of mixed organic/radioactive waste without creating unacceptable secondary waste products or resulting in extremely high treatment costs. An innovative solution to the mixed waste problem is on-site photochemical oxidation. Liquid-phase photochemical oxidation has a long- standing history of successful application to the destruction of organic compounds. By using photochemical oxidation, the organic contaminants are destroyed on-site leaving the water, with radionuclides, that can be reused or disposed of as appropriate. This technology offers advantages that include zero air emissions, no solid or liquid waste formation, and relatively low treatment cost. Discussion of the photochemical process will be described, and several case histories from recent design testing, including cost analyses for the resulting full-scale installations, will be presented as examples.

  5. Comet Halley as an aggregate of interstellar dust and further evidence for the photochemical formation of organics in the interstellar medium

    NASA Technical Reports Server (NTRS)

    Briggs, R.; Ertem, G.; Ferris, J. P.; Greenberg, J. M.; Mccain, P. J.; Mendoza-Gomez, C. X.; Schutte, W.

    1992-01-01

    Photolysis of mixtures of CO:NH3:H2O at 12 K results in the formation of an organic residue which is not volatile in high vacuum at room temperature. Analysis of this fraction by GC-MS resulted in the detection of C2-C3 hydroxy acids and hydroxy amides, glycerol, urea, glycine, hexamethylene tetramine, formamidine and ethanolamine. Use of isotopically labeled gases made it possible to establish that the observed products were not contaminants. The reaction pathways for the formation of these products were determined from the position of the isotopic labels in the mass spectral fragments. The significance of these findings to the composition of comets and the origins of life is discussed.

  6. Polyimides by photochemical cyclopolymerization

    NASA Technical Reports Server (NTRS)

    Meador, Michael A. (Inventor)

    2005-01-01

    The novel polyimides of this invention are derived from Diels-Alder cyclopolymerization of photochemically generated bisdienes with dienophiles, such as bismaleimides, trismaleimides and mixtures thereof with maleimide end-caps. Irradiation of one or more diketones produces two distinct hydroxy o-quinodimethane (photoenol) intermediates. These intermediates are trapped via Diels-Alder cycloaddition with appropriate dienophiles, e.g., bismaleimide and/or trismaleimides to give the corresponding polyimides in quantitative yields. When bismaleimides, trismaleimides or mixtures thereof with maleimide end-caps are used as the dienophile, the resulting polyimides have glass transition temperatures (Tg) as high as 300? C. Polyimide films can be prepared by ultraviolet irradiation of high solids content varnishes of the monomers in a small amount of solvent, e.g., cyclohexanone, dimethyl formamide, N-methylpyrollidone and the like. These novel polyimides are characterized as having high glass transition temperatures, good mechanical properties and improved processing in the manufacture of adhesives, electronic materials and films.

  7. Polyimides by Photochemical Cyclopolymerization

    NASA Technical Reports Server (NTRS)

    Meador, Michael A. (Inventor)

    2005-01-01

    The novel polyimides of this invention are derived from Diels-Alder cyclopolymerization of photochemically generated bisdienes with dienophiles, such as bismaleimides, trismaleimides and mixtures thereof with maleimide endcaps. Irradiation of one or more diketones produces two distinct hydroxy o-quinodimethane (photoenol) intermediates. These intermediates are trapped via Diels-Alder cycloaddition with appropriate dienophiles, e.g., bismaleimide and/or trismaleimides to give the corresponding polyimides in quantitative yields. When bismaleimides, trismaleimides or mixtures thereof with maleimide end-caps are used as the dienophile, the resulting polyimides have glass transition temperatures (Tg) as high as 300 C. Polyimide films can be prepared by ultraviolet irradiation of high solids content varnishes of the monomers in a small amount of solvent, e.g., cyclohexanone, dimethyl formamide, N-methylpyrollidone and the like. These novel polyimides are characterized as having high glass transition temperatures, good mechanical properties and improved processing in the manufacture of adhesives, electronic materials and films.

  8. Autonomous Ozone and Aerosol Lidar Platform: Preliminary Results

    NASA Astrophysics Data System (ADS)

    Strawbridge, K. B.

    2014-12-01

    Environment Canada is developing an autonomous tropospheric ozone and aerosol lidar system for deployment in support of short-term field studies. Tropospheric ozone and aerosols (PM10 and PM2.5) are important atmospheric constituents in low altitude pollution affecting human health and vegetation. Ozone is photo-chemically active with nitrogen oxides and can have a distinct diurnal variability. Aerosols contribute to the radiative budget, are a tracer for pollution transport, undergo complex mixing, and contribute to visibility and cloud formation. This particular instrument will employ two separate lidar transmitter and receiver assemblies. The tropospheric ozone lidar, based on the differential absorption lidar (DIAL) technique, uses the fourth harmonics of a Nd:YAG laser directed into a CO2 Raman cell to produce 276 nm, 287nm and 299 nm (first to third Stokes lines) output wavelengths. The aerosol lidar is based on the 3+2 design using a tripled Nd:YAG to output 355 nm, 532 nm and 1064nm wavelengths. Both lidars will be housed in a modified cargo trailer allowing for easy deployment to remote areas. The unit can be operated and monitored 24 hours a day via an internet link and requires an external power source. Simultaneous ozone and aerosol lidar measurements will provide the vertical context necessary to understand the complex mixing and transformation of pollutants - particularly when deployed near other ground-based in-situ sensors. Preliminary results will be shown from a summer field study at the Centre For Atmospheric Research Experiments (CARE).

  9. Photochemical oxidation of 2-aminofluorene: correlation between the induction of direct-acting mutagenicity and the formation of nitro and nitroso aromatics.

    PubMed

    Strniste, G F; Nickols, J W; Okinaka, R T

    1985-08-01

    The kinetics of near ultraviolet light-mediated phototransformation of 2-aminofluorene (2-AF) was studied using high performance liquid chromatography (HPLC) and the Ames/Salmonella mutagenicity bioassay. Employing tester strains TA98, TA1538, and the nitroreductase-deficient TA98NR without the addition of exogenous metabolic enzymes, we were able to detect and discriminate between the UVA exposure-dependent formation of two stable photoproducts, 2-nitrosofluorene (2-NOF) and 2-nitrofluorene (2-NO2F). Mutagenicity of irradiated 2-AF solutions (using dimethyl sulfoxide as a solvent) in the various tester strains indicates the rapid formation of the photo-labile 2-NOF, after which 2-NO2F accounts for the preponderance of mutagenic activity. Continued UVA irradiation (greater than 72 h at 6.8 J/m2/s) of 2-AF results in the formation of greater than 30 photoproducts resolvable on HPLC, several of which, in addition to 2-NOF and 2-NO2F, are mutagenic on Salmonella but are chemically undefined to date. Prolonged irradiation ultimately destroys the photo-induced mutagenicity of 2-AF. However, UVA-induced 2-AF photoproducts are stable for several weeks when stored in sealed vials in the dark. Light potentiated oxidation of aromatic amines constitutes an alternative mechanism for the transformation of aromatic amines into proximate mutagens/carcinogens. PMID:3894951

  10. A single exposure to photochemical smog causes airway irritation and cardiac dysrhythmia in mice

    EPA Science Inventory

    The data presented here shows that a single exposure to photochemical smog causes airway irritation and cardiac dysrhythmia in mice. Smog, which is a complex mixture of particulate matter and gaseous irritants (ozone, sulfur dioxide, reactive aldehydes), as well as components whi...

  11. PHOTOCHEMICAL PRODUCTS IN URBAN MIXTURES ENHANCE INFLAMMATORY RESPONSES IN LUNG CELLS

    EPA Science Inventory

    Complex urban air mixtures that realistically mimic urban smog can be generated for investigating adverse health effects. "Smog chambers" have been used for over 30 yr to conduct experiments for developing and testing photochemical models that predict ambient ozone (O(3)) concent...

  12. Chemical kinetics and photochemical data for use in stratospheric modeling: Evaluation number 11

    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.

    1994-01-01

    This is the eleventh in a series of evaluated sets of rate constants and photochemical cross sections compiled by the NASA Panel for Data Evaluation. The primary application of the data is in the modeling of stratospheric processes, with special emphasis on the ozone layer and its possible perturbation by anthropogenic and natural phenomena.

  13. Has the Performance of Regional-Scale Photochemical Modelling Systems Changed over the Past Decade?

    EPA Science Inventory

    This study analyzed summertime ozone concentrations that have been simulated by various regional-scale photochemical modelling systems over the Eastern U.S. as part of more than ten independent studies. Results indicate that there has been a reduction of root mean square errors ...

  14. Chemical Kinetics and Photochemical Data for Use in Stratospheric Modeling. Evaluation No. 12

    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.

    1997-01-01

    This is the twelfth in a series of evaluated sets of rate constants and photochemical cross sections compiled by the NASA Panel for Data Evaluation. The primary application of the data is in the modeling of stratospheric processes, with special emphasis on the ozone layer and its possible perturbation by anthropogenic and natural phenomena.

  15. 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. PMID:22355557

  16. An Integrative Study of Photochemical Air Pollution in Hong Kong: an Overview

    NASA Astrophysics Data System (ADS)

    Wang, T.

    2014-12-01

    Hong Kong is situated in the Pearl River delta of Southern China. This region has experienced phenomenal economic growth in the past 30 years. Emissions of large amount of pollutants from urban areas and various industries coupled with subtropical climate have led to frequent occurrences of severe photochemical air pollution. Despite the long-term control efforts of the Hong Kong government, the atmospheric levels of ozone have been increasing in the past decade. To obtain an updated and more complete understanding of photochemical smog, an integrative study has been conducted during 2010-2014. Several intensive measurement campaigns were carried out at urban, suburban and rural sites in addition to the routine observations at fourteen air quality monitoring stations in Hong Kong. Meteorological, photochemical, and chemical-transport modeling studies were conducted to investigate the causes/processes of elevated photochemical pollution . The main activities of this study were to (1) examine the situation and trends of photochemical air pollution in Hong Kong, (2) understand some underlying chemical processes in particular the poorly-understood heterogeneous processes of reactive nitrogen oxides, (3) quantify the local, regional, and super-regional contributions to the ozone pollution in Hong Kong, and (4) review the control policy and make further recommendations based on the science. This paper will give an overview of this study and present some key results on the trends and chemistry of the photochemical pollution in this polluted subtropical region.

  17. Contribution of biogenic emissions to the formation of ozone and particulate matter in the eastern United States.

    PubMed

    Pun, Betty K; Wu, Shiang-Yuh; Seigneur, Christian

    2002-08-15

    As anthropogenic emissions of ozone (O3) precursors, fine particulate matter (PM2.5), and PM2.5 precursors continue to decrease in the United States, the fraction of O3 and PM2.5 attributable to natural sources may become significant in some locations, reducing the efficacy that can be expected from future controls of anthropogenic sources. Modeling studies were conducted to estimate the contribution of biogenic emissions to the formation of O3 and PM2.5 in Nashville/TN and the northeastern United States. Two approaches were used to bound the estimates. In an anthropogenic simulation, biogenic emissions and their influence at the domain boundaries were eliminated. Contributions of biogenic compounds to the simulated concentrations of O3 and PM2.5 were determined by the deviation of the concentrations in the anthropogenic case from those in the base case. A biogenic simulation was used to assess the amounts of O3 and PM2.5 produced in an environment free from anthropogenic influences in emissions and boundary conditions. In both locations, the contribution of biogenic emissions to O3 was small (<23%) on a domain-wide basis, despite significant biogenic volatile organic compounds (VOC) emissions (65-89% of total VOC emissions). However, the production of O3 was much more sensitive to biogenic emissions in urban areas (22-34%). Therefore, the effects of biogenic emissions on O3 manifested mostly via their interaction with anthropogenic emissions of NOx. In the anthropogenic simulations, the average contribution of biogenic and natural sources to PM2.5 was estimated at 9% in Nashville/TN and 12% in the northeast domain. Because of the long atmospheric lifetimes of PM2.5, the contribution of biogenic/natural PM2.5 from the boundary conditions was higher than the contribution of biogenic aerosols produced within the domain. The elimination of biogenic emissions also affected the chemistry of other secondary PM2.5 components. Very little PM2.5 was formed in the biogenic

  18. Contribution of biogenic emissions to the formation of ozone and particulate matter in the eastern United States.

    PubMed

    Pun, Betty K; Wu, Shiang-Yuh; Seigneur, Christian

    2002-08-15

    As anthropogenic emissions of ozone (O3) precursors, fine particulate matter (PM2.5), and PM2.5 precursors continue to decrease in the United States, the fraction of O3 and PM2.5 attributable to natural sources may become significant in some locations, reducing the efficacy that can be expected from future controls of anthropogenic sources. Modeling studies were conducted to estimate the contribution of biogenic emissions to the formation of O3 and PM2.5 in Nashville/TN and the northeastern United States. Two approaches were used to bound the estimates. In an anthropogenic simulation, biogenic emissions and their influence at the domain boundaries were eliminated. Contributions of biogenic compounds to the simulated concentrations of O3 and PM2.5 were determined by the deviation of the concentrations in the anthropogenic case from those in the base case. A biogenic simulation was used to assess the amounts of O3 and PM2.5 produced in an environment free from anthropogenic influences in emissions and boundary conditions. In both locations, the contribution of biogenic emissions to O3 was small (<23%) on a domain-wide basis, despite significant biogenic volatile organic compounds (VOC) emissions (65-89% of total VOC emissions). However, the production of O3 was much more sensitive to biogenic emissions in urban areas (22-34%). Therefore, the effects of biogenic emissions on O3 manifested mostly via their interaction with anthropogenic emissions of NOx. In the anthropogenic simulations, the average contribution of biogenic and natural sources to PM2.5 was estimated at 9% in Nashville/TN and 12% in the northeast domain. Because of the long atmospheric lifetimes of PM2.5, the contribution of biogenic/natural PM2.5 from the boundary conditions was higher than the contribution of biogenic aerosols produced within the domain. The elimination of biogenic emissions also affected the chemistry of other secondary PM2.5 components. Very little PM2.5 was formed in the biogenic

  19. Laboratory evaluation of a prototype photochemical chamber designed to investigate the health effects of fresh and aged vehicular exhaust emissions

    PubMed Central

    Papapostolou, Vasileios; Lawrence, Joy E.; Diaz, Edgar A.; Wolfson, Jack M.; Ferguson, Stephen T.; Long, Mark S.; Godleski, John J.; Koutrakis, Petros

    2013-01-01

    Laboratory experiments simulating atmospheric aging of motor vehicle exhaust emissions were conducted using a single vehicle and a photochemical chamber. A compact automobile was used as a source of emissions. The vehicle exhaust was diluted with ambient air to achieve carbon monoxide (CO) concentrations similar to those observed in an urban highway tunnel. With the car engine idling, it is expected that the CO concentration is a reasonable surrogate for volatile organic compounds (VOCs) emissions. Varying the amount of dilution of the exhaust gas to produce different CO concentrations, allowed adjustment of the concentrations of VOCs in the chamber to optimize production of secondary organic aerosol (SOA) needed for animal toxicological exposures. Photochemical reactions in the chamber resulted in nitric oxide (NO) depletion, nitrogen dioxide (NO2) formation, ozone (O3) accumulation, and SOA formation. A stable SOA concentration of approximately 40 µg m−3 at a chamber mean residence time of 30 min was achieved. This relatively short mean residence time provided adequate chamber flow output for both particle characterization and animal exposures. The chamber was operated as a continuous flow reactor for animal toxicological tests. SOA mass generated from the car exhaust diluted with ambient air was almost entirely in the ultrafine mode. Chamber performance was improved by using different types of seed aerosol to provide a surface for condensation of semivolatile reaction products, thus increasing the yield of SOA. Toxicological studies using Sprague-Dawley rats found significant increases of in vivo chemiluminescence in lungs following exposure to SOA. PMID:21689011

  20. Laboratory evaluation of a prototype photochemical chamber designed to investigate the health effects of fresh and aged vehicular exhaust emissions.

    PubMed

    Papapostolou, Vasileios; Lawrence, Joy E; Diaz, Edgar A; Wolfson, Jack M; Ferguson, Stephen T; Long, Mark S; Godleski, John J; Koutrakis, Petros

    2011-07-01

    Laboratory experiments simulating atmospheric aging of motor vehicle exhaust emissions were conducted using a single vehicle and a photochemical chamber. A compact automobile was used as a source of emissions. The vehicle exhaust was diluted with ambient air to achieve carbon monoxide (CO) concentrations similar to those observed in an urban highway tunnel. With the car engine idling, it is expected that the CO concentration is a reasonable surrogate for volatile organic compounds (VOCs) emissions. Varying the amount of dilution of the exhaust gas to produce different CO concentrations, allowed adjustment of the concentrations of VOCs in the chamber to optimize production of secondary organic aerosol (SOA) needed for animal toxicological exposures. Photochemical reactions in the chamber resulted in nitric oxide (NO) depletion, nitrogen dioxide (NO₂) formation, ozone (O₃) accumulation, and SOA formation. A stable SOA concentration of approximately 40 μg m⁻³ at a chamber mean residence time of 30 min was achieved. This relatively short mean residence time provided adequate chamber flow output for both particle characterization and animal exposures. The chamber was operated as a continuous flow reactor for animal toxicological tests. SOA mass generated from the car exhaust diluted with ambient air was almost entirely in the ultrafine mode. Chamber performance was improved by using different types of seed aerosol to provide a surface for condensation of semivolatile reaction products, thus increasing the yield of SOA. Toxicological studies using Sprague-Dawley rats found significant increases of in vivo chemiluminescence in lungs following exposure to SOA.

  1. CO2 and O3 vertical distributions over the Showa Station, Antarctica before and during the ozone hole formation in 2014, measured by balloon-borne CO2 and O3 instruments

    NASA Astrophysics Data System (ADS)

    Miyaji, K.; Matsumi, Y.; Nakayama, T.; Ouchi, M.; Imasu, R.; Kawasaki, M.

    2015-12-01

    The vertical and horizontal distributions of CO2 mixing ratio in the troposphere and stratosphere are considered to include the information on the source and sink of CO2, as well as transport of air masses in the atmosphere. However, only a limited number of vertical profiles for CO2 mixing ratio, which were typically obtained based on aircraft-based observations, are available. We have originally developed a new balloon-born instrument (CO2 sonde) to measure CO2 vertical profile from surface up to about 10 km in altitude. The ozone hole formation is typically observed in the early spring over Antarctica. To our knowledge, no study focusing on the change in the CO2 vertical profile before and after the ozone hole formation has been reported. In the present study, we launched four CO2 sondes at Syowa Station, Antarctica between June and October in 2014 to obtain CO2 vertical distributions before and during the ozone hole formation. Observations of ozone vertical distributions using traditional ozone sondes were also conducted on the same days. In the presentation, we will report the relationships between the vertical distributions of CO2 and ozone.

  2. Source attribution of tropospheric ozone

    NASA Astrophysics Data System (ADS)

    Butler, T. M.

    2015-12-01

    Tropospheric ozone is a harmful pollutant with adverse effects on human health and ecosystems. As well as these effects, tropospheric ozone is also a powerful greenhouse gas, with an anthropogenic radiative forcing one quarter of that of CO2. Along with methane and atmospheric aerosol, tropospheric ozone belongs to the so-called Short Lived Climate forcing Pollutants, or SLCP. Recent work has shown that efforts to reduce concentrations of SLCP in the atmosphere have the potential to slow the rate of near-term climate change, while simultaneously improving public health and reducing crop losses. Unlike many other SLCP, tropospehric ozone is not directly emitted, but is instead influenced by two distinct sources: transport of air from the ozone-rich stratosphere; and photochemical production in the troposphere from the emitted precursors NOx (oxides of nitrogen), CO (Carbon Monoxide), and VOC (volatile organic compounds, including methane). Better understanding of the relationship between ozone production and the emissions of its precursors is essential for the development of targeted emission reduction strategies. Several modeling methods have been employed to relate the production of tropospheric ozone to emissions of its precursors; emissions perturbation, tagging, and adjoint sensitivity methods all deliver complementary information about modelled ozone production. Most studies using tagging methods have focused on attribution of tropospheric ozone production to emissions of NOx, even though perturbation methods have suggested that tropospheric ozone is also sensitive to VOC, particularly methane. In this study we describe the implementation into a global chemistry-climate model of a scheme for tagging emissions of NOx and VOC with an arbitrary number of labels, which are followed through the chemical reactions of tropospheric ozone production in order to perform attribution of tropospehric ozone to its emitted precursors. Attribution is performed to both

  3. Effects of bromide and iodide ions on the formation of disinfection by-products during ozonation and subsequent chlorination of water containing biological source matters.

    PubMed

    Zha, Xiao-song; Liu, Yan; Liu, Xiang; Zhang, Qiang; Dai, Rui-hua; Ying, Ling-wen; Wu, Jin; Wang, Jing-ting; Ma, Luming

    2014-02-01

    This study aims to investigate the influence of the coexistence of halogen ions (bromide/iodide) and biological source matters on the speciation and yield of trihalomethanes (THMs), haloacetic acids (HAAs), and N-nitrosodimethylamine (NDMA) during the ozonation and subsequent chlorination of water. The results show that the concentrations of brominated THMs and iodinated THMs increased with increasing bromide and iodide concentration. These results may be attributed to the higher reactivity of hypobromous acid and hypoiodous acid generated from the ozonation and subsequent chlorination in the presence of bromide or iodide ions. The presence of bromide increased the species of brominated HAAs. There was a shift from chlorinated HAAs to brominated HAAs after increasing the concentration of bromide. The effect of iodide on HAA formation was more complex than bromide. For most samples, the concentration of total HAAs (T-HAAs) increased to the maximum and then decreased with increasing iodide concentration. The components of the organic precursors also significantly influenced the formation of brominated and iodinated disinfection by-products (Br-DBPs and I-DBPs). Humic acids produced more CHBr3 (596.60 μg/L) than other organic materials. Microcystis aeruginosa cells produced the most tribromoacetic acid (TBAA, 84.16 μg/L). Furthermore, the yield of NDMA decreased with increasing bromide concentration, indicating that the formation of NDMA was inhibited by the high concentration of bromide.

  4. 76 FR 76725 - Notification of a Public Meeting of the Clean Air Scientific Advisory Committee (CASAC); Ozone...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-12-08

    ... AGENCY Notification of a Public Meeting of the Clean Air Scientific Advisory Committee (CASAC); Ozone... Advisory Board (SAB) Staff Office announces a public meeting of the CASAC Ozone Review Panel to conduct a peer review of EPA's Integrated Science Assessment for Ozone and Related Photochemical Oxidants...

  5. 77 FR 46755 - Notification of a Public Meeting of the Clean Air Scientific Advisory Committee (CASAC) Ozone...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-08-06

    ... peer review of EPA's Integrated Science Assessment for Ozone and Related Photochemical Oxidants (Third External Review Draft) (June 2012), Health Risk and Exposure Assessment for Ozone--First External Review Draft (July 2012), Welfare Risk and Exposure Assessment for Ozone-- First External Review Draft...

  6. EXAMINING THE INFLAMMATORY RESPONSES OF HAPS: THE ROLE OF OZONE AND OTHER PHTOTCHEMICAL TRANSFORMATION PRODUCTS

    EPA Science Inventory

    The chemistry and health effects of individual hazardous air pollutants (HAPS) have been studied for many years. Once released into the atmosphere, HAPS interact with hydroxyl radicals and ozone (created by photochemical processes), to produce many different products, whose toxic...

  7. Photochemical Formation of Hydroxylated Polybrominated Diphenyl Ethers (OH-PBDEs) from Polybrominated Diphenyl Ethers (PBDEs) in Aqueous Solution under Simulated Solar Light Irradiation.

    PubMed

    Zhao, Qian; Zhao, Huimin; Quan, Xie; He, Xin; Chen, Shuo

    2015-08-01

    Hydroxylated polybrominated diphenyl ethers (OH-PBDEs) are of great concern due to their higher toxicity compared to PBDEs. However, the abiologic process whereby PBDEs are converted to OH-PBDEs in the aquatic environment is not well understood. To explore the possibility of OH-PBDEs photoformation in natural water, the photohydroxylation of BDE-47 has been investigated in aqueous Fe(III) and/or fulvic acid (FA) solutions and in natural lake water under simulated solar light irradiation. The results showed that 6-OH-BDE-47 and 2'-OH-BDE-68 were generated from BDE-47 under these conditions. Based on the identification of derivatives and reactive radicals, OH-PBDEs formation can be ascribed to an addition reaction of ortho-tetra-BDE radical and hydroxyl radical ((•)OH), with or without a subsequent Smiles rearrangement reaction. Since the ortho-tetra-BDE radical could be readily produced by the photolysis of BDE-47, even in pure water, (•)OH production was considered as critical for the photoformation of OH-PBDEs. Thus, it is reasonable to deduce that the photoreactive components (Fe(III), FA) in aqueous solution played an important role through influencing (•)OH generation. Although the yields of OH-PBDEs did not increase regularly with increasing concentration of these photoreactive components in solution, this study suggests a possible abiotic origin of OH-PBDEs formation in the aquatic environment. PMID:26134578

  8. Evaluation of the Community Multiscale Air Quality Model for Simulating Winter Ozone Formation in the Uinta Basin

    EPA Science Inventory

    Areas with close proximity to oil and natural gas operations in rural Utah have experienced winter ozone levels that exceed EPA’s National Ambient Air Quality Standards (NAAQS). Through a collaborative effort, EPA Region 8 – Air Program, ORD, and OAQPS used the Commun...

  9. Products of ozonized arachidonic acid potentiate the formation of DNA single strand breaks in cultured human lung cells

    SciTech Connect

    Kozumbo, W.J.; Hanley, N.M.; Agarwal, S.

    1996-12-31

    In this study we examined the potential for environmental levels of ozone (O{sub 3}) to degrade arachidonic acid (AA), a polyunsaturated fatty acid abundantly present in the lung, into products that can produce DNA single strand breaks (ssb) in cultured human lung cells. Human lung fibroblasts were incubated with 60 {mu}M AA that had been previously exposed to an degraded by 0.4 ppm O{sub 3} (1 hr). Incubation of the cells with O{sub 3}-exposed AA (but not with vehicle alone) for 1 hr at 4{degrees}C and 37{degrees}C produced 555 and 245 rad-equivalents of DNA ssb, respectively, as determined by the DNA alkaline elution technique. These breaks were completely eliminated when the ozonized AA solution was incubated with catalase prior to cell treatment, indicating that H{sub 2}O{sub 2} was solely responsible for damaging DNA. Superoxide dismutase, bovine serum albumin, or heat-inactivated catalase showed little, if any, inhibitory activity. The H{sub 2}O{sub 2} content for only about 40% of the observed breaks. Potentiation of the H{sub 2}O{sub 2}-induced DNA ssb persisted after removal of the carbonyl substances by chromatographic procedures, suggesting that the non-carbonyl component of ozonized AA was the responsible component for inducing augmentation of the observed increases in DNA ssb. Ozonized AA also induced DNA ssb in cultures of the human bronchial epithelial cell line BEAS-2B. Again, these breaks were shown to exceed levels that could be attributed to the presence of H{sub 2}O{sub 2} alone. These results indicate that products of ozonized AA can interact to potentiate DNA ssb in human lung cells. 42 refs., 6 figs., 3 tabs.

  10. Surface ozone in the urban area of Manaus, Amazonas, Brazil

    NASA Astrophysics Data System (ADS)

    Souza, R. A. F. D.; Costa, P. S.; Silva, C.; Godoi, R. M.; Martin, S. T.; Tota, J.; Barbosa, H. M.; Pauliquevis, T.; Ferreira De Brito, J.; Artaxo, P.; Manzi, A. O.; Wolf, S. A.; Cirino, G. G.

    2014-12-01

    When nitrogen oxides from vehicle and industrial emissions mix with volatile organic compounds from trees and plants with exposure to sunlight, a chemical reaction occurs contributing to ground-level ozone pollution. The preliminary results of the surface ozone study in urban area of Manaus, Amazonas State, Brazil, are presented for the first intensive operating period (IOP1) of the GoAmazon experiment (February/March 2014). Photochemical ozone production was found to be a regular process, with an afternoon maximum of the ozone mixing ratio of lower than 20 ppbv for cloudy days or clear sky weather. Typical ozone concentrations at mid-day were low (about 10 ppb). On the other hand, several high-value ozone episodes with surface ozone mixing ratios up to three times larger were registered during the dry season of 2013 (September/October). At the beginning of the wet season, the ozone concentration in Manaus decreased significantly, but diurnal variations can be found during the days with rainfall and other fast changes of meteorological conditions. Possible explanations of the nature of pulsations are discussed. Photochemical ozone production by local urban plumes of Manaus is named as a first possible source of the ozone concentration and biomass burning or power plant emissions are suggested as an alternative or an additional source.

  11. Sulfate aerosols and polar stratospheric cloud formation

    SciTech Connect

    Tolbert, M.A. )

    1994-04-22

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

  12. Evidence of the mid-latitude impact of Antarctic ozone depletion

    NASA Technical Reports Server (NTRS)

    Atkinson, Roger J.; Matthews, W. Andrew; Newman, Paul A.; Plumb, R. Alan

    1989-01-01

    Record low ozone values found over Australia and New Zealand during December 1987 following the record low Antarctic values of October 1987 are analyzed. The sudden decline of ozone amounts in midmonth rule out photochemical effects as a cause and permit the underlying processes to be investigated on a case study basis. Using data from ozone sondes, radiosondes, the Nimbus-7 total ozone mapping spectrometer, and meteorological analyses from the National Meteorological Center, it is argued that these low values resulted from transport of ozone-poor air from higher latitudes. Thus, it seems that the chemical destruction of ozone over Antarctica in early spring is having an impact on lower latitudes.

  13. Polyimides by Photochemical Cyclopolymerization

    NASA Technical Reports Server (NTRS)

    Meador, Michael A. (Inventor)

    2003-01-01

    The polyimides of this invention are derived from a Diels-Alder cyclopolymerization of a photochemically generated bisdiene with dienophiles, such as bismaleimides, trismaleimides and mixtures thereof with maleimide end-caps. Irradiation of one or more diketones produces two distinct hydroxy o-quinodimethane (photoenol) intermediates. These intermediates are trapped via a Diels-Alder cycloaddition with appropriate dienophiles, e.g., bismaleimide and/or trismaleimides to give the corresponding polyimides in quantitative yields. When bismaleimides, trismaleimides or mixtures thereof with maleimide end-caps are used as the dienophile, the resulting polyimides have glass transition temperatures (Tg) as high as 300 C. Polyimide films can be prepared by ultraviolet irradiation of high solids content varnishes of the monomers in a small amount of solvent, e.g., cyclohexanone, dimethyl formamide, N-methylpyrollidone and the like. These polyimides are characterized as having high glass transition temperatures, good mechanical properties and improved processing in the manufacture of adhesives, electronic materials and films.

  14. Polyesters by Photochemical Cyclopolymerization

    NASA Technical Reports Server (NTRS)

    Meador, Michael A. (Inventor)

    2002-01-01

    The polyesters of this invention are derived from a Diels-Alder cyclopolymerization of a photochemically generated bisdiene with dienophiles, such as di(acrylates), tri (acrylates), di(methacrylates), tri(methacrylates) and mixtures thereof with mono(methacrylates) or mono(acrylate) end-caps. Irradiation of one or more diketones produces two distinct hydroxy o-quinodimethane (photoenol) intermediates. These intermediates are trapped via a Diels-Alder cycloaddition with appropriate dienophiles, e.g., di(acrylates) to give the corresponding in polyesters quantitative yields. When di(acrylates), tri(acrylates) and di and tri(methacrylates) or mixtures thereof with monoacrylate end-caps are used as the dienophile, the resulting polyesters have glass transition temperatures (Tg) as high as 200 C. Polyesters films can be prepared by ultraviolet irradiation of high solids content varnishes of the monomers in a small amount of solvent, e.g., cyclohexanone, dimethyl formamide, N-methylpyrollidone and the like. These polyesters, i.e. polyesters are characterized as having high glass transition temperatures, good mechanical properties and improved processing in the manufacture of composites, adhesives, electronic materials and films.

  15. Photochemical Explanation for Sprites

    NASA Technical Reports Server (NTRS)

    Borucki, W. J.; Cuzzi, Jeffrey N. (Technical Monitor)

    1994-01-01

    Lightning-induced discharges occurring well above clouds showing vigorous lightning activity have recently been observed from high flying aircraft and the space shuttle. The nature of, and mechanisms that produce, these "sprites" are unknown. A numerical model has been constructed to investigate the possibility that ultraviolet light emitted by the hot discharge columns at the cloud top penetrate to sufficiently high altitudes that atomic and molecular species present at those altitudes are excited and then produce the visible light by fluorescence. calculations show that at altitudes above the clouds, strong absorption by oxygen and ozone removes most of radiation at photoreactive wavelengths with the exception of a narrow band at 200 nm. Further calculations are being performed to identify the species responsible for the radiation.

  16. Mesospheric ozone measurements by SAGE II

    NASA Astrophysics Data System (ADS)

    Chu, D. A.; Cunnold, D. M.

    1994-04-01

    SAGE II observations of ozone at sunrise and sunset (solar zenith angle = 90 deg) at approximately the same tropical latitude and on the same day exhibit larger concentrations at sunrise than at sunset between 55 and 65 km. Because of the rapid conversion between atomic oxygen and ozone, the onion-peeling scheme used in SAGE II retrievals, which is based on an assumption of constant ozone, is invalid. A one-dimensional photochemical model is used to simulate the diurnal variation of ozone particularly within the solar zenith angle of 80 deg - 100 deg. This model indicates that the retrieved SAGE II sunrise and sunset ozone values are both overestimated. The Chapman reactions produce an adequate simulation of the ozone sunrise/sunset ratio only below 60 km, while above 60 km this ratio is highly affected by the odd oxygen loss due to odd hydrogen reactions, particularly OH. The SAGE II ozone measurements are in excellent agreement with model results to which an onion peeling procedure is applied. The SAGE II ozone observations provide information on the mesospheric chemistry not only through the ozone profile averages but also from the sunrise/sunset ratio.

  17. Mesospheric ozone measurements by SAGE II

    NASA Technical Reports Server (NTRS)

    Chu, D. A.; Cunnold, D. M.

    1994-01-01

    SAGE II observations of ozone at sunrise and sunset (solar zenith angle = 90 deg) at approximately the same tropical latitude and on the same day exhibit larger concentrations at sunrise than at sunset between 55 and 65 km. Because of the rapid conversion between atomic oxygen and ozone, the onion-peeling scheme used in SAGE II retrievals, which is based on an assumption of constant ozone, is invalid. A one-dimensional photochemical model is used to simulate the diurnal variation of ozone particularly within the solar zenith angle of 80 deg - 100 deg. This model indicates that the retrieved SAGE II sunrise and sunset ozone values are both overestimated. The Chapman reactions produce an adequate simulation of the ozone sunrise/sunset ratio only below 60 km, while above 60 km this ratio is highly affected by the odd oxygen loss due to odd hydrogen reactions, particularly OH. The SAGE II ozone measurements are in excellent agreement with model results to which an onion peeling procedure is applied. The SAGE II ozone observations provide information on the mesospheric chemistry not only through the ozone profile averages but also from the sunrise/sunset ratio.

  18. An improved tropospheric ozone database retrieved from SCIAMACHY Limb-Nadir-Matching method

    NASA Astrophysics Data System (ADS)

    Jia, Jia; Rozanov, Alexei; Ladstätter-Weißenmayer, Annette; Ebojie, Felix; Rahpoe, Nabiz; Bötel, Stefan; Burrows, John

    2015-04-01

    Tropospheric ozone is one of the most important green-house gases and the main component of photochemical smog. It is either transported from the stratosphere or photochemically produced during pollution events in the troposphere that threaten the respiratory system. To investigate sources, transport mechanisms of tropospheric ozone in a global view, limb nadir matching (LNM) technique applied with SCIAMACHY instrument is used to retrieve tropospheric ozone. With the fact that 90% ozone is located in the stratosphere and only about 10% can be observed in the troposphere, the usage of satellite data requires highly qualified nadir and limb data. In this study we show an improvement of SCIAMACHY limb data as well as its influence on tropospheric ozone results. The limb nadir matching technique is also refined to increase the quality of the tropospheric ozone. The results are validated with ozone sonde measurements.

  19. Progress in understanding the formation of fine particulate matter and ground-level ozone in Pearl River Delta region, China

    NASA Astrophysics Data System (ADS)

    Wang, Xuemei; Wang, Tao; Zheng, Junyu; Shao, Min; Wang, Xinming

    2015-12-01

    In the past three decades, the Pearl River Delta of China has been suffered from severe air pollution due to the rapid increase in energy consumption associated with industrialization and urbanization of the region. The number of hazy days, increased from below 20 days in a year before 1970, to more than 150 days a year during 1980 and 2000. The ground-level ozone levels have also on the rise, with hourly concentration of 160 ppbv being observed in Guangzhou and 201 ppbv in nearby Hong Kong (Zhang et al., 2008). The ozone pollution has been difficult to reduce even in air quality improvement program for the Guangzhou Asian Games (Liu et al., 2013).

  20. Evidence for midwinter chemical ozone destruction over Antartica

    SciTech Connect

    Voemel, H.; Hoffmann, D.J.; Oltmans, S.J.; Harris, J.M.

    1995-09-01

    Two ozone profiles on June 15 and June 19, obtained over McMurdo, Antartica, showed a strong depletion in stratospheric ozone, and a simultaneous profile of water vapor on June 19 showed the first clear signs of dehydration. The observation of Polar Stratospheric Clouds (PSCs) beginning with the first sounding showing ozone depletion, the indication of rehydration layers, which could be a sign for recent dehydration, and trajectory calculations indicate that the observed low ozone was not the result of transport from lower latitudes. during this time the vortex was strongly distorted, transporting PSC processed air well into sunlit latitudes where photochemical ozone destruction may have occurred. The correlation of ozone depletion and dehydration indicates that water ice PSCs provided the dominant surface for chlorine activation. An analysis of the time when the observed air masses could have formed type II PSCs for the first time limits the time scale for the observed ozone destruction to about 4 days.

  1. Ozone-Induced Responses in Croton floribundus Spreng. (Euphorbiaceae): Metabolic Cross-Talk between Volatile Organic Compounds and Calcium Oxalate Crystal Formation

    PubMed Central

    Cardoso-Gustavson, Poliana; Bolsoni, Vanessa Palermo; de Oliveira, Debora Pinheiro; Guaratini, Maria Tereza Gromboni; Aidar, Marcos Pereira Marinho; Marabesi, Mauro Alexandre; Alves, Edenise Segala; de Souza, Silvia Ribeiro

    2014-01-01

    Here, we proposed that volatile organic compounds (VOC), specifically methyl salicylate (MeSA), mediate the formation of calcium oxalate crystals (COC) in the defence against ozone (O3) oxidative damage. We performed experiments using Croton floribundus, a pioneer tree species that is tolerant to O3 and widely distributed in the Brazilian forest. This species constitutively produces COC. We exposed plants to a controlled fumigation experiment and assessed biochemical, physiological, and morphological parameters. O3 induced a significant increase in the concentrations of constitutive oxygenated compounds, MeSA and terpenoids as well as in COC number. Our analysis supported the hypothesis that ozone-induced VOC (mainly MeSA) regulate ROS formation in a way that promotes the opening of calcium channels and the subsequent formation of COC in a fast and stable manner to stop the consequences of the reactive oxygen species in the tissue, indeed immobilising the excess calcium (caused by acute exposition to O3) that can be dangerous to the plant. To test this hypothesis, we performed an independent experiment spraying MeSA over C. floribundus plants and observed an increase in the number of COC, indicating that this compound has a potential to directly induce their formation. Thus, the tolerance of C. floribundus to O3 oxidative stress could be a consequence of a higher capacity for the production of VOC and COC rather than the modulation of antioxidant balance. We also present some insights into constitutive morphological features that may be related to the tolerance that this species exhibits to O3. PMID:25165889

  2. Ozone-induced responses in Croton floribundus Spreng. (Euphorbiaceae): metabolic cross-talk between volatile organic compounds and calcium oxalate crystal formation.

    PubMed

    Cardoso-Gustavson, Poliana; Bolsoni, Vanessa Palermo; de Oliveira, Debora Pinheiro; Guaratini, Maria Tereza Gromboni; Aidar, Marcos Pereira Marinho; Marabesi, Mauro Alexandre; Alves, Edenise Segala; de Souza, Silvia Ribeiro

    2014-01-01

    Here, we proposed that volatile organic compounds (VOC), specifically methyl salicylate (MeSA), mediate the formation of calcium oxalate crystals (COC) in the defence against ozone (O3) oxidative damage. We performed experiments using Croton floribundus, a pioneer tree species that is tolerant to O3 and widely distributed in the Brazilian forest. This species constitutively produces COC. We exposed plants to a controlled fumigation experiment and assessed biochemical, physiological, and morphological parameters. O3 induced a significant increase in the concentrations of constitutive oxygenated compounds, MeSA and terpenoids as well as in COC number. Our analysis supported the hypothesis that ozone-induced VOC (mainly MeSA) regulate ROS formation in a way that promotes the opening of calcium channels and the subsequent formation of COC in a fast and stable manner to stop the consequences of the reactive oxygen species in the tissue, indeed immobilising the excess calcium (caused by acute exposition to O3) that can be dangerous to the plant. To test this hypothesis, we performed an independent experiment spraying MeSA over C. floribundus plants and observed an increase in the number of COC, indicating that this compound has a potential to directly induce their formation. Thus, the tolerance of C. floribundus to O3 oxidative stress could be a consequence of a higher capacity for the production of VOC and COC rather than the modulation of antioxidant balance. We also present some insights into constitutive morphological features that may be related to the tolerance that this species exhibits to O3.

  3. Photochemical Aging of Organic Aerosol Particles

    NASA Astrophysics Data System (ADS)

    Nizkorodov, S. A.; Bateman, A. P.; Dailo, M.; Do, T.; Mang, S. A.; Pan, X.; Underwood, J. S.; Walser, M. L.

    2007-05-01

    Secondary Organic Aerosol (SOA) particles are produced in the atmosphere as a result of oxidation of volatile organic compounds (VOC). Primary Organic Aerosol (POA) particles are directly emitted in the atmosphere by their sources. This research focuses on the mechanisms of direct photochemical processes taking place in model SOA and POA particles, the role of such processes in aging of organic aerosol particles, and the effect of photochemistry on particles' physicochemical properties. To address these questions, artificial SOA and POA particles are investigated with several laboratory-based approaches relying on cavity ring-down spectroscopy and mass-spectrometry. SOA particles generated by dark oxidation of d-Limonene, alpha-Pinene, and beta-Pinene by ozone are all found to absorb radiation in the tropospheric actinic window. The UV absorption photolyzes SOA constituents resulting in a release of small VOC molecules back in the gas-phase, and considerable change in SOA chemical composition. For terpenes featuring a terminal double bond, the main SOA photolysis products are invariably found to be formaldehyde and formic acid. Similar observations are obtained for products of ozonolysis of thin films of unsaturated fatty acids and self-assembled monolayers of unsaturated alkenes. For the case of fatty acids, a very detailed mechanism of ozonolysis and subsequent photolysis is proposed. The photolytic activity is primarily attributed to organic peroxides and aldehydes. These results convincingly demonstrate that photochemical processes occurring inside SOA and POA particles age the particles on time scales that are shorter than typical lifetimes of aerosol particles in the atmosphere.

  4. Hairlike Percutaneous Photochemical Sensors

    NASA Technical Reports Server (NTRS)

    George, Thomas; Loeb, Gerald

    2004-01-01

    Instrumentation systems based on hairlike fiber-optic photochemical sensors have been proposed as minimally invasive means of detecting biochemicals associated with cancer and other diseases. The fiber-optic sensors could be mass-produced as inexpensive, disposable components. The sensory tip of a fiber-optic sensor would be injected through the patient's skin into subcutaneous tissue. A biosensing material on the sensory tip would bind or otherwise react with the biochemical(s) of interest [the analyte(s)] to produce a change in optical properties that would be measured by use of an external photonic analyzer. After use, a fiber-optic sensor could be simply removed by plucking it out with tweezers. A fiber-optic sensor according to the proposal would be of the approximate size and shape of a human hair, and its sensory tip would resemble a follicle. Once inserted into a patient's subcutaneous tissue, the sensor would even more closely resemble a hair growing from a follicle (see Figure 1). The biosensing material on the sensory tip could consist of a chemical and/or cells cultured and modified for the purpose. The biosensing material would be contained within a membrane that would cover the tip. If the membrane were not permeable by an analyte, then it would be necessary to create pores in the membrane that would be large enough to allow analyte molecules to diffuse to the biosensing material, but not so large as to allow cells (if present as part of the biosensing material) to diffuse out. The end of the fiber-optic sensor opposite the sensory tip would be inserted in a fiberoptic socket in the photonic analyzer.

  5. [Effects of synoptic type on surface ozone pollution in Beijing].

    PubMed

    Tang, Gui-qian; Li, Xin; Wang, Xiao-ke; Xin, Jin-yuan; Hu, Bo; Wang, Li-li; Ren, Yu-fen; Wang, Yue-Si

    2010-03-01

    Ozone (O), influenced by meteorological factors, is a primary gaseous photochemical pollutant during summer to fall in Beijing' s urban ambient. Continuous monitoring during July to September in 2008 was carried out at four sites in Beijing. Analyzed with synoptic type, the results show that the ratios of pre-low cylonic (mainly Mongolia cyclone) and pre-high anticylonic to total weather conditions are about 42% and 20%, illustrating the high-and low-ozone episodes, respectively. At the pre-low cylonic conditions, high temperature, low humidity, mountain and valley winds caused by local circulation induce average hourly maximum ozone concentration (volume fraction) up to 102.2 x 10(-9), negative correlated with atmospheric pressure with a slope of -3.4 x 10(-9) Pa(-1). The time of mountain wind changed to valley wind dominates the diurnal time of maximum ozone, generally around 14:00. At the pre-high anticylonic conditions, low temperature, high humidity and systematic north wind induce average hourly maximum ozone concentration (volume fraction) only 49.3 x 10(-9), the diurnal time of maximum ozone is deferred by continuous north wind till about 16:00. The consistency of photochemical pollution in Beijing region shows that good correlation exists between synoptic type and ozone concentration. Therefore, getting an eye on the structure and evolution of synoptic type is of great significances for forecasting the photochemical pollution.

  6. Rocket Ozone Data Recovery for Digital Archival

    NASA Astrophysics Data System (ADS)

    Hwang, S. H.; Krueger, A. J.; Hilsenrath, E.; Haffner, D. P.; Bhartia, P. K.

    2014-12-01

    Ozone distributions in the photochemically-controlled upper stratosphere and mesosphere were first measured using spectrometers on V-2 rockets after WWII. The IGY(1957-1958) spurred development of new optical and chemical instruments for flight on meteorological and sounding rockets. In the early 1960's, the US Navy developed an Arcas rocket-borne optical ozonesonde and NASA GSFC developed chemiluminescent ozonesonde onboard Nike_Cajun and Arcas rocket. The Navy optical ozone program was moved in 1969 to GSFC where rocket ozone research was expanded and continued until 1994 using Super Loki-Dart rocket at 11 sites in the range of 0-65N and 35W-160W. Over 300 optical ozone soundings and 40 chemiluminescent soundings were made. The data have been used to produce the US Standard Ozone Atmosphere, determine seasonal and diurnal variations, and validate early photochemical models. The current effort includes soundings conducted by Australia, Japan, and Korea using optical techniques. New satellite ozone sounding techniques were initially calibrated and later validated using the rocket ozone data. As satellite techniques superseded the rocket methods, the sponsoring agencies lost interest in the data and many of those records have been discarded. The current task intends to recover as much of the data as possible from the private records of the experimenters and their publications, and to archive those records in the WOUDC (World Ozone and Ultraviolet Data Centre). The original data records are handwritten tabulations, computer printouts that are scanned with OCR techniques, and plots digitized from publications. This newly recovered digital rocket ozone profile data from 1965 to 2002 could make significant contributions to the Earth science community in atmospheric research including long-term trend analysis.

  7. Potential ozone impacts of excess NO2 emissions from diesel particulate filters for on- and off-road diesel engines.

    PubMed

    Bar-llan, Amnon; Johnson, Jeremiah R; Denbleyker, Allison; Chan, Lit-Mian; Yarwood, Gregory; Hitchcock, David; Pinto, Joseph P

    2010-08-01

    This study considers potential impacts of increased use of diesel oxidation catalysts (DOCs) and catalyzed diesel particulate filters (DPFs) on ozone formation in the Dallas/ Fort Worth (DFW) area. There is concern that excess nitrogen dioxide (NO2) emissions from vehicles equipped with these devices could increase ambient ozone levels. The approach involved developing two scenarios for use of these devices, quantifying excess NO2 emissions in each scenario, and using a photochemical model to estimate the resulting ozone changes. In the "maximum penetration" scenario, DOC/DPF devices in a 2009 fleet of heavy-duty on-road trucks, school buses, and construction equipment were significantly increased by accelerating turnover of these vehicles and equipment to models that would require DOCs/DPFs. In the "realistic" scenario, current fractional usage of these devices was assessed for 2009. For both scenarios, excess NO2 emissions from DOCs/DPFs were estimated using U.S. Environmental Protection Agency's MOBILE6 and NONROAD emissions inventory modeling tools. The emissions analyses were used to adjust the DFW photochemical modeling emissions inventories and the Comprehensive Air Quality Model with extensions air quality model was rerun for the DFW area to determine the impact of these two scenarios on ozone formation. The maximum penetration scenario, which showed an overall reduction in oxides of nitrogen (NO(x)) because of the accelerated turnover of equipment to cleaner models, resulted in a net decrease in daily maximum 8-hr ozone of 4-5 parts per billion (ppb) despite the increase in NO2 emissions. The realistic scenario resulted in a small increase in daily maximum 8-hr ozone of less than 1 ppb for the DFW area. It was concluded that the excess NO2 emissions from DOC/DPF devices result in very small ozone impacts, particularly for the realistic scenario, in the DFW area. There are noticeable decreases in ozone for the maximum penetration scenario because NO

  8. Comparison of a 2D Photochemical Model to Data Using Statistical Trend Analysis

    NASA Technical Reports Server (NTRS)

    Bhartia, P. K. (Technical Monitor); Stolarski, Richard; Jackman, Charles; Fleming, Eric; Frith, Stacey Hollandsworth

    2002-01-01

    We have analyzed our 23-year merged ozone data set for variability and trends with a statistical time-series model. To assist in that analysis, we have analyzed the Goddard 2D photochemical model for the same time period with the same time-series model. Multiple runs of the photochemical model allow us to separate the effects of various terms on ozone, such as solar cycle and volcanic eruptions. We use this to help us separate those signals from each other in the data. We also used a smoothed version of the photochemical model's prediction of global ozone change in place of a simple linear trend. We find a number of interesting results. This particular photochemical model is more sensitive to chlorine perturbations than the atmosphere appears to be. It is less sensitive to solar cycle. It predicts an effect from the Pinatubo eruption that is nearly symmetric in the two hemispheres, but the data appears to have not responded to Pinatubo in the southern mid-latitudes. These results and their uncertainties will be discussed.

  9. Photochemical urban airshed modeling using diagnostic and dynamic meteorological fields

    NASA Astrophysics Data System (ADS)

    Godowitch, J. M.; Vukovich, J. M.

    1994-06-01

    Spatial pollutant patterns and peak concentrations are strongly influenced by meteorological parameters. Therefore, accurate hourly, gridded meteorological data sets are crucial inputs for photochemical modeling. An effort has been underway to apply both diagnostic and dynamic meteorological models in order to generate inputs needed in photochemical grid model simulations. The model being employed is a modified version of the Urban Airshed Model (UAM), which was designed to accept input files generated from both meteorological approaches. The diagnostic meteorological model (UAMMET) relies on routine or intensive measurements to generate hourly 3-D gridded fields of winds, temperatures, vertical eddy diffusivities, photolytic rates, and hourly spatially-varying fields of mixing height and deposition velocities. The diagnostic wind model (DWM) is a key module used generate 3-D wind fields. A dynamic mesoscale meteorological model (a numerical hydrostatic code equipped with a four-dimensional data assimilation technique) generates a gridded meteorological output file, which is post-processed through an interface program to create UAM-compatible wind and mixing height files. In this effort, both meteorological models were exercised in two different urban domains situated next to water bodies and with significant terrain features (i.e., greater metropolitan NYC and LA basin). Results of simulations with the modified UAM model were evaluated in order to investigate the impact on modeled ozone patterns and peak concentrations using inputs from these two meteorological approaches. A historical high ozone day in the NYC domain was simulated which exhibited a strong large scale flow pattern conducive to interurban transport along the northeastern coast. The evaluation results revealed absolute errors were comparable (about 22%) among the simulations, however, higher peak ozone was obtained using dynamically generated wind fields. Results from simulations of an ozone episode

  10. Ozone hole won`t worsen?

    SciTech Connect

    Kerr, R.A.

    1995-10-20

    The timing was fitting. Last week, the chemistry Nobel Prize went to the researchers who first linked chlorine-containing pollutants with stratospheric ozone loss. And last week brought the climax in the annual drama of Antarctic ozone destruction, which begins when the spring sun triggers the ozone-depleting reactions. Satellite and balloon observations showed that the ozone hole is about as deep and wide as ever. But new computer modeling of hole formation suggests that future holes will be no larger.

  11. Mars Ozone Mapping with MAVEN IUVS

    NASA Astrophysics Data System (ADS)

    Lefèvre, F.; Montmessin, F.; Schneider, N. M.; Deighan, J.; Jain, S.; Stewart, I. F.; Stiepen, A.; Chaffin, M.; McClintock, W. E.; Lo, D.; Clarke, J. T.; Holsclaw, G.; Jakosky, B. M.

    2015-12-01

    Ozone (O3) on Mars is a product of the CO2 photolysis by ultraviolet radiation. It is destroyed with a timescale of less than ~1 hour during the day by the H, OH, and HO2 radicals. This tight coupling between O3 and HOx species makes ozone a sensitive tracer of the odd hydrogen chemistry that stabilizes the CO2 atmosphere of Mars, and ozone measurements offer a powerful constraint for photochemical models. Ozone is also expected to be anti-correlated to water vapour, the source of hydrogen radicals HOx. At high latitudes in winter, the absence of H2O prevents the production of HOx and the chemical lifetime of ozone may increase up to several days. In these conditions, the ozone column abundance usually reaches its largest values of the Martian year and ozone turns into a measurable tracer of the polar vortex dynamics. The Imaging Ultraviolet Spectrograph (IUVS) is one of nine science instruments aboard the Mars Atmosphere and Volatile and Evolution (MAVEN) spacecraft. In the apoapse imaging phase, the spacecraft motion carries the IUVS lines-of-sight across the Martian disk while the scan mirror is used to make transverse swaths. This observation mode allows mapping the ozone vertically-integrated column from its signature in the solar ultraviolet flux backscattered by the surface and the atmosphere. This paper will present an overview of the first year of ozone mapping by IUVS. We will describe in particular the last Mars northern winter (2015) when the largest ozone columns have been observed since the beginning of the MAVEN mission. The data will be compared to prior Earth-based observations and to the SPICAM and MARCI ozone datasets. We will also test our quantitative understanding of the Martian ozone by comparing the IUVS observations to our three-dimensional model with photochemistry.

  12. Research opportunities in photochemical sciences

    SciTech Connect

    1996-07-01

    The workshop entitled {open_quotes}Research Opportunities in Photochemical Sciences{close_quotes} was initiated by the U.S. Department of Energy (DOE), Office of Energy Research (ER), Office of Basic Energy Sciences (BES), Division of Chemical Sciences. The National Renewable Energy Laboratory (NREL) in Golden, Colorado was requested by ER to host the workshop. It was held February 5-8, 1996 at the Estes Park Conference Center, Estes Park, CO, and at