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

EPA Science Inventory

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

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...

Analysis of photochemical pollution in summer and winter using a photochemical box model in the center of Tokyo, Japan.

PubMed

Huang, H; Akustu, Y; Arai, M; Tamura, M

2001-07-01

In order to give an effective and rapid analysis of the photochemical pollution and information for emission control strategies, a photochemical box model (PBM) was applied to one moderate summer episode, 11 July 1996, and one typical winter episode, 3 December 1996, in the center of Tokyo, Japan. The box model gave a good prediction of the photochemical pollution with minimal investment. As expected, the peak ozone in summer is higher than in winter. The NOx concentrations in winter are higher than those in summer. In summer, NO and NO2 have one peak in the morning. In winter, NO and NO2 show two peaks during the day. Three model runs including no reactions, a zero ozone boundary condition and dark reactions were conducted to understand the photochemical processes. The effects of emission reduction on the formation of the photochemical pollution in the center of Tokyo have been studied. The results show that the reduction of NMHC emission can decrease the ozone, however, the reduction of NOx emission can increase the ozone. It can be concluded that if the NOx emission are reduced, the reduction of NMHC should be more emphasized in order to decrease the ozone concentration in the center of Tokyo, Japan, especially the reduction of the NMHC from stationary source emission.

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.

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

NASA Technical Reports Server (NTRS)

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

1989-01-01

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

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.

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.

Ozone photochemical production in urban Shanghai, China: Analysis based on ground level observations

NASA Astrophysics Data System (ADS)

Ran, Liang; Zhao, Chunsheng; Geng, Fuhai; Tie, Xuexi; Tang, Xu; Peng, Li; Zhou, Guangqiang; Yu, Qiong; Xu, Jianmin; Guenther, Alex

2009-08-01

Ozone and its precursors were measured from 15 June 2006 to 14 June 2007 at an urban site in Shanghai and used to characterize photochemical oxidant production in this region. During the observation period, ozone displays a seasonal variation with a maximum in spring. Observed nitrogen oxides (NOx) and carbon monoxide (CO) reached a maximum in winter and a minimum in summer. NOx and CO has a similar double-peak diurnal cycle, implying that they are largely of motor vehicle origin. Total nonmethane organic compounds (NMOC) concentrations averaged over the morning, and the 24-hour periods have a large day-to-day variation with no apparent seasonal cycle. Aromatics play a dominant role in contributing to total NMOC reactivity and ozone-forming potential. Anthropogenic NMOC of diverse sources are major components of total NMOC and consist mainly of moderate and low reactivity species. In contrast, relatively low levels of biogenic NMOC concentrations were observed in urban Shanghai. The early morning NMOC/NOx ratios are typically below 8:1 with an average of around 4:1, indicating that the sampling location is situated in a NMOC-limited regime. Model simulations confirm that potential photochemical ozone production in Shanghai is NMOC-sensitive. It is presently difficult to predict the impact of future human activities, such as the increase of automobiles and vegetation-covered landscapes and the reduction of aerosol on ozone pollution in the fast developing megacities of China, and additional studies are needed to better understand the highly nonlinear ozone problem.

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.

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

EPA Science Inventory

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

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

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

Kim, Saewung; Kim, So-Young; Lee, Meehye

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, andmore » 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

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.

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

NASA Technical Reports Server (NTRS)

Thompson, Anne M.; Stewart, Richard W.

1991-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2017-05-01

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

Photochemical modeling and analysis of meteorological parameters during ozone episodes in Kaohsiung, Taiwan

NASA Astrophysics Data System (ADS)

Chen, K. S.; Ho, Y. T.; Lai, C. H.; Chou, Youn-Min

The events of high ozone concentrations and meteorological conditions covering the Kaohsiung metropolitan area were investigated based on data analysis and model simulation. A photochemical grid model was employed to analyze two ozone episodes in autumn (2000) and winter (2001) seasons, each covering three consecutive days (or 72 h) in the Kaohsiung City. The potential influence of the initial and boundary conditions on model performance was assessed. Model performance can be improved by separately considering the daytime and nighttime ozone concentrations on the lateral boundary conditions of the model domain. The sensitivity analyses of ozone concentrations to the emission reductions in volatile organic compounds (VOC) and nitrogen oxides (NO x) show a VOC-sensitive regime for emission reductions to lower than 30-40% VOC and 30-50% NO x and a NO x-sensitive regime for larger percentage reductions. Meteorological parameters show that warm temperature, sufficient sunlight, low wind, and high surface pressure are distinct parameters that tend to trigger ozone episodes in polluted urban areas, like Kaohsiung.

Products of BVOC oxidation: ozone and organic aerosols

NASA Astrophysics Data System (ADS)

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

2015-04-01

Biogenic Volatile Organic Compounds (BVOC) are important precursors in photochemical O3 and secondary organic aerosol (SOA) formation. We conducted a series of laboratory experiments with OH-induced oxidation of monoterpenes to elucidate pathways and efficiencies of O3 and SOA formation. At high NOx conditions ([BVOC] / [NOx] < 7 ppbC / ppb) photochemical ozone formation was observed. For -pinene as individual BVOC as well as for the monoterpene mixes emitted from different plant species we observed increasing ozone formation with increasing [NOX]. Between 2 and 3 O3-molecules were formed from 1 monoterpene when ozone formation was BVOC limited. Under such high NOX conditions, new particle formation was suppressed. Increasing [BVOC] / [NOX] ratios caused increasing efficiency of new particle formation indicating that peroxy radicals are the key intermediates in both, photochemical ozone- and new particle formation. The classical chemistry of peroxy radicals is well established (e.g. Master Chemical Mechanism). Peroxy radicals are produced by addition of molecular oxygen to the alkyl radical formed after OH attack at the BVOC. They either react with NO which leads to ozone formation or they react with other peroxy radicals and form chemically stable products (hydroperoxides, alkoholes and ketones). Much less knowledge exists on such reactions for Highly Oxidized Peroxy Radicals, (HOPR). Such HOPR were observed during ozonolysis of several volatiles and, in case of monoterpenes as precursors, they can contain more than 12 Oxygen atoms (Mentel et al., 2015). Although the OH-initiated formation of HOPR is yet not fully understood, their basic gas phase reactions seem to follow classical photochemical rules. In reactions with NO they can act as precursor for O3 and in reactions with other HOPR or with classical less oxidized peroxy radicals they can form highly oxidized stable products and alkoxy radicals. In addition, HOPR-HOPR reactions lead to the formation of

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

EPA Science Inventory

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

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

EPA Science Inventory

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

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

NASA Technical Reports Server (NTRS)

Berntsen, Terje; Isaksen, Ivar S. A.

1994-01-01

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

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

EPA Science Inventory

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

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

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

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.

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

NASA Astrophysics Data System (ADS)

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

2017-04-01

/NOx ratios being well above 20. Hence, ozone production rates are expected to be controlled by regional NOx emissions and their complex interplay with both natural and anthropogenic sources of VOCs. The quantitative contribution of aromatic VOCs to ozone formation in urban areas and in Russian regions along the railway is estimated. The greatest impact of aromatic VOCs to ozone formation (up to 7.5 ppb of O3) is obtained in the large cities along the Trans-Siberian Railway, with the highest concentrations of aromatic VOCs (1-1.7 ppb) and nitrogen oxides (> 20 ppb) being observed. The results show a significant contribution of anthropogenic emissions of VOCs to the photochemical ozone generation (30-50%) in the large cities along the Trans-Siberian railway in hot and dry weather conditions against natural isoprene emissions determining the regional balance of ground-level ozone in summer. This study was supported by the Russian Science Foundation (grant no. 14-47-00049) and by the Russian Foundation for Basic Research (grant no. 16-35-00158). References: 1. Xie, X., Shao, M., Liu, Y., Lu, S., Chang, C. C., and Chen, Z. M. // Atmos. Environ., 2008, 42, pp. 6000-6010. 2. Guenther, A., Geron, C., Pierce, T., Lamb, B., Harley, P., Fall, R. // Atmospheric Environment, 2000, 34, pp. 2205-2230. 3. Dreyfus, G. B., Schade G. W., Goldstein A. H. // J. Geophys. Res., 2002, 107(D19): 4365, doi:10.1029/2001JD001490.

Photo-chemical transport modelling of tropospheric ozone: A review

NASA Astrophysics Data System (ADS)

Sharma, Sumit; Sharma, Prateek; Khare, Mukesh

2017-06-01

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

Impact of Enhanced Ozone Deposition and Halogen Chemistry on Tropospheric Ozone over the Northern Hemisphere.

PubMed

Sarwar, Golam; Gantt, Brett; Schwede, Donna; Foley, Kristen; Mathur, Rohit; Saiz-Lopez, Alfonso

2015-08-04

Fate of ozone in marine environments has been receiving increased attention due to the tightening of ambient air quality standards. The role of deposition and halogen chemistry is examined through incorporation of an enhanced ozone deposition algorithm and inclusion of halogen chemistry in a comprehensive atmospheric modeling system. The enhanced ozone deposition treatment accounts for the interaction of iodide in seawater with ozone and increases deposition velocities by 1 order of magnitude. Halogen chemistry includes detailed chemical reactions of organic and inorganic bromine and iodine species. Two different simulations are completed with the halogen chemistry: without and with photochemical reactions of higher iodine oxides. Enhanced deposition reduces mean summer-time surface ozone by ∼3% over marine regions in the Northern Hemisphere. Halogen chemistry without the photochemical reactions of higher iodine oxides reduces surface ozone by ∼15% whereas simulations with the photochemical reactions of higher iodine oxides indicate ozone reductions of ∼48%. The model without these processes overpredicts ozone compared to observations whereas the inclusion of these processes improves predictions. The inclusion of photochemical reactions for higher iodine oxides leads to ozone predictions that are lower than observations, underscoring the need for further refinement of the halogen emissions and chemistry scheme in the model.

Better estimates of Entrainment Mixing, Subsidence, and Photochemical Ozone Production using Aircraft and WRF data during the California Baseline Ozone Transport Study (CABOTS)

NASA Astrophysics Data System (ADS)

Trousdell, J.; Faloona, I. C.

2017-12-01

In situ flight data collected in the San Joaquin Valley of California during the summer of 2016 is used to measure boundary layer entrainment rates, ozone photochemical production, regional methane and NOx emissions. The San Joaquin Valley is plagued with air quality issues including a high frequency of ozone exceedances in the summer and an aerosol issue in the winter exacerbated by a complex mesoscale environment with a different mountain range on three sides creating an effective cul-de-sac which limits outflow and ventilation. In addition, higher elevation air brought over top of the valley can influence the valley air by entrainment at the top of the turbulent daytime atmospheric boundary layer. The flights were conducted during the California Baseline Ozone Transport Study (CABOTS). Flights are valley wide between the cities of Fresno and Visalia with a thorough probing of the atmospheric boundary layer (ABL) including vertical profiling to diagnose the ABL height and its growth rate. Entrainment velocities, which are the parameterized mixing of free tropospheric air into the boundary layer, are determined by a detailed budget equation of the inversion height. A novel scalar budgeting technique is then applied to expose residual terms of individual equations that amount to ozone photochemical production and emission rates, including; NOx and methane. The budget equations are closed out by our predicted entrainment velocities, time rate of change and horizontal advection all determined via flight data. The results of our NOx budget suggests that the California Air Resources Board emission estimates for soil NOx is grossly underestimated. A strong relationship between entrainment rates and vertical wind shear has been observed, suggesting a significant contribution to entrainment driven by vertical shear compared to the surface buoyancy flux which drives the turbulent vertical motions in the boundary layer.

Solar-QBO Interaction and Its Impact on Stratospheric Ozone in a Zonally Averaged Photochemical Transport Model of the Middle Atmosphere

DTIC Science & Technology

2007-08-28

Solar- QBO interaction and its impact on stratospheric ozone in a zonally averaged photochemical transport model of the middle atmosphere J. P...investigate the solar cycle modulation of the quasi-biennial oscillation ( QBO ) in stratospheric zonal winds and its impact on stratospheric ozone with an...updated version of the zonally averaged CHEM2D middle atmosphere model. We find that the duration of the westerly QBO phase at solar maximum is 3 months

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

PubMed

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

2007-04-01

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

Secondary organic aerosol and ozone formation from photo-oxidation of unburned diesel fuel in a surrogate atmospheric environment

NASA Astrophysics Data System (ADS)

Li, Weihua; Cocker, David R.

2018-07-01

Diesel fuel is a complex mixture of intermediate volatility organic compounds (IVOCs). Previous studies focused on secondary organic aerosol (SOA) and ozone formation from photo-oxidation of organic vapor from diesel exhaust and their components such as aromatics and heavy alkanes. However, there are few studies on atmospheric behavior of unburnt diesel. Therefore, in this study, ten unburnt #2 commercial diesel samples and one FACE9A research diesel fuel were photo-oxidized in the University of California Riverside, College of Engineering-Center for Environmental Research & Technology dual environmental chambers to investigate their SOA and ozone production potential. Photochemical aging rapidly produced significant SOA (yield ∼20.3-37.7%) in the presence of a surrogate reactive organic gas (ROG) mixture used to mimic urban atmospheric reactivity. SOA yields were consistent with n-Heptadecane yields under similar conditions. Doubling NOx concentrations within relevant urban concentration levels enhanced SOA formation by 33% and ozone formation by 48%. SOA formation in this study was approximately fourteen times higher than previously reported for very high NOx conditions. An SOA experiment designed to mimic the previous work achieved similar yields to the earlier work. SOA formed under urban relevant NOx concentrations were consistent with semi-volatile-oxygenated organic aerosol (SV-OOA) and underwent little further chemical processing once produced.

The photochemical pollution episode of 5-16 July 1983 in North-West England

NASA Astrophysics Data System (ADS)

Colbeck, I.; Harrison, Roy M.

Ground level ozone, NO x and specific C 2-C 6 hydrocarbon measurements from a rural site in N-W England during a photochemical pollution episode are presented. Maximum hourly ozone concentrations exceeded 80 ppb for ten consecutive days with a maximum of 156 ppb. Mid-morning ozone concentrations were found to be indicative of the amount of ozone from continental sources. The air mass trajectories, total NMHC and alkane : alkene ratios all indicate that in the early to middle stages of the episode the air had been exposed to recent precursor emissions relative to more aged air before and after this period. The measurements are compared with the predictions of recent theoretical models of ozone formation over England.

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.

ASSESSMENT OF THE ROLE OF NITROGEN OXIDES IN NONURBAN OZONE FORMATION

EPA Science Inventory

This assessment is the fourth and final assessment of technical issues related to ozone and other photochemically generated products formed in the atmosphere requested by the Office of Air Quality Planning and Standards. A survey of information available on the role of NO(sup x) ...

Photochemical and Spectroscopic Effects Resulting from Excimer Laser Excitation.

NASA Astrophysics Data System (ADS)

Wang, Xuan Xiao

I. Photochemical production of ozone from pure oxygen using excimer lasers. Production of ozone was observed from experiments when oxygen was under a broadband pulsed KrF laser radiation. The production process was found to be autocatalytic. Mechanisms for the ozone formation were proposed. Experimental results over a range of oxygen pressure and laser pulse energy (irradiance) provided evidences in favor of the proposed mechanisms. Experiments were also numerically modeled. Good agreement between the experimental and the numerical results were observed, which provided further evidence to support the proposed mechanisms. Cross sections for some photochemical processes in the mechanisms were estimated. Production of ozone from pure oxygen under a ArF excimer laser radiation (193 nm) was also studied and numerically modeled. Effects of ambient water vapor on ozone production were investigated. Experimental results showed a fast ozone destruction when water vapor was present in the cell. However, numerical results obtained from the well-known OH and HO _2 chain ozone destruction mechanism predicted a slower ozone destruction. Possible reasons for the discrepancy are discussed. II. Resonance-enhanced multiphoton ionization of N_2 at 193 and 248 nm detected by N_sp{2}{+} fluorescence. Using a broadband excimer laser operating at 193 and 248 nm multiphoton ionization at high pressures in air and pure nitrogen has been detected by fluorescence from N_sp{2}{+} in the B-X firstnegative system. Measurements of the fluorescence intensity as a function of beam irradiance indicate resonance in N_2 at the energy of two 193 nm photons (2 + 1 REMPI) and three 248 nm photons (3 + 1 REMPI). Possible intermediate states are discussed. III. Excimer laser-induced fluorescence from some organic solvents. Fluorescence was observed from vapor phase benzene, toluene, p-xylene, benzyl chloride, methyl benzoate, acetic anhydride, ether, methanol, ethyl acetone, acetone, and 2-butanone using

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 ...

Photochemical Modeling Applications

EPA Pesticide Factsheets

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

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

NASA Technical Reports Server (NTRS)

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

1991-01-01

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

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.

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

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

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

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, NO x, SO 2,more » 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 HO x (OH, HO 2, and RO 2) 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 HO x distributions, especially OH levels (up to 2.5 times), and (2) radical destruction (HO 2 + HO 2 or HO 2 + RO 2) could be more efficient than radical recycling (RO 2 + NO), especially in the afternoon. Implications of the uncertainties in radical chemistry are discussed with respect to ozone–VOC–NO x sensitivity and VOC oxidation product formation rates. Overall, the NO x limited regime is assessed except for the morning hours (8 a.m. to 12 p.m. local standard time), but the degree

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

DOE PAGES

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

2015-04-29

Rapid urbanization and economic development in East Asia in past decades has led to photochemical air pollution problems such as excess photochemical ozone and aerosol formation. Asian megacities such as Seoul, Tokyo, Shanghai, Guangzhou, and Beijing are surrounded by densely forested areas, and recent research has consistently demonstrated the importance of biogenic volatile organic compounds (VOCs) from vegetation in determining oxidation capacity in the suburban Asian megacity regions. Uncertainties in constraining tropospheric oxidation capacity, dominated by hydroxyl radical, undermine our ability to assess regional photochemical air pollution problems. We present an observational data set of CO, NO x, SO 2,more » 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 HO x (OH, HO 2, and RO 2) 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 HO x distributions, especially OH levels (up to 2.5 times), and (2) radical destruction (HO 2 + HO 2 or HO 2 + RO 2) could be more efficient than radical recycling (RO 2 + NO), especially in the afternoon. Implications of the uncertainties in radical chemistry are discussed with respect to ozone–VOC–NO x sensitivity and VOC oxidation product formation rates. Overall, the NO x limited regime is assessed except for the morning hours (8 a.m. to 12 p.m. local standard time), but the degree

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

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. Copyright © 2015 Elsevier Ltd. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

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.

Diagnostic analysis of two-dimensional monthly average ozone balance with Chapman chemistry

NASA Technical Reports Server (NTRS)

Stolarski, Richard S.; Jackman, Charles H.; Kaye, Jack A.

1986-01-01

Chapman chemistry has been used in a two-dimensional model to simulate ozone balance phenomenology. The similarity between regions of ozone production and loss calculated using Chapman chemistry and those computed using LIMS and SAMS data with a photochemical equilibrium model indicate that such simplified chemistry is useful in studying gross features in stratospheric ozone balance. Net ozone production or loss rates are brought about by departures from the photochemical equilibrium (PCE) condition. If transport drives ozone above its PCE condition, then photochemical loss dominates production. If transport drives ozone below its PCE condition, then photochemical production dominates loss. Gross features of ozone loss/production (L/P) inferred for the real atmosphere from data are also simulated using only eddy diffusion. This indicates that one must be careful in assigning a transport scheme for a two-dimensional model that mimics only behavior of the observed ozone L/P.

PHOTOCHEMICAL REACTIVITY OF PERCHLOROETHYLENE

EPA Science Inventory

Perchloroethylene (PCE), a solvent used in dry cleaning, has been suspected of contributing significantly to photochemical ozone/oxidant (O3/Ox) problems in urban atmospheres. Past evidence, however, was neither complete nor consistent. To interpret more conclusively the past evi...

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

Treesearch

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

2003-01-01

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

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

Radiative-photochemical response of the mesosphere to dynamical forcing

NASA Technical Reports Server (NTRS)

Frederick, J. E.

1981-01-01

Combination of the chemical continuity equation for odd oxygen with the second law of thermodynamics yields analytic solutions which describe the coupled behavior of temperature and ozone perturbations in response to an externally specified forcing. The results appear in a form which allows easy physical interpretation of the coupling between radiative and photochemical processes. When the forcing is chosen to mimic a planetary scale wave, the theory shows that photochemical acceleration of radiative damping reduces the amplitude of the temperature perturbation by an amount which increases with the wave period. Although ozone fluctuations are anti-correlated with those in temperature, minima in ozone do not coincide exactly in longitude with temperature maxima. The percentage variation in ozone increases upward and is always larger than that in temperature at the same pressure. This demonstrates that variations in ozone on constant pressure surfaces may serve as a sensitive indicator of wave activity in the mesosphere.

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

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

Jackman, C.H.; Douglass, A.R., Chandra, S.; Stolarski, R.S.

1991-03-20

Eight years of NMC (National Meteorological Center) temperature and SBUV (solar backscattered ultraviolet) ozone data were used to calculate the monthly mean heating rates and residual circulation for use in a two-dimensional photochemical model in order to examine the interannual variability of modeled ozone. Fairly good correlations were found in the interannual behavior of modeled and measured SBUV ozone in the upper stratosphere at middle to low latitudes, where temperature dependent photochemistry is thought to dominate ozone behavior. The calculated total ozone is found to be more sensitive to the interannual residual circulation changes than to the interannual temperature changes.more » The magnitude of the modeled ozone variability is similar to the observed variability, but the observed and modeled year to year deviations are mostly uncorrelated. The large component of the observed total ozone variability at low latitudes due to the quasi-biennial oscillation (QBO) is not seen in the modeled total ozone, as only a small QBO signal is present in the heating rates, temperatures, and monthly mean residual circulation. Large interanual changes in tropospheric dynamics are believed to influence the interannual variability in the total ozone, especially at middle and high latitudes. Since these tropospheric changes and most of the QBO forcing are not included in the model formulation, it is not surprising that the interannual variability in total ozione is not well represented in the model computations.« less

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

NASA Astrophysics Data System (ADS)

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

2012-05-01

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

Photochemical Assessment Monitoring Stations (PAMS)

EPA Pesticide Factsheets

Photochemical Assessment Monitoring Stations (PAMS). This file provides information on the numbers and distribution (latitude/longitude) of air monitoring sites which measure ozone precursors (approximately 60 volatile hydrocarbons and carbonyl), as required by the 1990 Clean Air Act Amendments, in areas with persistently high ozone levels (mostly large metropolitan areas). In these areas, the States have established ambient air monitoring sites which collect and report detailed data for volatile organic compounds, nitrogen oxides, ozone and meteorological parameters. This file displays 199 monitoring sites reporting measurements for 2010. A wide range of related monitoring site attributes is also provided.

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)

Photochemical Haze Formation in the Atmospheres of Super-Earths and Mini-Neptunes

NASA Technical Reports Server (NTRS)

He, Chao; Hoerst, Sarah M.; Lewis, Nikole K.; Yu, Xinting; Moses, Julianne I.; Kempton, Eliza M.- R.; Marley, Mark S.; McGuiggan, Patricia; Morley, Caroline V.; Valenti, Jeff A.;

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.

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

PubMed

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

2011-11-01

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

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

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.

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

NASA Astrophysics Data System (ADS)

Stricker, J.; Parker, J. G.

1984-12-01

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

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

PubMed

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

2015-04-01

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

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…

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.

Factors dominating 3-dimensional ozone distribution during high tropospheric ozone period.

PubMed

Chen, Xiaoyang; Liu, Yiming; Lai, Anqi; Han, Shuangshuang; Fan, Qi; Wang, Xuemei; Ling, Zhenhao; Huang, Fuxiang; Fan, Shaojia

2018-01-01

Data from an in situ monitoring network and five ozone sondes are analysed during August of 2012, and a high tropospheric ozone episode is observed around the 8th of AUG. The Community Multi-scale Air Quality (CMAQ) model and its process analysis tool were used to study factors and mechanisms for high ozone mixing ratio at different levels of ozone vertical profiles. A sensitive scenario without chemical initial and boundary conditions (ICBCs) from MOZART4-GEOS5 was applied to study the impact of stratosphere-troposphere exchange (STE) on vertical ozone. The simulation results indicated that the first high ozone peak near the tropopause was dominated by STE. Results from process analysis showed that: in the urban area, the second peak at approximately 2 km above ground height was mainly caused by local photochemical production. The third peak (near surface) was mainly caused by the upwind transportation from the suburban/rural areas; in the suburban/rural areas, local photochemical production of ozone dominated the high ozone mixing ratio from the surface to approximately 3 km height. Furthermore, the capability of indicators to distinguish O 3 -precursor sensitivity along the vertical O 3 profiles was investigated. Two sensitive scenarios, which had cut 30% anthropogenic NO X or VOC emissions, showed that O 3 -precursor indicators, specifically the ratios of O 3 /NOy, H 2 O 2 /HNO 3 or H 2 O 2 /NO Z , could partly distinguish the O 3 -precursor sensitivity between VOCs-sensitive and NOx-sensitive along the vertical profiles. In urban area, the O 3 -precursor relationship transferred from VOCs-sensitive within the boundary layer to NOx-sensitive at approximately 1-3 km above ground height, further confirming the dominant roles of transportation and photochemical production in high O 3 peaks at the near-ground layer and 2 km above ground height, respectively. Copyright © 2017 Elsevier Ltd. All rights reserved.

Aqueous-Phase Photochemical Production of Oxidants in Atmospheric Waters.

NASA Astrophysics Data System (ADS)

Allen, John Morrison

1992-01-01

The photochemical formation and subsequent reactions of oxidants plays an important role in the overall chemistry of the atmosphere. Much of the interest in atmospheric oxidation reactions has been fueled by the environmental consequences of the oxidation of sulfur dioxide (SO _2) forming sulfuric acid (H_2 SO_4). Oxidation reactions also play a crucial role in other atmospheric chemical transformations such as: (1) the destruction of tropospheric ozone, (2) redox cycling of transition metals, and (3) oxidation of organic compounds. Much of the research pertaining to atmospheric oxidant formation and the reactions that these oxidants undergo has centered upon gas-phase photochemical oxidant formation and: (1) subsequent reactions in the gas phase, or (2) partitioning of oxidants into cloud and fog drops and subsequent reactions in the aqueous phase. Only a very limited amount of data is available concerning aqueous -phase photochemical sources of oxidants in cloud and fog drops. The focus of one aspect of the work presented in this dissertation is upon the aqueous-phase sunlight photochemical formation of oxidants in authentic cloud and fog water samples from across the United States and Canada. It will be demonstrated that atmospheric waters typically absorb solar ultraviolet radiation at wavelengths ranging from 290 to 340 nm. This absorption is due to the presence of chemical constituents in the cloud and fog waters that contain chromophoric functional groups that give rise to the formation of: (1) singlet molecular oxygen O_2(^1Delta_ {rm g}), (2) peroxyl radicals (HO _2cdot and RO_2 cdot), (3) peroxides (HOOH, ROOH, and ROOR '), and (4) hydroxyl radical ( cdotOH). This work will demonstrate that aqueous-phase photochemical reactions are a significant and in some cases dominant source of these oxidants in cloud and fog drops. The transition metal catalyzed oxidation of SO _2 to H_2SO _4 by molecular oxygen has been extensively studied. This reaction is thought

Suppression of new particle formation from monoterpene oxidation by NOx

NASA Astrophysics Data System (ADS)

Wildt, J.; Mentel, T. F.; Kiendler-Scharr, A.; Hoffmann, T.; Andres, S.; Ehn, M.; Kleist, E.; Müsgen, P.; Rohrer, F.; Rudich, Y.; Springer, M.; Tillmann, R.; Wahner, A.

2013-10-01

The impact of nitrogen oxides (NOx = NO + NO2) on new particle formation (NPF) and on photochemical ozone production from real plant volatile organic compound (BVOC) emissions was studied in a laboratory set up. At high NOx conditions (BVOC/NOx < 7, NOx > 23 ppb) no new particles were formed. Instead photochemical ozone formation was observed resulting in higher hydroxyl radical (OH) and lower nitrogen monoxide (NO) concentrations. As soon as [NO] was reduced to below 1 ppb by OH reactions, NPF was observed. Adding high amounts of NOx caused NPF orders of magnitude slower than in analogous experiments at low NOx conditions (NOx ~ 300 ppt), although OH concentrations were higher. Varying NO2 photolysis enabled showing that NO was responsible for suppression of NPF suggesting that peroxy radicals are involved in NPF. The rates of NPF and photochemical ozone production were related by power law dependence with an exponent of approximately -2. This exponent indicated that the overall peroxy radical concentration must have been the same whenever NPF appeared. Thus permutation reactions of first generation peroxy radicals cannot be the rate limiting step in NPF from monoterpene oxidation. It was concluded that permutation reactions of higher generation peroxy radical like molecules limit the rate of new particle formation. In contrast to the strong effects on the particle numbers, the formation of particle mass was less sensitive to NOx concentrations, if at all. Only at very high NOx concentrations yields were reduced by about an order of magnitude.

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

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.

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

PubMed

Lv, Juan; Wang, Lin; Li, Yongmei

2017-08-01

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

Suppression of new particle formation from monoterpene oxidation by NOx

NASA Astrophysics Data System (ADS)

Wildt, J.; Mentel, T. F.; Kiendler-Scharr, A.; Hoffmann, T.; Andres, S.; Ehn, M.; Kleist, E.; Müsgen, P.; Rohrer, F.; Rudich, Y.; Springer, M.; Tillmann, R.; Wahner, A.

2014-03-01

The impact of nitrogen oxides (NOx = NO + NO2) on new particle formation (NPF) and on photochemical ozone production from real plant volatile organic compound (BVOC) emissions was studied in a laboratory setup. At high NOx conditions ([BVOC] / [NOx] < 7, [NOx] > 23 ppb) new particle formation was suppressed. Instead, photochemical ozone formation was observed resulting in higher hydroxyl radical (OH) and lower nitrogen monoxide (NO) concentrations. When [NO] was reduced back to levels below 1 ppb by OH reactions, NPF was observed. Adding high amounts of NOx caused NPF to be slowed by orders of magnitude compared to analogous experiments at low NOx conditions ([NOx] ~300 ppt), although OH concentrations were higher. Varying NO2 photolysis enabled showing that NO was responsible for suppression of NPF. This suggests that peroxy radicals are involved in NPF. The rates of NPF and photochemical ozone production were related by power law dependence with an exponent approaching -2. This exponent indicated that the overall peroxy radical concentration must have been similar when NPF occurred. Thus, permutation reactions of first-generation peroxy radicals cannot be the rate limiting step in NPF from monoterpene oxidation. It was concluded that permutation reactions of higher generation peroxy-radical-like intermediates limit the rate of new particle formation. In contrast to the strong effects on the particle numbers, the formation of particle mass was substantially less sensitive to NOx concentrations. If at all, yields were reduced by about an order of magnitude only at very high NOx concentrations.

Distribution and urban-suburban differences in ground-level ozone and its precursors over Shenyang, China

NASA Astrophysics Data System (ADS)

Liu, Ningwei; Ren, Wanhui; Li, Xiaolan; Ma, Xiaogang; Zhang, Yunhai; Li, Bingkun

2018-03-01

Hourly mixing ratio data of ground-level ozone and its main precursors at ambient air quality monitoring sites in Shenyang during 2013-2015 were used to survey spatiotemporal variations in ozone. Then, the transport of ozone and its precursors among urban, suburban, and rural sites was examined. The correlations between ozone and some key meteorological factors were also investigated. Ozone and O x mixing ratios in Shenyang were higher during warm seasons and lower during cold ones, while ozone precursors followed the opposite cycle. Ozone mixing ratios reached maximum and minimum values in the afternoon and morning, respectively, reflecting the significant influence of photochemical production during daytime and depletion via titration during nighttime. Compared to those in downtown Shenyang, ozone mixing ratios were higher and the occurrence of peak values were later in suburban and rural areas downwind of the prevailing wind. The differences were most significant in summer, when the ozone mixing ratios at one suburban downwind site reached a maximum value of 35.6 ppb higher than those at the downtown site. This suggests that photochemical production processes were significant during the transport of ozone precursors, particularly in warm seasons with sufficient sunlight. Temperature, total radiation, and wind speed all displayed positive correlations with ozone concentration, reflecting their important role in accelerating ozone formation. Generally, the correlations between ozone and meteorological factors were slightly stronger at suburban sites than in urban areas, indicating that ozone levels in suburban areas were more sensitive to these meteorological factors.

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

PubMed

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

2015-12-15

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

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

PubMed

Lv, Juan; Li, Yong M

2018-06-07

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

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.

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

PubMed

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

2017-10-01

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

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

PubMed

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

2016-02-01

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

An insight into the formation of severe ozone episodes: modeling the 21/03/01 event in the ESCOMPTE region

NASA Astrophysics Data System (ADS)

Lasry, Fanny; Coll, Isabelle; Buisson, Emmanuel

2005-03-01

High ozone concentrations are observed more and more frequently in the lower troposphere. The development of such polluted episodes is linked to a complex set of chemical, physical and dynamical parameters that interact with each other. To improve air quality, it is necessary to understand and quantify the role of all these processes on the intensity of ozone formation. The ESCOMPTE program, especially dedicated to the numerical simulation of photochemical episodes, offers an ideal frame to investigate details of the roles of many of these processes through 3D modeling. This paper presents the analysis, with a 3D eulerian model, of a severe and local episode of ozone pollution that occurred on the 21st of March 2001 in the ESCOMPTE region. This episode is particularly interesting due to the intensity of the observed ozone peaks (450 μg/m 3 during 15 mn) but also because it did not occur in summer but at the beginning of spring. As part of the premodeling work of the ESCOMPTE program, this study focuses on the sensitivity of the simulated ozone peaks to various chemical and physical phenomena (long-range transport, industrial emissions, local dynamic phenomena…) to determine their influence on the rise of high local photooxidant concentrations and to better picture the photochemistry of the ESCOMPTE region. Through sensitivity tests to dynamical calculation resolution and emissions, this paper shows how the combination of sea and pond breezes with emissions of reactive VOCs can generate local intense ozone peaks.

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.

Open burning of rice, corn and wheat straws: primary emissions, photochemical aging, and secondary organic aerosol formation

NASA Astrophysics Data System (ADS)

Fang, Zheng; Deng, Wei; Zhang, Yanli; Ding, Xiang; Tang, Mingjin; Liu, Tengyu; Hu, Qihou; Zhu, Ming; Wang, Zhaoyi; Yang, Weiqiang; Huang, Zhonghui; Song, Wei; Bi, Xinhui; Chen, Jianmin; Sun, Yele; George, Christian; Wang, Xinming

2017-12-01

Agricultural residues are among the most abundant biomass burned globally, especially in China. However, there is little information on primary emissions and photochemical evolution of agricultural residue burning. In this study, indoor chamber experiments were conducted to investigate primary emissions from open burning of rice, corn and wheat straws and their photochemical aging as well. Emission factors of NOx, NH3, SO2, 67 non-methane hydrocarbons (NMHCs), particulate matter (PM), organic aerosol (OA) and black carbon (BC) under ambient dilution conditions were determined. Olefins accounted for > 50 % of the total speciated NMHCs emission (2.47 to 5.04 g kg-1), indicating high ozone formation potential of straw burning emissions. Emission factors of PM (3.73 to 6.36 g kg-1) and primary organic carbon (POC, 2.05 to 4.11 gC kg-1), measured at dilution ratios of 1300 to 4000, were lower than those reported in previous studies at low dilution ratios, probably due to the evaporation of semi-volatile organic compounds under high dilution conditions. After photochemical aging with an OH exposure range of (1.97-4.97) × 1010 molecule cm-3 s in the chamber, large amounts of secondary organic aerosol (SOA) were produced with OA mass enhancement ratios (the mass ratio of total OA to primary OA) of 2.4-7.6. The 20 known precursors could only explain 5.0-27.3 % of the observed SOA mass, suggesting that the major precursors of SOA formed from open straw burning remain unidentified. Aerosol mass spectrometry (AMS) signaled that the aged OA contained less hydrocarbons but more oxygen- and nitrogen-containing compounds than primary OA, and carbon oxidation state (OSc) calculated with AMS resolved O / C and H / C ratios increased linearly (p < 0.001) with OH exposure with quite similar slopes.

Ozone budgets from the Dynamics and Chemistry of Marine Stratocumulus experiment

NASA Technical Reports Server (NTRS)

Kawa, S. R.; Pearson, R., Jr.

1989-01-01

Measurements from the Dynamics and Chemistry of marine Stratocumulus experiment have been used to study components of the regional ozone budget. The surface destruction rate is determined by eddy correlation of ozone and vertical velocity measured by a low-flying aircraft. Significant variability is found in the measured surface resistance; it is partially correlated with friction velocity but appears to have other controlling influences as well. The mean resistance is 4190 s/m which is higher (slower destruction) than most previous estimates for seawater. Flux and mean measurements throughout the marine boundary layer are used to estimate the net rate of in situ photochemical production/destruction of ozone. Averaged over the flights, ozone concentration is found to be near steady state, and a net of photochemical destruction of 0.02-0.07 ng/cu m per sec is diagnosed. This is an important confirmation of photochemical model results for the remote marine boundary layer. Ozone vertical distributions above the boundary layer show a strongly layered structure with very sharp gradients. These distributions are possibly related to the stratospheric ozone source.

Photochemical model estimated fire impacts on ozone and aerosol evaluated with field studies and routine data sources

NASA Astrophysics Data System (ADS)

Baker, K. R.

2017-12-01

Highly instrumented field studies provide a unique opportunity to evaluate multiple aspects of photochemical grid model representation of fire emissions, dispersion, and chemical evolution. Fuel information and burn area for a specific fire coupled with near-fire and downwind chemical measurements provides information needed to constrain model predicted fire plume transport and chemical evolution of important pollutants such as ozone and particulate matter (PM2.5) that have deleterious health effects. Most local to regional scale field campaigns to date have made relatively few transects through plumes from fires with well characterized fuel type and consumption. While more comprehensive field studies are being planned for 2018 and beyond (WE-CAN, FIREX, FIRE-CHEM, and FASMEE), existing measurement data from multiple field campaigns including 2013 SEAC4RS, satellite data, and routine surface networks are used to assess how a regulatory modeling system captures fire impacts on local to regional scale ozone and PM2.5. Key aspects of the regulatory modeling system include fire location and burn area from SMARTFIRE2, emissions from BlueSky framework, and predictions of ambient O3 and PM2.5 from the Community Multiscale Air Quality (CMAQ) photochemical transport model. A comparison of model estimated O3 from specific fires with routine surface measurements at rural locations in proximity to the 2013 Rim fire, 2011 Wallow fire, and 2011 Flint Hills fires suggest the modeling system over-estimates smoke impacts on hourly ozone. Sensitivity simulations where solar radiation and photolysis rates are more aggressively attenuated by smoke reduced O3 predictions but did not ameliorate the over prediction bias. PM2.5 organic carbon tends to be overpredicted at rural surface sites downwind from the 2011 Flint Hills prescribed fires while results were mixed at rural sites downwind of the 2013 Rim fire and 2011 Wallow fire suggesting differences in fuel characterization (e

Seasonal variations of C1-C4 alkyl nitrates at a coastal site in Hong Kong: Influence of photochemical formation and oceanic emissions.

PubMed

Song, Junwei; Zhang, Yingyi; Huang, Yu; Ho, Kin Fai; Yuan, Zibing; Ling, Zhenhao; Niu, Xiaojun; Gao, Yuan; Cui, Long; Louie, Peter K K; Lee, Shun-Cheng; Lai, Senchao

2018-03-01

Five C 1 -C 4 alkyl nitrates (RONO 2 ) were measured at a coastal site in Hong Kong in four selected months of 2011 and 2012. The total mixing ratios of C 1 -C 4 RONO 2 (Σ 5 RONO 2 ) ranged from 15.4 to 143.7 pptv with an average of 65.9 ± 33.0 pptv. C 3 -C 4 RONO 2 (2-butyl nitrate and 2-propyl nitrate) were the most abundant RONO 2 during the entire sampling period. The mixing ratios of C 3 -C 4 RONO 2 were higher in winter than those in summer, while the ones of methyl nitrate (MeONO 2 ) were higher in summer than those in winter. Source analysis suggests that C 2 -C 4 RONO 2 were mainly derived from photochemical formation along with biomass burning (58.3-71.6%), while ocean was a major contributor to MeONO 2 (53.8%) during the whole sampling period. The photochemical evolution of C 2 -C 4 RONO 2 was investigated, and found to be dominantly produced by the parent hydrocarbon oxidation. The notable enrichment of MeONO 2 over C 3 -C 4 RONO 2 was observed in a summer episode when the air masses originating from the South China Sea (SCS) and MeONO 2 was dominantly derived from oceanic emissions. In order to improve the accuracy of ozone (O 3 ) prediction in coastal environment, the relative contribution of RONO 2 from oceanic emissions versus photochemical formation and their coupling effects on O 3 production should be taken into account in future studies. Copyright © 2017 Elsevier Ltd. All rights reserved.

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...

PHOTOCHEMICAL REACTIVITY OF PERCHLOROETHYLENE: A NEW APPRAISAL

EPA Science Inventory

Perchloroethylene (PCE), a solvent used in dry cleaning, has been suspected of contributing significantly to photochemical ozone/oxidant (O3/O(x)) problems in urban atmospheres. Past evidence, however, was neither complete nor consistent. To interpret more conclusively the past e...

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.

Ozone Production and Control Strategies for Southern Taiwan

NASA Astrophysics Data System (ADS)

Shiu, C.; Liu, S.; Chang, C.; Chen, J.; Chou, C. C.; Lin, C.

2006-12-01

An observation-based modeling (OBM) approach is used to estimate the ozone production efficiency and production rate of O3 (P(O3)) in southern Taiwan. The approach can also provide an indirect estimate of the concentration of OH. Measured concentrations of two aromatic hydrocarbons, i.e. ethylbenzene/m,p-xylene, are used to estimate the degree of photochemical processing and the amounts of photochemically consumed NOx and NMHCs. In addition, a one-dimensional (1d) photochemical model is used to compare with the OBM results. The average ozone production efficiency during the field campaign in Kaohsiung-Pingtung area in Fall 2003 is found to be about 5, comparable to previous works. The relationship of P(O3) with NOx is examined in detail and compared to previous studies. The derived OH concentrations from this approach are in fair agreement with values calculated from the 1d photochemical model. The relationship of total oxidants (e.g. O3+NO2) versus initial NOx and NMHCs suggests that reducing NMHCs are more effective in controlling total oxidants than reducing NOx. For O3 control, reducing NMHC is even more effective than NOx due to the NO titration effect. This observation-based approach provides a good alternative for understanding the production of ozone and formulating ozone control strategy in urban and suburban environment without measurements of peroxy radicals.

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.

Changes in the photochemical environment of the temperate North Pacific troposphere in response to increased Asian emissions

NASA Astrophysics Data System (ADS)

Parrish, D. D.; Dunlea, E. J.; Atlas, E. L.; Schauffler, S.; Donnelly, S.; Stroud, V.; Goldstein, A. H.; Millet, D. B.; McKay, M.; Jaffe, D. A.; Price, H. U.; Hess, P. G.; Flocke, F.; Roberts, J. M.

2004-12-01

Measurements during the Intercontinental Transport and Chemical Transformation 2002 (ITCT 2K2) field study characterized the springtime, eastern Pacific ozone distribution at two ground sites, from the National Oceanic and Atmospheric Administration WP-3D aircraft, and from a light aircraft operated by the University of Washington. D. Jaffe and colleagues compared the 2002 ozone distribution with measurements made in the region over the two previous decades and show that average ozone levels over the eastern midlatitude Pacific have systematically increased by ˜10 ppbv in the last two decades. Here we provide substantial evidence that a marked change in the photochemical environment in the springtime troposphere of the North Pacific is responsible for this increased O3. This change is evidenced in the eastern North Pacific ITCT 2K2 study region by (1) larger increases in the minimum observed ozone levels compared to more modest increases in the maximum levels, (2) increased peroxyacetyl nitrate (PAN) levels that parallel trends in NOx emissions, and (3) decreased efficiency of photochemical O3 destruction, i.e., less negative O3 photochemical tendency (or net rate of O3 photochemical production; P(O3)). This changed photochemical environment is hypothesized to be due to anthropogenic emissions from Asia, which are believed to have substantially increased over the two decades preceding the study. We propose that their influence has changed the springtime Pacific tropospheric photochemistry from predominately ozone destroying to more nearly ozone producing. However, chemical transport model calculations indicate the possible influence of a confounding factor; unusual transport of tropical air to the western North Pacific during one early field study may have played a role in this apparent change in the photochemistry.

Photochemical grid model implementation and application of ...

EPA Pesticide Factsheets

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

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.

Photochemical Formation of Sulfur-Containing Aerosols

NASA Astrophysics Data System (ADS)

Kroll, Jay A.; Vaida, Veronica

2017-06-01

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

[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.

OZONE BYPRODUCT FORMATION

EPA Science Inventory

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

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.

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

NASA Astrophysics Data System (ADS)

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

2011-12-01

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

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

NASA Astrophysics Data System (ADS)

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

2012-04-01

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

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

Ozone production in remote oceanic and industrial areas derived from ship based measurements of peroxy radicals during TexAQS 2006

NASA Astrophysics Data System (ADS)

Sommariva, R.; Brown, S. S.; Roberts, J. M.; Brookes, D. M.; Parker, A. E.; Monks, P. S.; Bates, T. S.; Bon, D.; de Gouw, J. A.; Frost, G. J.; Gilman, J. B.; Goldan, P. D.; Herndon, S. C.; Kuster, W. C.; Lerner, B. M.; Osthoff, H. D.; Tucker, S. C.; Warneke, C.; Williams, E. J.; Zahniser, M. S.

2011-03-01

During the Texas Air Quality Study II (TexAQS 2006) campaign, a PEroxy Radical Chemical Amplifier (PERCA) was deployed on the NOAA research vessel R/V Brown to measure total peroxy radicals (HO2+Σ RO2). Day-time mixing ratios of HO2+Σ RO2 between 25 and 110 ppt were observed throughout the study area - the Houston/Galveston region and the Gulf coast of the US - and analyzed in relation to measurements of nitrogen oxides, volatile organic compounds (VOC) and photolysis rates to assess radical sources and sinks in the region. The measurements of HO2+Σ RO2 were used to calculate the in-situ net photochemical formation of ozone. Measured median values ranged from 0.6 ppb/h in clean oceanic air masses up to several tens of ppb/h in the most polluted industrial areas. The results are consistent with previous studies and generally agree with observations made during the previous TexAQS 2000 field campaign. The net photochemical ozone formation rates determined at Barbours Cut, a site immediately south of the Houston Ship Channel, were analyzed in relation to local wind direction and VOC reactivity to understand the relationship between ozone formation and local VOC emissions. The measurements of HO2+Σ RO2 made during the R/V Brown TexAQS 2006 cruise indicate that ozone formation is NOx-limited in the Houston/Galveston region and influenced by highly reactive hydrocarbons, especially alkenes from urban and industrial sources and their photo-oxidation products, such as formaldehyde.

Ozone production in remote oceanic and industrial areas derived from ship based measurements of peroxy radicals during TexAQS 2006

NASA Astrophysics Data System (ADS)

Sommariva, R.; Brown, S. S.; Roberts, J. M.; Brookes, D. M.; Parker, A. E.; Monks, P. S.; Bates, T. S.; Bon, D.; de Gouw, J. A.; Frost, G. J.; Gilman, J. B.; Goldan, P. D.; Herndon, S. C.; Kuster, W. C.; Lerner, B. M.; Osthoff, H. D.; Tucker, S. C.; Warneke, C.; Williams, E. J.; Zahniser, M. S.

2010-10-01

During the Texas Air Quality Study II (TexAQS 2006) campaign, a PEroxy Radical Chemical Amplifier (PERCA) was deployed on the NOAA research vessel R/V Brown to measure total peroxy radicals (HO2+ΣRO2). Day-time mixing ratios of HO2+ΣRO2 between 25 and 110 ppt were observed throughout the study area - the Houston/Galveston region and the Gulf coast of the U.S. - and analyzed in relation to measurements of nitrogen oxides, volatile organic compounds (VOC) and photolysis rates to assess radical sources and sinks in the region. The measurements of HO2+ΣRO2 were used to calculate the in-situ net photochemical formation of ozone. Measured median values ranged from 0.6 ppb/h in clean oceanic air masses up to several tens of ppb/h in the most polluted industrial areas. The results are consistent with previous studies and generally agree with observations made during the previous TexAQS 2000 field campaign. The net photochemical ozone formation rates determined at Barbours Cut, a site immediately south of the Houston Ship Channel, were analyzed in relation to local wind direction and VOC reactivity to understand the relationship between ozone formation and local VOC emissions. The measurements of HO2+ΣRO2 made during the R/V Brown TexAQS 2006 cruise indicate that ozone formation is NOx-limited in the Houston/Galveston region and influenced by highly reactive hydrocarbons, especially alkenes from urban and industrial sources and their photooxidation products, such as formaldehyde.

LaRC Modeling of Ozone Formation in San Antonio, Texas

NASA Astrophysics Data System (ADS)

Guo, F.; Griffin, R. J.; Bui, A.; Schulze, B.; Wallace, H. W., IV; Flynn, J. H., III; Erickson, M.; Kotsakis, A.; Alvarez, S. L.; Usenko, S.; Sheesley, R. J.; Yoon, S.

2017-12-01

Ozone (O3) is one of the most important trace species within the troposphere and results from photochemistry involving emissions from a complex array of sources. Ground-level O3 is detrimental to ecosystems and causes a variety of human health problems including respiratory irritation, asthma and reduction in lung capacity. However, the O3 Design Value in San Antonio, Texas, was in violation of the federal threshold set by the EPA (70 ppb, 8-hr max) based on the average for the most recent three-year period (2014-2016). To understand the sources of high O3 concentrations in this nonattainment area, we assembled and deployed a mobile air quality laboratory and operated it in two locations in the southeast (Traveler's World RV Park) and northwest (University of Texas at San Antonio) of downtown San Antonio during summer 2017 to measure O3 and its precursors, including total nitrogen oxides (NOx) and volatile organic compounds (VOCs). Additional measurements included temperature, relative humidity, pressure, solar radiation, wind speed, wind direction, total reactive nitrogen (NOy), carbon monoxide (CO), and aerosol composition and concentration. We will use the campaign data and the NASA Langley Research Center (LaRC) Zero-Dimensional Box Model (Crawford et al., 1999; Olson et al., 2006) to calculate O3 production rate, NOx and hydroxyl radical chain length, and NOx versus VOCs sensitivity at different times of a day with different photochemical and meteorological conditions. A key to our understanding is to combine model results with measurements of precursor gases, particle chemistry and particle size to support the identification of O3 sources, its major formation pathways, and how the ozone production efficiency (OPE) depends on various factors. The resulting understanding of the causes of high O3 concentrations in the San Antonio area will provide insight into future air quality protection.

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.

[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.

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

... and Related Photochemical Oxidants (Second External Review Draft--September 2011). DATES: The CASAC... second external review draft of the Integrated Science Assessment for Ozone and Related Photochemical... reviewed EPA's first external review draft of the Integrated Science Assessment for Ozone and Related...

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.

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

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

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

1994-06-01

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

POGO-FAN: Remarkable Empirical Indicators for the Local Chemical Production of Smog- Ozone and NOx-Sensitivity of Air Parcels

NASA Astrophysics Data System (ADS)

Chatfield, R. B.; Browell, E. V.; Brune, W. H.; Crawford, J. H.; Esswein, R.; Fried, A.; Olson, J. R.; Shetter, R. E.; Singh, H. B.

2006-12-01

We propose and evaluate two related and surprisingly simple empirical estimators for the local chemical production term for photochemical ozone; each uses two moderate-technology chemical measurements and a measurement of ultraviolet light. We nickname the techniques POGO-FAN: Production of Ozone by Gauging Oxidation: Formaldehyde and NO. (1) A non-linear function of a single three-factor index-variable, j (HCHO=>rads) [HCHO] [NO] seems to provide a good estimator of the largest single term in the production of smog ozone, the HOO+NO term, over a very wide range of situations. (2) By considering empirical contour plots summarizing isopleths of HOO+NO using j (HCHO=>rads) [HCHO] and [NO] separately as coordinates, we provide a slightly more complex 2-d indicator of smog ozone production that additionally allows an estimate of the NOx-sensitivity or NOx-saturation (i.e., VOC-sensitivity) of sampled air parcels. ~85 to >90 % of the variance is explained. The correspondence to "EKMA" contour plots, estimating afternoon ozone based on morningtime organics and NOx mixes, is not coincidental. We utilize a broad set of urban plume, regionally polluted and cleaner NASA DC-8 PBL samples from the Intercontinental Transport Experiment-North America (INTEX-NA), in which each of the variables was measured, to help establish our relationship. The estimator is described in terms both both of asymptotic smog photochemistry theory; primarily this suggests appropriate statistical approaches which can capture some of the complex interrelations of lower-tropospheric smog mix through correlation of reactive mixture components. HCHO is not only an important source of HOO radicals, but it more important serves as a "gauge" of all photochemical processing of volatile organic compounds. It probably captures information related to coincident VOC sources of various compounds and parallels in photochemical processing. Constrained modeling of observed atmospheric concentrations suggests that

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

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

Jung, Haesung; Chadha, Tandeep S.; Kim, Doyoon

This study introduces a new and previously unconsidered fast abiotic formation of Mn(IV) oxides. We report photochemically assisted fast abiotic oxidation of Mn 2+ (aq) to Mn(IV) (s) by superoxide radicals generated from nitrate photolysis. This photochemical pathway generates randomly stacked layered birnessite (δ-MnO 2) nanosheets.

Near-field photochemical and radiation-induced chemical fabrication of nanopatterns of a self-assembled silane monolayer

PubMed Central

Hentschel, Carsten; Fontein, Florian; Stegemann, Linda; Hoeppener, Christiane; Fuchs, Harald; Hoeppener, Stefanie

2014-01-01

Summary A general concept for parallel near-field photochemical and radiation-induced chemical processes for the fabrication of nanopatterns of a self-assembled monolayer (SAM) of (3-aminopropyl)triethoxysilane (APTES) is explored with three different processes: 1) a near-field photochemical process by photochemical bleaching of a monomolecular layer of dye molecules chemically bound to an APTES SAM, 2) a chemical process induced by oxygen plasma etching as well as 3) a combined near-field UV-photochemical and ozone-induced chemical process, which is applied directly to an APTES SAM. All approaches employ a sandwich configuration of the surface-supported SAM, and a lithographic mask in form of gold nanostructures fabricated through colloidal sphere lithography (CL), which is either exposed to visible light, oxygen plasma or an UV–ozone atmosphere. The gold mask has the function to inhibit the photochemical reactions by highly localized near-field interactions between metal mask and SAM and to inhibit the radiation-induced chemical reactions by casting a highly localized shadow. The removal of the gold mask reveals the SAM nanopattern. PMID:25247126

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.

Impact of synoptic controls and boundary layer processes on ground-level ozone evolution at an urban site

NASA Astrophysics Data System (ADS)

Haman, Christine Lanier

Houston, Texas frequently exceeds the standard for ground-level ozone during the spring and fall. The large commuting population and vast number of industrial sources provide the necessary ingredients for photochemical ozone production in the presence of favorable meteorological conditions. The lack of continuous boundary layer (BL) observations prevents a comprehensive understanding of its role in ozone evolution. In this study, almost two years of BL observations are utilized to investigate the impacts of synoptic and micrometeorological-scale forcings on ozone. Aerosol gradients derived from ceilometer backscatter retrievals are used to identify the BL and residual layers (RL). Overall agreement is found between ceilometer and sonde estimates of the RL and BL heights (BLH), but difficulty detecting the layers occurs during cloud periods or immediately following precipitation. Large monthly variability is present in the peak afternoon BLH (e.g. mean August and December peaks are ˜2000 and 1100 m, respectively). Monthly nocturnal BLHs display much smaller differences. The majority of ozone exceedances occur during large-scale subsidence and weak winds in a postfrontal environment. These conditions result in turbulent kinetic energy, mechanical mixing, and ventilation processes that are 2--3 times weaker on exceedance days, which inhibit morning BL growth by an average of ˜100 m·hr-1 compared to low ozone days. The spring has higher nocturnal ozone levels, which is likely attributable to longer day lengths (˜78 minutes), stronger winds (˜0.78 m·s -1), and higher background ozone (˜5 ppbv) compared to the fall. Boundary layer entrainment plays an important role in ozone evolution. Exceedance days show a characteristic early morning rapid rise of ozone. Vertical ozone profiles indicate the RL ozone peak is ˜60 ppbv on exceedance days, which is ˜25 ppbv (+/- 10 ppbv) greater than low ozone days. The Integrated Profile Mixing (IPM) and Photochemical Budget (PB

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.

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

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.

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.

Modelling the photochemical pollution over the metropolitan area of Porto Alegre, Brazil

NASA Astrophysics Data System (ADS)

Borrego, C.; Monteiro, A.; Ferreira, J.; Moraes, M. R.; Carvalho, A.; Ribeiro, I.; Miranda, A. I.; Moreira, D. M.

2010-01-01

The main purpose of this study is to evaluate the photochemical pollution over the Metropolitan Area of Porto Alegre (MAPA), Brazil, where high concentrations of ozone have been registered during the past years. Due to the restricted spatial coverage of the monitoring air quality network, a numerical modelling technique was selected and applied to this assessment exercise. Two different chemistry-transport models - CAMx and CALGRID - were applied for a summer period, driven by the MM5 meteorological model. The meteorological model performance was evaluated comparing its results to available monitoring data measured at the Porto Alegre airport. Validation results point out a good model performance. It was not possible to evaluate the chemistry models performance due to the lack of adequate monitoring data. Nevertheless, the model intercomparison between CAMx and CALGRID shows a similar behaviour in what concerns the simulation of nitrogen dioxide, but some discrepancies concerning ozone. Regarding the fulfilment of the Brazilian air quality targets, the simulated ozone concentrations surpass the legislated value in specific periods, mainly outside the urban area of Porto Alegre. The ozone formation is influenced by the emission of pollutants that act as precursors (like the nitrogen oxides emitted at Porto Alegre urban area and coming from a large refinery complex) and by the meteorological conditions.

Balloon-Borne Measurements of Stratospheric Radicals and their Precursors: Implications for the Production and Loss of Ozone

NASA Technical Reports Server (NTRS)

Osterman, G. B.; Salawitch, R. J.; Sen, B.; Toon, G. C.; Stachnik, R. A.; Pickett, H. M.; Margitan, J. J.; Blavier, J.-F.; Peterson, D. B.

1997-01-01

Measurements of hydrogen, nitrogen and chlorine radicals from a balloon flight on 25 September 1993 from Ft. Sumner, NM provide an opportunity to quantify photochemical production and loss of stratospheric ozone. Ozone loss rates determined using measured radical concentrations agree fairly well with loss rates calculated using a photochemical model. Catalytic cycles involving OH and HO2 are shown to dominate photochemical loss of ozone for altitudes between 44 and 50 km. Reactions involving NO and NO2 are the dominant sink for ozone between 25 and 38 km. The total ozone loss rate determined from the measurements balances calculated production rates for altitudes between 30 and 40 km. However, loss of ozone exceeds production by -35% between 42 and 50 km. The imbalance between production and loss of ozone above 42 km is larger than the uncertainty of any one of the critical kinetic parameters or species concentrations. No single adjustment to any of these parameters can simultaneously resolve the imbalance and satisfy constraints imposed by measured OH, HO2, NO2 and ClO. Our results are consistent with an additional mechanism for ozone production above 40 km other than photolysis of ground state O2.

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

NASA Astrophysics Data System (ADS)

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

2017-04-01

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

Ozone Observations using Ozonesonde over the Himalaya from Pokhara, Nepal.

NASA Astrophysics Data System (ADS)

Dhungel, S.; Cullis, P.; Johnson, B.; Thompson, A. M.; Witte, J. C.; Panday, A. K.

2016-12-01

In recent years, transport of emissions from the Indo-Gangetic Plains (IGP), which covers parts of Pakistan, Nepal, India, Bangladesh has increased. Ozone pre-cursors like methane, nitrogen oxides, volatile organic carbons, and carbon monoxide from diesel based vehicular emission, biofuel and biomass burning, agricultural activities dominate the total emissions from the IGP. Synoptic circulation patterns along with local weather systems transport pollutants from the IGP up the Himalayan valleys to the Tibetan plateau. After being emitted, these pollutants are photochemically converted into tropospheric ozone - a short-lived climate pollutant that can increase atmospheric warming, alter processes of cloud formation, and in turn, influence precipitation levels and reduce carbon absorptivity in plants leading to decline in crop yields. However, little is known about vertical profiles of ozone concentration on the southern slopes of the Himalaya. Vertical ozone profiles were sampled from December 18th, 2015 to January 8th, 2016 from Pokhara (28.23°N, 83.99°E, 827m asl), Nepal using ozonesondes. Pokhara is located about 30km south of the Annapurna Himalaya, thus providing an ideal location to profile vertical ozone concentration south of the Himalaya. We launched one, two or four ozonesondes per day to examine the vertical resolution of ozone south of the Himalaya for the first time, and to understand the contribution of tropospheric and stratospheric sources. Here we present results from the 37 ozonesonde launches from Pokhara to examine: (i) how emissions from the IGP contribute to the vertical resolution of ozone, and (ii) if Himalayan orography provides an efficient path for stratosphere-troposphere air mass exchange under dry conditions. Our results show no signals of stratospheric air mass exchange. The results indicate higher levels of ozone within the boundary layer and lower troposphere. These higher values in the lower troposphere during winter seasons may

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.

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.

Formation of fatty acids in photochemical conversions of saturated hydrocarbons

NASA Technical Reports Server (NTRS)

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

1977-01-01

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

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

PubMed

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

2017-02-01

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

Analysis of a 7 year tropospheric ozone vertical distribution at the Observatoire de Haute Provence

NASA Technical Reports Server (NTRS)

Beekmann, Matthias; Ancellet, Gerard; Megie, Gerard

1994-01-01

A seven year (1984-90) climatology of tropospheric vertical ozone soundings, performed by electrochemical sondes at the OHP (44 deg N, 6 deg E, 700 m ASL) in Southern France, is presented. Its seasonal variation shows a broad spring/summer maximum in the troposphere. The contribution of photochemical ozone production and transport from the stratosphere to this seasonal variation are studied by a correlative analysis of ozone concentrations and meteorological variables, with emphasis on potential vorticity. This analysis shows the impact of dynamical and photochemical processes on the spatial and temporal ozone variability. In particular, a positive correlation (r = 04.0, significance greater than 99.9 percent) of ozone with potential vorticity is observed in the middle troposphere, reflecting the impact of stratosphere-troposphere exchange on the vertical ozone distribution.

Tropospheric Ozone Lidar Network (TOLNet) - Long-term Tropospheric Ozone and Aerosol Profiling for Satellite Continuity and Process Studies

NASA Astrophysics Data System (ADS)

Newchurch, M.; Al-Saadi, J. A.; Alvarez, R. J.; Burris, J.; Cantrell, W.; Chen, G.; De Young, R.; Hardesty, R.; Hoff, R. M.; Kaye, J. A.; kuang, S.; Langford, A. O.; LeBlanc, T.; McDermid, I. S.; McGee, T. J.; Pierce, R.; Senff, C. J.; Sullivan, J. T.; Szykman, J.; Tonnesen, G.; Wang, L.

2012-12-01

An interagency research initiative for ground-based ozone and aerosol lidar profiling recently funded by NASA has important applications to air-quality studies in addition to the goal of serving the GEO-CAPE and other air-quality missions. Ozone is a key trace-gas species, a greenhouse gas, and an important pollutant in the troposphere. High spatial and temporal variability of ozone affected by various physical and photochemical processes motivates the high spatio-temporal lidar profiling of tropospheric ozone for improving the simulation and forecasting capability of the photochemical/air-quality models, especially in the boundary layer where the resolution and precision of satellite retrievals are fundamentally limited. It is well known that there are large discrepancies between the surface and upper-air ozone due to titration, surface deposition, diurnal processes, free-tropospheric transport, and other processes. Near-ground ozone profiling has been technically challenging for lidars due to some engineering difficulties, such as near-range saturation, field-of-view overlap, and signal processing issues. This initiative provides an opportunity for us to solve those engineering issues and redesign the lidars aimed at long-term, routine ozone/aerosol observations from the near surface to the top of the troposphere at multiple stations (i.e., NASA/GSFC, NASA/LaRC, NASA/JPL, NOAA/ESRL, UAHuntsville) for addressing the needs of NASA, NOAA, EPA and State/local AQ agencies. We will present the details of the science investigations, current status of the instrumentation development, data access/protocol, and the future goals of this lidar network. Ozone lidar/RAQMS comparison of laminar structures.

Quantification of source region influences on the ozone burden

NASA Astrophysics Data System (ADS)

Treffeisen, Renate; Grunow, Katja; Möller, Detlev; Hainsch, Andreas

A project was performed to quantify different influences on the ozone burden. It could be shown that large-scale meteorological influences determine a very large percentage of the ozone concentration. Local measures intended to reduce peak ozone concentrations in summer turn out to be not very effective as a result. The aim of this paper is to quantify regional emission influences on the ozone burden. The investigation of these influences is possible by comparison of the ozone (O 3) and oxidant (O x=O 3+NO 2) concentrations at high-elevation sites downwind and upwind of a source region by using back trajectories. It has been shown that a separation between large-scale influenced meteorological and regional ozone burdens at these sites is possible. This method is applied for an important emission area in Germany—the Ruhrgebiet. On average, no significant ozone contribution of this area to the regional ozone concentration could be found. A large part of the ozone concentration is highly correlated with synoptic weather systems, which exhibit a dominant influence on the local ozone concentrations. Significant contributions of related photochemical ozone formation of the source area of 13-15% have been found only during favourable meteorological situations, identified by the hourly maximum day temperature being above 25°C. This is important with respect to the EU daughter directive to EU 96/62/EC (Official Journal L296 (1996) 55) because Member States should explore the possibilities of local measures to avoid the exceedance of threshold values and, if effective local measures exist, to implement them.

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.

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

PubMed

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

2018-05-01

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

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

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

Surface ozone characterization at Larsemann Hills and Maitri, Antarctica.

PubMed

Ali, Kaushar; Trivedi, D K; Sahu, S K

2017-04-15

Data are analyzed in terms of daily average ozone, its diurnal variation and its relation with meteorological parameters like dry bulb temperature (T), wet bulb temperature (T w ), atmospheric pressure and wind speed based on measurement of these parameters at two Indian Antarctic stations (Larsemann Hills, and Maitri) during 28th Indian Scientific Expedition of Antarctica (ISEA) organized during Antarctic summer of the year 2008-09. The work has been carried out to investigate summer time ozone level and its day-to-day and diurnal variability at these coastal locations and to highlight possible mechanism of ozone production and destruction. The result of the analysis indicates that daily average ozone concentration at Larsemann Hills varied from ~13 and ~20ppb with overall average value of ~16ppb and at Maitri, it varied from ~16 and ~21ppb with overall average value of ~18ppb. Photochemistry is found to partially contribute occasionally to the surface layer ozone at both the stations. Lower concentration of ozone at Maitri during beginning of the observational days may be due to destruction of ozone through activated halogens, whereas higher ozone on latter days may be due to photochemistry and advective transport from east to south-east areas. Ozone concentration during blizzard episodes at both the stations is reduced due to slow photochemical production of ozone, its photochemical removal and removal through deposition of ozone molecules on precipitation particles. Diurnal variation of ozone at Larsemann Hills and Maitri has been found to be absent. Copyright © 2017 Elsevier B.V. All rights reserved.

Measurements of in situ chemical ozone (oxidant) production rates

NASA Astrophysics Data System (ADS)

Huang, Hao; Faloon, Kate; Najera, Juan; Bloss, William

2013-04-01

Tropospheric ozone is a major air pollutant, harmful to human health, agricultural crops and vegetation, the main precursor to the atmospheric oxidants which initiate the degradation of most reactive gases emitted to the atmosphere, and an important greenhouse gas in its own right. The capacity to understand and predict tropospheric ozone levels is a key goal for atmospheric science - but one which is challenging, as ozone is formed in the atmosphere from the complex oxidation of VOCs in the presence of NOx and sunlight, on a timescale such that in situ chemical processes, deposition and transport all affect ozone levels. Known uncertainties in emissions, chemistry, dynamics and deposition affect the accuracy of predictions of current and future ozone levels, and hinder development of optimal air quality policies to mitigate against ozone exposure. Recently new approaches to directly measure the local chemical ozone production rate, bypassing the many uncertainties in emissions and chemical schemes, have been developed (Cazorla & Brune, AMT 2010). Here, we describe the development of an analogous Ozone Production Rate (OPR) approach: Air is sampled into parallel reactors, within which ozone formation either occurs as in the ambient atmosphere, or is suppressed. Comparisons of ozone levels exiting a pair of such reactors determines the net chemical oxidant production rate, after correction for perturbation of the NOx-O3 photochemical steady state, and when operated under conditions such that wall effects are minimised. We report preliminary measurements of local chemical ozone production made during the UK NERC ClearfLo (Clean Air for London) campaign at an urban background location in London in January and July 2012. The OPR system was used to measure the local chemical oxidant formation rate, which is compared with observed trends in O3 and NOx and the prevailing meteorology, and with the predictions of a detailed zero-dimensional atmospheric chemistry model

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.

3D analysis of high ozone production rates observed during the ESCOMPTE campaign

NASA Astrophysics Data System (ADS)

Coll, Isabelle; Pinceloup, Stéphanie; Perros, Pascal E.; Laverdet, Gérard; Le Bras, Georges

2005-03-01

The development of environmental policies to reduce the ozone levels around large agglomerations requires a good understanding of the development of ozone episodes. In particular, it is necessary to know the location and photochemical activity of the plume where ozone is formed. Measurement campaigns make it possible not only to characterize the concentration fields of ozone and its precursors but also to identify the zones of strong ozone production, by means of specific measurements and kinetic calculations. The combination of the observation-based data with numerical simulations allows to better characterize photochemical pollution. This paper presents a study carried out within the ESCOMPTE program and based on the determination of ozone production rates by experimental and numerical methods: ground measurements of peroxy radicals, NO x at a rural site, airborne measurements of NO X and O 3, Eulerian modeling. The reported case is of particular interest since it corresponds to an episode with very different photochemical situations. The diurnal variations of the peroxy radical concentration are analyzed in relation to those of ozone and its precursors. Ozone production rates— P(O 3)-are studied over one particular day. The results show particularly high concentrations of RO 2+HO 2 at ground level (up to 200 pptv) under the influence of the urban and industrial plume, but also highlight very high production rates of ozone (60 to 80 ppbv h -1) a few tens of kilometers from the sources. The results show satisfactory agreement between the various approaches. Modeling provides a four-dimensional (4D) description of the plumes, in particular the relation between the ozone precursor concentrations and P(O 3) on the ground.

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.

Charge-Transfer Complexes and Photochemistry of Ozone with Ferrocene and n-Butylferrocene: A UV-vis Matrix-Isolation Study.

PubMed

Pinelo, Laura F; Kugel, Roger W; Ault, Bruce S

2015-10-15

The reactions of ozone with ferrocene (cp2Fe) and with n-butylferrocene (n-butyl cp2Fe) were studied using matrix isolation, UV-vis spectroscopy, and theoretical calculations. The codeposition of cp2Fe with O3 and of n-butyl cp2Fe with O3 into an argon matrix led to the production of 1:1 charge-transfer complexes with absorptions at 765 and 815 nm, respectively. These absorptions contribute to the green matrix color observed upon initial deposition. The charge-transfer complexes underwent photochemical reactions upon irradiation with red light (λ ≥ 600 nm). Theoretical UV-vis spectra of the charge-transfer complexes and photochemical products were calculated using TD-DFT at the B3LYP/6-311G++(d,2p) level of theory. The calculated UV-vis spectra were in good agreement with the experimental results. MO analysis of these long-wavelength transitions showed them to be n→ π* on the ozone subunit in the complex and indicated that the formation of the charge-transfer complex between ozone and cp2Fe or n-butyl cp2Fe affects how readily the π* orbital on O3 is populated when red light (λ ≥ 600 nm) is absorbed. 1:1 complexes of cp2Fe and n-butyl cp2Fe with O2 were also observed experimentally and calculated theoretically. These results support and enhance previous infrared studies of the mechanism of photooxidation of ferrocene by ozone, a reaction that has considerable significance for the formation of iron oxide thin films for a range of applications.

Integrated Science Assessment (ISA) of Ozone and Related ...

EPA Pesticide Factsheets

EPA announced the availability of the final report, Integrated Science Assessment of Ozone and Related Photochemical Oxidants. This document represents a concise synthesis and evaluation of the most policy-relevant science and will ultimately provide the scientific bases for EPA’s decision regarding the adequacy of the current national ambient air quality standards for ozone to protect human health, public welfare, and the environment. Critical evaluation and integration of the evidence on health and environmental effects of ozone to provide scientific support for the review of the NAAQS for ozone.

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...

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.

Decrease of summer tropospheric ozone concentrations in Antarctica

NASA Technical Reports Server (NTRS)

Schnell, R. C.; Stone, R. S.; Liu, S. C.; Oltmans, S. J.; Hofmann, D. J.

1991-01-01

It is shown here that surface ozone concentrations at the South Pole in the austral summer decreased by 17 percent over the period 1976-90. Over the same period, solar irradiance at the South Pole in January and February decreased by 7 percent as a result of a 25 percent increase in cloudiness. It is suggested that the trend in the summer ozone concentrations is caused by enhanced photochemical destruction of ozone in the lower troposphere caused by the increased penetration of UV radiation associated with stratospheric ozone depletion, coupled with enhanced transport of ozone-poor marine air from lower latitudes to the South Pole.

Understanding Differences in Upper Stratospheric Ozone Response to Changes in Chlorine and Temperature as Computed Using CCMVal Models

NASA Technical Reports Server (NTRS)

Douglass, A. R.; Stolarski, R. S.; Strahan, S. E.; Oman, L. D.

2012-01-01

Projections of future ozone levels are made using models that couple a general circulation model with a representation of atmospheric photochemical processes, allowing interactions among photochemical processes, radiation, and dynamics. Such models are known as chemistry and climate models (CCMs). Although developed from common principles and subject to the same boundary conditions, simulated ozone time series vary for projections of changes in ozone depleting substances (ODSs) and greenhouse gases. In the upper stratosphere photochemical processes control ozone level, and ozone increases as ODSs decrease and temperature decreases due to greenhouse gas increase. Simulations agree broadly but there are quantitative differences in the sensitivity of ozone to chlorine and to temperature. We obtain insight into these differences in sensitivity by examining the relationship between the upper stratosphere annual cycle of ozone and temperature as produced by a suite of models. All simulations conform to expectation in that ozone is less sensitive to temperature when chlorine levels are highest because chlorine catalyzed loss is nearly independent of temperature. Differences in sensitivity are traced to differences in simulated temperature, ozone and reactive nitrogen when chlorine levels are close to background. This work shows that differences in the importance of specific processes underlie differences in simulated sensitivity of ozone to composition change. This suggests a) the multi-model mean is not a best estimate of the sensitivity of upper ozone to changes in ODSs and temperature; b) the spread of values is not an appropriate measure of uncertainty.

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.

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.

Impacts of stratospheric sulfate geoengineering on tropospheric ozone

NASA Astrophysics Data System (ADS)

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

2017-10-01

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

Nighttime Ozone Chemical Equilibrium in the Mesopause Region

NASA Astrophysics Data System (ADS)

Kulikov, M. Yu.; Belikovich, M. V.; Grygalashvyly, M.; Sonnemann, G. R.; Ermakova, T. S.; Nechaev, A. A.; Feigin, A. M.

2018-03-01

We examine the applicability of the assumption that nighttime ozone is in photochemical equilibrium. The analysis is based on calculations with a 3-D chemical transport model. These data are used to determine the ratio of correct (calculated) O3 density to its equilibrium value for the conditions of the nighttime mesosphere depending on the altitude, latitude, and month in the annual cycle. The results obtained demonstrate that the retrieval of O and H distributions using the assumption of photochemical ozone equilibrium may lead to a significant error below 81-87 km depending on season. Possible modifications of the currently used approach that allow improving the quality of retrieval of O and H mesospheric distributions from satellite-based observations are discussed.

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.

Impact of Anthropogenic Emissions on Isoprene Photochemical Oxidation Pathways in Central Amazonia

NASA Astrophysics Data System (ADS)

Thayer, M. P.; Dorris, M. R.; Keutsch, F. N.; Goldstein, A. H.; Guenther, A. B.; Isaacman-VanWertz, G. A.; Jimenez, J. L.; Kim, S.; Liu, Y.; Martin, S. T.; Palm, B. B.; Park, J. H.; Seco, R.; Sjostedt, S. J.; Springston, S. R.; Wernis, R. A.; Yee, L.

2016-12-01

The atmosphere over the Amazon rainforest is characterized by high concentrations of biogenic volatile organic compounds (BVOCs) - most notably isoprene, which is the most abundant non-methane VOC both locally and globally. These BVOCs are photochemically oxidized, forming oVOCs, especially via reaction with the hydroxyl radical (OH). This photochemical processing can result in formation of secondary pollutants such as ozone (O3) and secondary organic aerosol (SOA). During the Green Ocean Amazon campaign (GoAmazon2014/5), we obtained formaldehyde and glyoxal measurements together with OH, peroxy radicals (RO2+HO2), nitrogen oxides (NOx), CO, CO2, O3, (o)VOCs, and aerosol particle size distribution. Here we present data collected during 2014 at the T3 field site, 60 km to the west of Manaus, Brazil (3°12'47.82"S, 60°35'55.32"W). The T3 GoAmazon site varies between sampling strictly pristine (biogenic) emissions and influence from anthropogenic emissions from Manaus, depending on meteorological conditions. The day-to-day oscillation provides an ideal setting for evaluating the impact of pollution from biomass burning and urban emissions on VOC oxidation and resultant secondary pollutant production. Anthropogenic plumes contain not only additional VOC precursors, but also enhanced NOx, which drastically alters the relative importance of various isoprene oxidation pathways. We utilize a 0-D photochemical box model to examine how these factors impact reactivity and pollutant formation. Due to ongoing expansion of human influence and emissions in previously-pristine areas, understanding the sensitivity of biogenic oxidation to anthropogenic influence has significant impacts for tropospheric air quality, both in the rapidly-developing Amazon Basin and other BVOC-dominated regions.

Surface ozone variability at Kislovodsk Observatory

NASA Technical Reports Server (NTRS)

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

1994-01-01

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

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...

Ozone in Lombardy: Years 1998-1999

NASA Astrophysics Data System (ADS)

Sesana, L.; Begnini, S.; Toscani, D.; Facchini, U.; Balasso, A.; Borelli, P.

2003-11-01

Photochemical pollutants, especially ozone, have reached very high levels in Lombardy in recent years, with peaks of up to 150 ppb in late spring and summer. Lombardy, lying on the Po Plain, supports a large number of cities and industries and these, along with heavy traffic, produce copious amounts of primary pollutants such as nitrogen oxides and numerous volatile organic compounds. Furthermore, the peculiar orography of this region fosters the stagnation of air masses on a basin-scale and the presence of diurnal breezes towards northern areas, along with the evolution of the Mixing Layer, spread the polluted air masses over a large territory. Numerous stations in Lombardy give the concentrations of ozone and of nitrogen oxides. In this paper, ozone measurements carried out at the plain area around Milan and at pre-alpine sites in the spring and summer 1998 and 1999 will be shown and discussed, focusing on the months of May and July. The study of temporal and spatial behaviour of ozone goes hand in hand with the analysis of the Boundary Layer's evolution. A number of radon stations were operating in Milan and in other sites in Lombardy. Measurements of atmospheric concentrations of radon yield an index of atmospheric stability, of the formation of thermal inversion, of convective turbulence, and of the movement of air masses, and hence they are very relevant to the understanding of the conditions of atmospheric pollutants.

77 FR 6796 - Notification of a Public Meeting of the Clean Air Scientific Advisory Committee (CASAC); Ozone...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-02-09

... Scientific Advisory Committee (CASAC); Ozone Review Panel AGENCY: Environmental Protection Agency (EPA... teleconference of the CASAC Ozone Review Panel to discuss its draft review of EPA's Integrated Science Assessment for Ozone and Related Photochemical Oxidants (Second External Review Draft--September 2011). DATES...

An Extended View of Ozone and Chemistry in the Atmosphere of Mars

NASA Technical Reports Server (NTRS)

Smith, Ramsey L.; Fast, Kelly E.; Kostiuk, T.; Lefevre, Frank; Hewagama, Tilak; Livengood, Timothy A.

2011-01-01

We present an ongoing effort to characterize chemistry in Mars' atmosphere in multiple seasons on timescales longer than spaceflight missions through coordinated efforts by GSFC's HIPWAC spectrometer and Mars Express SPICAM, archival measurements, and tests/application of photochemical models. The trace species ozone (03) is an effective probe of Mars' atmospheric chemistry because it is destroyed by odd-hydrogen species (HOx, from water vapor photolysis). Observed ozone is a critical test for specific predictions by 3-D photochemical models (spatial, diurnal, seasonal). Coordinated measurements by HIPWAC and SPICAM quantitatively linked mission data to the 23-year GSFC ozone data record and also revealed unanticipated inter-decadal variability of same-season ozone abundances, a possible indicator of changing cloud activity (heterogeneous sink for HOx). A detailed study of long-term conditions is critical to characterizing the predictability of Mars' seasonal chemical behavior, particularly in light of the implications of and the lack of explanation for reported methane behavior.

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.

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.

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.

Processes Affecting Tropospheric Ozone over Africa

NASA Technical Reports Server (NTRS)

Diab, Roseanne D.; Thompson, Anne M.

2004-01-01

This is a Workshop Report prepared for Eos, the weekly AGU magazine, The workshop took place between 26-28 January 2004 at the University of KwaZulu-Natal in Durban, South Africa and was attended by 26 participants (http//www.geography.und.ac.za). Considerable progress has been made in ozone observations except for northern Africa (large data gaps) and west Africa (to be covered by the French-sponsored AMMA program). The present-day ozone findings were evaluated and reviewed by speakers using Aircraft data (MOZAIC program), NASA satellites (MOPITT, TRMM, TOMS) and ozone soundings (SHADOZ). Besides some ozone gaps, there are challenges posed by the need to assess the relative strengths of photochemical and dynamic influences on the tropospheric ozone budget. Biogenic, biofuels, biomass burning sources of ozone precursors remain highly uncertain. Recent findings (by NASA's Chatfield and Thompson, using satellite and sounding data) show significant impact of Indian Ocean pollution on African ozone. European research on pollutants over the Mediterranean and the middle east, that suggests that ozone may be exported to Africa from these areas, also needs to be considered.

Quantifying Ozone Production throughout the Boundary Layer from High Frequency Tethered Profile Measurements during a High Ozone Episode in the Uinta Basin, Utah

NASA Astrophysics Data System (ADS)

Sterling, C. W.; Johnson, B.; Schnell, R. C.; Oltmans, S. J.; Cullis, P.; Hall, E. G.; Jordan, A. F.; Windell, J.; McClure-Begley, A.; Helmig, D.; Petron, G.

2015-12-01

During the Uinta Basin Winter Ozone Study (UBWOS) in Jan - Feb 2013, 735 tethered ozonesonde profiles were obtained at 3 sites including during high wintertime photochemical ozone production events that regularly exceeded 125 ppb. High resolution profiles of ozone and temperature with altitude, measured during daylight hours, showed the development of approximately week long high ozone episodes building from background levels of ~40 ppb to >150 ppb. The topography of the basin combined with a strong temperature inversion trapped oil and gas production effluents in the basin and the snow covered surface amplified the sun's radiation driving the photochemical ozone production at rates up to 13 ppb/hour in a cold layer capped at 1600-1700 meters above sea level. Beginning in mid-morning, ozone mixing ratios throughout the cold layer increased until late afternoon. Ozone mixing ratios were generally constant with height indicating that ozone production was nearly uniform throughout the depth of the cold pool. Although there was strong diurnal variation, ozone mixing ratios increased during the day more than decreased during the night, resulting in elevated levels the next morning; an indication that nighttime loss processes did not compensate for daytime production. Even though the 3 tethersonde sites were at elevations differing by as much as 140 m, the top of the high ozone layer was nearly uniform in altitude at the 3 locations. Mobile van surface ozone measurements across the basin confirmed this capped structure of the ozone layer; the vehicle drove out of high ozone mixing ratios at an elevation of ~1900 meters above sea level, above which free tropospheric ozone mixing ratios of ~50 ppb were measured. Exhaust plumes from a coal-fired power plant in the eastern portion of the basin were intercepted by the tethersondes. The structure of the profiles clearly showed that effluents in the plumes were not mixed downward and thus did not contribute precursor nitrogen

A cloud-ozone data product from Aura OMI and MLS satellite measurements

NASA Astrophysics Data System (ADS)

Ziemke, Jerald R.; Strode, Sarah A.; Douglass, Anne R.; Joiner, Joanna; Vasilkov, Alexander; Oman, Luke D.; Liu, Junhua; Strahan, Susan E.; Bhartia, Pawan K.; Haffner, David P.

2017-11-01

Ozone within deep convective clouds is controlled by several factors involving photochemical reactions and transport. Gas-phase photochemical reactions and heterogeneous surface chemical reactions involving ice, water particles, and aerosols inside the clouds all contribute to the distribution and net production and loss of ozone. Ozone in clouds is also dependent on convective transport that carries low-troposphere/boundary-layer ozone and ozone precursors upward into the clouds. Characterizing ozone in thick clouds is an important step for quantifying relationships of ozone with tropospheric H2O, OH production, and cloud microphysics/transport properties. Although measuring ozone in deep convective clouds from either aircraft or balloon ozonesondes is largely impossible due to extreme meteorological conditions associated with these clouds, it is possible to estimate ozone in thick clouds using backscattered solar UV radiation measured by satellite instruments. Our study combines Aura Ozone Monitoring Instrument (OMI) and Microwave Limb Sounder (MLS) satellite measurements to generate a new research product of monthly-mean ozone concentrations in deep convective clouds between 30° S and 30° N for October 2004-April 2016. These measurements represent mean ozone concentration primarily in the upper levels of thick clouds and reveal key features of cloud ozone including: persistent low ozone concentrations in the tropical Pacific of ˜ 10 ppbv or less; concentrations of up to 60 pphv or greater over landmass regions of South America, southern Africa, Australia, and India/east Asia; connections with tropical ENSO events; and intraseasonal/Madden-Julian oscillation variability. Analysis of OMI aerosol measurements suggests a cause and effect relation between boundary-layer pollution and elevated ozone inside thick clouds over landmass regions including southern Africa and India/east Asia.

Photochemical oxidant transport - Mesoscale lake breeze and synoptic-scale aspects

NASA Technical Reports Server (NTRS)

Lyons, W. A.; Cole, H. S.

1976-01-01

Data from routine ozone monitoring in southeastern Wisconsin and limited monitoring of the Milwaukee area by the Environmental Protection Agency are examined. Hourly averages as high as 30 pphm have been recorded in southeastern Wisconsin, and high readings have been reported in rural regions throughout the state. The observations indicate that photochemical oxidants and their nitrogen oxide and reactive hydrocarbon precursers advect from Chicago and northern Indiana into southeastern Wisconsin. There is evidence that synoptic-scale transport of photochemical oxidants occurs, allowing the pollution of entire anticyclones. These results cast doubt on the validity of the Air Quality Control Regions established by amendment to the Clean Air Act of 1970.

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

PubMed

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

2016-11-15

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

Results of ozone measurements in Northern Germany: A case study

NASA Technical Reports Server (NTRS)

Schmidt, Manfred

1994-01-01

At most of the German ozone recording stations which have records over a sufficiently long period, the results of the summer months of 1989 showed the highest values since the beginning of the measurements. One of the reasons for this phenomenon was the high duration of sunshine in that summer; for example, in Potsdam near Berlin in May 1989 the sunshine duration was the highest in May since the beginning of the records in 1893. For that reason we selected this summer for a case study. The basis for the study was mainly the ozone measuring stations of the network of Lower Saxony and the Federal Office of Environment (Umweltbundesamt). The results of these summer measurements point to intense sources of ozone, probably in form of gaseous precursors, in the Middle German industrial areas near Leipzig and Halle and in Northwestern Czechoslovakia, with coal-mining, chemical and petrochemical industries, coking plants and others. The maps of average ozone concentrations, number or days with high ozone maxima, ozone-windroses of the stations, etc., suggest that these areas could be a main source of precursors and of photochemical ozone production in summer smog episodes in Central Europe. Stations on the North Sea coast, at which early ozone measurements were made by our institute in 1973/74 are compared with similarly located stations of the Lower Saxon network in 1989 and the results show a reversal of the ozone-windroses. In 1973/74, the highest ozone concentrations were correlated with wind directions from the sea while in 1989 these concentrations were correlated with directions from the continent. In the recent years, photochemical ozone production on the continent is probably predominant, while in former years the higher ozone content of the maritime subpolar air masses has been explained by stratospheric-tropospheric exchange.

EXPERIMENTS ON PHOTOCHEMICAL AMINE FORMATION (in German)

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

Flemming, K.

It is shown that phenylalanine, tryptophan, and tyrosine in aqueous solutions are decarboxylized to phenylethylamine, tryptamine, and tyramine by uv- irradiation: therefore, production of dopamine in uv-irradiated dioxyphenylalanine solutions is considered probable. Therefore, not only vasodilating (histamine, serotonine) but also vasoconstrictor amines are produced by the photochemical amino acid decomposition. A substance in its effect similar to histamine is formed in addition to tyramine in uv-irradiated tyrosine solutions. Its chemical nature is unknown. The photochemical production of amines is increased by oxygen, reducing substances, and H/sub 2/O/sub 2/. It is assumed that it is caused not only directly by energymore » absorption but also indirectiy by the influence of OH- radicals. The radiobiological importance of the results is discussed. (auth)« less

Analysis of Ozone Levels from 2006 to 2016 in the Atlanta-Sandy Springs-Roswell Metropolitan Area

NASA Astrophysics Data System (ADS)

Dickinson, E.

2016-12-01

Ozone is a significant component of smog that persists in many large urban areas. Ozone is regulated by the U.S Environmental Protection Agency (EPA) as a criteria pollutant, and can lead to a variety of respiratory problems in sensitive groups. This study examines ozone concentrations in Atlanta-Sandy Springs- Roswell (Atlanta) metropolitan area, one of the largest urban areas in the Southeastern United States. Photochemical reactions involving oxides of nitrogen (NOx) and a variety of volatile organic compounds (VOCs) lead to ozone formation. The rate of ozone formation is exacerbated by Atlanta's hot and humid climate during the summers. Using data from EPA's Air Quality Systems database, this study analyzes ozone concentration data from regulatory monitoring sites in several counties that are in the metropolitan statistical area of Atlanta-Sandy Springs-Roswell, over a ten-year period (2006-2016). The study also looks at the meteorological conditions (such as temperature, wind speed, and humidity) over the same ten-year period (2006-2016) using data from the National Weather Service's Regional Airport Observations at Hartsfield-Jackson Airport in Atlanta. Based on a preliminary analysis of the ozone data, there is a downward trend in maximum daily 8-hour ozone concentration at all Atlanta-Sandy Springs-Roswell sites from 2006-2016. The decrease of ozone concentrations corresponds to three successively stricter National Ambient Air Quality Standards (NAAQS) for ozone (1997, 2008, and 2015) during the ten-year period of this study. The Atlanta area will be classified based on the 2015 ozone NAAQS, of 70 parts per billion, in the next few years. With EPA's upcoming attainment determination, this study looks at the recent trends in ozone concentrations and meteorology in the Atlanta area.

The 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

Simplified models were developed for radiative heating and cooling and for ozone photochemistry in the region 22-60 km. The latter permit the inclusion of nitrogen and hydrogen reactions in addition to simple oxygen reactions. The simplicity of the scheme facilitates the use of a wide variety of cooling and reaction rates. It is shown that joint radiative-photochemical equilibrium is appropriate to the mean state of the atmosphere between 35 and 60 km. The relaxation of perturbations from joint radiative-photochemical equilibrium was also investigated. In all cases the coupling between temperature dependent ozone photochemistry and radiation lead to a reduction of the thermal relaxation time from its purely radiative value. The latter, which amounts to about 10 days, is reduced to 2-4 days at heights of 31-35 km. This greatly enhances the dissipation of waves traveling through the stratosphere.

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

Treesearch

Karl Zeller

2000-01-01

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

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

PubMed

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

2014-09-02

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

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 ...

Effects of conventional ozonation and electro-peroxone pretreatment of surface water on disinfection by-product formation during subsequent chlorination.

PubMed

Mao, Yuqin; Guo, Di; Yao, Weikun; Wang, Xiaomao; Yang, Hongwei; Xie, Yuefeng F; Komarneni, Sridhar; Yu, Gang; Wang, Yujue

2018-03-01

The electro-peroxone (E-peroxone) process is an emerging ozone-based electrochemical advanced oxidation process that combines conventional ozonation with in-situ cathodic hydrogen peroxide (H 2 O 2 ) production for oxidative water treatment. In this study, the effects of the E-peroxone pretreatment on disinfection by-product (DBP) formation from chlorination of a synthetic surface water were investigated and compared to conventional ozonation. Results show that due to the enhanced transformation of ozone (O 3 ) to hydroxyl radicals (OH) by electro-generated H 2 O 2 , the E-peroxone process considerably enhanced dissolved organic carbon (DOC) abatement and significantly reduced bromate (BrO 3 - ) formation compared to conventional ozonation. However, natural organic matter (NOM) with high UV 254 absorbance, which is the major precursors of chlorination DBPs, was less efficiently abated during the E-peroxone process than conventional ozonation. Consequently, while both conventional ozonation and the E-peroxone process substantially reduced the formation of DBPs (trihalomethanes and haloacetic acids) during post-chlorination, higher DBP concentrations were generally observed during chlorination of the E-peroxone pretreated waters than conventional ozonation treated. In addition, because of conventional ozonation or the E-peroxone treatment, DBPs formed during post-chlorination shifted to more brominated species. The overall yields of brominated DBPs exhibited strong correlations with the bromide concentrations in water. Therefore, while the E-peroxone process can effectively suppress bromide transformation to bromate, it may lead to higher formation of brominated DBPs during post-chlorination compared to conventional ozonation. These results suggest that the E-peroxone process can lead to different DBP formation and speciation during water treatment trains compared to conventional ozonation. Copyright © 2017 Elsevier Ltd. All rights reserved.

Utilization of UARS Data in Validation of Photochemical and Dynamical Mechanisms in Stratospheric Models

NASA Technical Reports Server (NTRS)

Ko, M. K. W.; Rodriquez, J. M.; Hu, W.; Danilin, M. Y.; Shia, R.-L.

1998-01-01

The proposed work utilized Upper Atmosphere Research Satellite (UARS) measurements of short-lived and long-lived species, in conjunction with existing photochemical "box" models, trajectory models, and two-dimensional global models, to elucidate outstanding questions in our understanding of photochemical and dynamical mechanisms in the stratosphere. Particular emphasis was given to arriving at the best possible understanding of the chemical and dynamical contributions to the stratospheric ozone budget. Such understanding will increase confidence in the simulations carried out by assessment models.

Utilization of UARS Data in Validation of Photochemical and Dynamical Mechanisms in Stratospheric Models

NASA Technical Reports Server (NTRS)

Ko, Malcolm K. W.; Rodriquez, Jose M.; Hu, Wenjie; Danilin, Michael Y.; Shia, Run-Li

1998-01-01

The proposed work utilized Upper Atmosphere Research Satellite (UARS) measurements of short-lived and long-lived species, in conjunction with existing photochemical "box" models, trajectory models, and two-dimensional global models, to elucidate outstanding questions in our understanding of photochemical and dynamical mechanisms in the stratosphere. Particular emphasis was given to arriving at the best possible understanding of the chemical and dynamical contribution to the stratospheric ozone budget. Such understanding will increase confidence in the simulations carried out by assessment models.

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...

40 CFR 52.582 - Control strategy: Ozone.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 3 2010-07-01 2010-07-01 false Control strategy: Ozone. 52.582 Section 52.582 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED...—The Administrator approves the incorporation of the photochemical assessment ambient monitoring system...

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.

Vertical distribution of ozone at the terminator on Mars

NASA Astrophysics Data System (ADS)

Maattanen, Anni; Lefevre, Franck; Guilbon, Sabrina; Listowski, Constantino; Montmessin, Franck

2016-10-01

The SPICAM/Mars Express UV solar occultation dataset gives access to the ozone vertical distribution via the ozone absorption in the Hartley band (220-280 nm). We present the retrieved ozone profiles and compare them to the LMD Mars Global Climate Model (LMD-MGCM) results.Due to the photochemical reactivity of ozone, a classical comparison of local density profiles is not appropriate for solar occultations that are acquired at the terminator, and we present here a method often used in the Earth community. The principal comparison is made via the slant profiles (integrated ozone concentration on the line-of-sight), since the spherical symmetry hypothesis made in the onion-peeling vertical inversion method is not valid for photochemically active species (e.g., ozone) around terminator. For each occultation, we model the ozone vertical and horizontal distribution with high solar zenith angle (or local time) resolution around the terminator and then integrate the model results following the lines-of-sight of the occultation to construct the modeled slant profile. We will also discuss the difference of results between the above comparison method and a comparison using the local density profiles, i.e., the observed ones inverted by using the spherical symmetry hypothesis and the modeled ones extracted from the LMD-MGCM exactly at the terminator. The method and the results will be presented together with the full dataset.SPICAM is funded by the French Space Agency CNES and this work has received funding from the European Union's Horizon 2020 Programme (H2020-Compet-08-2014) under grant agreement UPWARDS-633127.

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. Copyright © 2016 Elsevier Ltd. All rights reserved.

On the link between martian total ozone and potential vorticity

NASA Astrophysics Data System (ADS)

Lewis, S.; Holmes, J.; Patel, M.

2016-12-01

We demonstrate for the first time that total ozone in the martian atmosphere is highly correlated with the dynamical tracer, potential vorticity, under certain conditions. The degree of correlation is investigated using a Mars global circulation model including a photochemical model. Potential vorticity is the quantity of choice to explore the dynamical nature of polar vortices because it contains information on winds and temperature in a single scalar variable.The correlation is found to display a distinct seasonal variation, with a strong positive correlation in both northern and southern winter at poleward latitudes in the northern and southern hemisphere respectively. The identified strong correlation implies variations in polar total ozone during winter are predominantly controlled by dynamical processes in these spatio-temporal regions. The weak correlation in northern and southern summer is due to the dominance of photochemical reactions resulting from extended exposure to sunlight. The total ozone/potential vorticity correlation is slightly weaker in southern winter due to topographical variations and the preference for ozone to accumulate in Hellas basin. In northern winter, total ozone can be used to track the polar vortex edge. The ozone/potential vorticity ratio is calculated for both northern and southern winter on Mars for the first time. Using the strong correlation in total ozone and potential vorticity in northern winter inside the polar vortex, it is shown that potential vorticity can be used as a proxy to deduce the distribution of total ozone where satellites cannot observe for the majority of northern winter. Where total ozone observations are available on the fringes of northern winter at poleward latitudes, the strong relationship of total ozone and potential vorticity implies that total ozone anomalies in the surf zone can be of use to investigate the origin of potential vorticity filaments.

On the link between martian total ozone and potential vorticity

NASA Astrophysics Data System (ADS)

Holmes, James A.; Lewis, Stephen R.; Patel, Manish R.

2017-01-01

We demonstrate for the first time that total ozone in the martian atmosphere is highly correlated with the dynamical tracer, potential vorticity, under certain conditions. The degree of correlation is investigated using a Mars global circulation model including a photochemical model. Potential vorticity is the quantity of choice to explore the dynamical nature of polar vortices because it contains information on winds and temperature in a single scalar variable. The correlation is found to display a distinct seasonal variation, with a strong positive correlation in both northern and southern winter at poleward latitudes in the northern and southern hemisphere respectively. The identified strong correlation implies variations in polar total ozone during winter are predominantly controlled by dynamical processes in these spatio-temporal regions. The weak correlation in northern and southern summer is due to the dominance of photochemical reactions resulting from extended exposure to sunlight. The total ozone/potential vorticity correlation is slightly weaker in southern winter due to topographical variations and the preference for ozone to accumulate in Hellas basin. In northern winter, total ozone can be used to track the polar vortex edge. The ozone/potential vorticity ratio is calculated for both northern and southern winter on Mars for the first time. Using the strong correlation in total ozone and potential vorticity in northern winter inside the polar vortex, it is shown that potential vorticity can be used as a proxy to deduce the distribution of total ozone where satellites cannot observe for the majority of northern winter. Where total ozone observations are available on the fringes of northern winter at poleward latitudes, the strong relationship of total ozone and potential vorticity implies that total ozone anomalies in the surf zone of the northern polar vortex can potentially be used to determine the origin of potential vorticity filaments.

Carbonyl compounds at Mount Tai in the North China Plain: Characteristics, sources, and effects on ozone formation

NASA Astrophysics Data System (ADS)

Yang, Xue; Xue, Likun; Yao, Lan; Li, Qinyi; Wen, Liang; Zhu, Yanhong; Chen, Tianshu; Wang, Xinfeng; Yang, Lingxiao; Wang, Tao; Lee, Shuncheng; Chen, Jianmin; Wang, Wenxing

2017-11-01

Carbonyl compounds, an important category of volatile organic compounds (VOCs), play important roles in ozone (O3) formation and atmospheric chemistry. To better understand the characteristics and sources of carbonyl compounds and their effects on O3 formation, C1-C8 carbonyls were measured at Mount Tai, the highest mountain in the North China Plain (NCP), in summer 2014. Acetone (3.57 ± 0.55 ppbv), formaldehyde (3.48 ± 0.98 ppbv) and acetaldehyde (1.27 ± 0.78 ppbv) are the three most abundant species, comprising as high as 90% of the total observed compounds. Isovaleraldehyde (0.37 ± 0.17 ppbv) presents another important carbonyl compound despite its high reactivity. Comparison with the observations available in China highlights the serious situation of carbonyls pollution in the NCP region. The sources of carbonyls are dominated by photo-oxidation of VOCs during the daytime and regional transport at night. Secondary sources from oxidation of hydrocarbons contribute on average 44% of formaldehyde, 31% of acetone, 85% of acetaldehyde, 78% of benzaldehyde, and 84% of isovaleraldehyde, demonstrating the dominant role of secondary formation in the ambient carbonyl levels. Formaldehyde, acetaldehyde and isovaleraldehyde are the most important contributors to the OH reactivity and O3 production among the measured carbonyls. This study shows that carbonyl compounds contribute significantly to the photochemical pollution in the NCP region and hence understanding their sources and characteristics is essential for developing the science-based O3 pollution control strategies.

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

NASA Astrophysics Data System (ADS)

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

2008-09-01

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

Potential biosignatures in super-Earth atmospheres II. Photochemical responses.

PubMed

Grenfell, J L; Gebauer, S; Godolt, M; Palczynski, K; Rauer, H; Stock, J; von Paris, P; Lehmann, R; Selsis, F

2013-05-01

Spectral characterization of super-Earth atmospheres for planets orbiting in the habitable zone of M dwarf stars is a key focus in exoplanet science. A central challenge is to understand and predict the expected spectral signals of atmospheric biosignatures (species associated with life). Our work applies a global-mean radiative-convective-photochemical column model assuming a planet with an Earth-like biomass and planetary development. We investigated planets with gravities of 1g and 3g and a surface pressure of 1 bar around central stars with spectral classes from M0 to M7. The spectral signals of the calculated planetary scenarios have been presented by in an earlier work by Rauer and colleagues. The main motivation of the present work is to perform a deeper analysis of the chemical processes in the planetary atmospheres. We apply a diagnostic tool, the Pathway Analysis Program, to shed light on the photochemical pathways that form and destroy biosignature species. Ozone is a potential biosignature for complex life. An important result of our analysis is a shift in the ozone photochemistry from mainly Chapman production (which dominates in Earth's stratosphere) to smog-dominated ozone production for planets in the habitable zone of cooler (M5-M7)-class dwarf stars. This result is associated with a lower energy flux in the UVB wavelength range from the central star, hence slower planetary atmospheric photolysis of molecular oxygen, which slows the Chapman ozone production. This is important for future atmospheric characterization missions because it provides an indication of different chemical environments that can lead to very different responses of ozone, for example, cosmic rays. Nitrous oxide, a biosignature for simple bacterial life, is favored for low stratospheric UV conditions, that is, on planets orbiting cooler stars. Transport of this species from its surface source to the stratosphere where it is destroyed can also be a key process. Comparing 1g with

TRANSPORT, RADIATIVE, AND DYNAMICAL EFFECTS OF THE ANTARCTIC OZONE HOLE: A GFDL "SKYHI" MODEL EXPERIMENT

EPA Science Inventory

The GFDL 'SKYHI' general circulation model has been used to simulate the effect of the Antarctic "ozone hole" phenomenon on the radiative and dynamical environment of the lower stratosphere. oth the polar ozone destruction and photochemical restoration chemistries are calculated ...

Contrasting physiological responses of ozone-tolerant Phaseolus vulgaris and Nicotiana tobaccum varieties to ozone and nitric acid

Treesearch

Cara M. Stripe; Louis S. Santiago; Pamela E. Padgett

2014-01-01

Ozone (O3) and nitric acid (HNO3) are synthesized by the same atmospheric photochemical processes and are almost always co-pollutants. Effects of O3 on plants have been well-elucidated, yet less is known about the effects of HNO3 on plants. We investigated the physiological...

A Cloud-Ozone Data Product from Aura OMI and MLS Satellite Measurements.

PubMed

Ziemke, Jerald R; Strode, Sarah A; Douglass, Anne R; Joiner, Joanna; Vasilkov, Alexander; Oman, Luke D; Liu, Junhua; Strahan, Susan E; Bhartia, Pawan K; Haffner, David P

2017-01-01

Ozone within deep convective clouds is controlled by several factors involving photochemical reactions and transport. Gas-phase photochemical reactions and heterogeneous surface chemical reactions involving ice, water particles, and aerosols inside the clouds all contribute to the distribution and net production and loss of ozone. Ozone in clouds is also dependent on convective transport that carries low troposphere/boundary layer ozone and ozone precursors upward into the clouds. Characterizing ozone in thick clouds is an important step for quantifying relationships of ozone with tropospheric H 2 O, OH production, and cloud microphysics/transport properties. Although measuring ozone in deep convective clouds from either aircraft or balloon ozonesondes is largely impossible due to extreme meteorological conditions associated with these clouds, it is possible to estimate ozone in thick clouds using backscattered solar UV radiation measured by satellite instruments. Our study combines Aura Ozone Monitoring Instrument (OMI) and Microwave Limb Sounder (MLS) satellite measurements to generate a new research product of monthly-mean ozone concentrations in deep convective clouds between 30°S to 30°N for October 2004 - April 2016. These measurements represent mean ozone concentration primarily in the upper levels of thick clouds and reveal key features of cloud ozone including: persistent low ozone concentrations in the tropical Pacific of ~10 ppbv or less; concentrations of up to 60 pphv or greater over landmass regions of South America, southern Africa, Australia, and India/east Asia; connections with tropical ENSO events; and intra-seasonal/Madden-Julian Oscillation variability. Analysis of OMI aerosol measurements suggests a cause and effect relation between boundary layer pollution and elevated ozone inside thick clouds over land-mass regions including southern Africa and India/east Asia.

Trends in surface ozone concentrations at Arosa (Switzerland)

NASA Astrophysics Data System (ADS)

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

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

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.

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) ...

Ozone production, nitrogen oxides, and radical budgets in Mexico City: observations from Pico de Tres Padres

NASA Astrophysics Data System (ADS)

Wood, E. C.; Herndon, S. C.; Onasch, T. B.; Kroll, J. H.; Canagaratna, M. R.; Kolb, C. E.; Worsnop, D. R.; Neuman, J. A.; Seila, R.; Zavala, M.; Knighton, W. B.

2008-08-01

Observations at a mountain-top site within the Mexico City basin are used to characterize ozone production and destruction, the nitrogen oxide budget, and the radical budget during the MILAGRO campaign. An ozone production rate of ~50 ppbv/h was observed in a stagnant air mass during the afternoon of 12 March 2006, which is among the highest observed anywhere in the world. Approximately half of the ozone destruction was due to the oxidation of NO2. During this time period ozone production was VOC-limited, deduced by a comparison of the radical production rates and the formation rate of NOx oxidation products (NOz) For [NOx]/[NOy] values between 0.2 and 0.8, gas-phase HNO3 typically accounted for less than 10% of NOz and accumulation-mode particulate nitrate (NO3-(PM)) accounted for 20% 70% of NOz, consistent with high ambient NH3 concentrations. The fraction of NOz accounted for by the sum of HNO3(g) and NO3-(PM) decreased with photochemical processing. This decrease is apparent even when dry deposition of HNO3 is accounted for, and indicates that HNO3 formation decreased relative to other NOx "sink" processes during the first 12 h of photochemistry and/or a significant fraction of the nitrate was associated with the coarse aerosol size mode. The ozone production efficiency of NOx on 11 and 12 March 2006 was approximately 7 on a time scale of one day. A new metric for ozone production efficiency that relates the dilution-adjusted ozone mixing ratio to cumulative OH exposure is proposed.

Photochemical Pollution over the suburban forest in Seoul South Korea

NASA Astrophysics Data System (ADS)

Kim, Saewung; Sanchez, Dianne; Jeong, Daun; Seco, Roger; Gu, Dasa; Guenther, Alex; Lee, Meehye

2017-04-01

We will present long term photo-chemical observations at Taehwa Research Forest a suburban forest near by Seoul Metropolitan Area a home of 23 million. The discussion is mainly about observations during KORUS-AQ 2016 a NASA-NIER collaborative field campaign in the late spring. There were a couple of pollution stagnation episodes during the campaign and we will present how intensified pollution elevate ozone forming potentials by interacting with BVOC from surrounding forest. During the campaign, we conducted a comprehensive suite of trace gas observations along with OH reactivity and radical precursor observations. We will comprehensively examine atmospheric oxidation capacity and reactivity to evaluate the accuracy of our photochemical understanding in diagnosing regional pollution.

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 ...

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...

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

EPA Science Inventory

The purpose of this 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. mphasis was placed on the photochemical smog formation mechanism under stagnant...

Contribution of ozone to airborne aldehyde formation in Paris homes.

PubMed

Rancière, Fanny; Dassonville, Claire; Roda, Célina; Laurent, Anne-Marie; Le Moullec, Yvon; Momas, Isabelle

2011-09-15

Indoor aldehydes may result from ozone-initiated chemistry, mainly documented by experimental studies. As part of an environmental investigation included in the PARIS birth cohort, the aim of this study was to examine ozone contribution to airborne aldehyde formation in Paris homes. Formaldehyde, acetaldehyde and hexaldehyde levels, as well as styrene, nitrogen dioxide and nicotine concentrations, comfort parameters and carbon dioxide levels, were measured twice during the first year of life of the babies. Ambient ozone concentrations were collected from the closest background station of the regional air monitoring network. Traffic-related nitrogen oxide concentrations in front of the dwellings were estimated by an air pollution dispersion model. Home characteristics and families' way of life were described by questionnaires. Stepwise multiple linear regression models were used to link aldehyde levels with ambient ozone concentrations and a few aldehyde precursors involved in oxidation reactions, adjusting for other indoor aldehyde sources, comfort parameters and traffic-related nitrogen oxides. A 4 and 11% increase in formaldehyde and hexaldehyde levels was pointed out when 8-hour ozone concentrations increased by 20 μg/m(3). The influence of potential precursors such as indoor styrene level and frequent use of air fresheners, containing unsaturated volatile organic compounds as terpenes, was also found. Thus, our results suggest that ambient ozone can significantly impact indoor air quality, especially with regard to formaldehyde and hexaldehyde levels. Copyright © 2011 Elsevier B.V. All rights reserved.

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

PubMed

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

2017-03-01

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

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).

In situ measurements of the photochemical formation rates and optical properties of organic aerosols in CH4/CO2 mixtures.

NASA Astrophysics Data System (ADS)

Adamkovics, M.; Boering, K. A.

2003-12-01

The presence of photochemically-generated hazes has a significant impact on radiative transfer in planetary atmospheres. While the rates of particle formation have been inferred from photochemical or microphysical models constrained to match observations, these rates have not been determined experimentally. Thus, the fundamental kinetics of particle formation are not known and remain highly parameterized in planetary atmospheric models. We have developed instrumentation for measuring the formation rates and optical properties of organic aerosols produced by irradiating mixtures of precursor gases via in situ optical (633nm) scattering and online quadrupole mass spectrometry (1-200 amu). Results for the generation of particulate hydrocarbons from the irradiation of pure, gas-phase CH4 as well as CH4/CO2 mixtures with vacuum ultraviolet (120-160nm) light, along with simultaneous measurements of the evolution of higher gas-phase hydrocarbons will be presented.

Evidence for midwinter chemical ozone destruction over Antartica

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

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

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 wheremore » 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.« less

Tropospheric Ozone Over North America

NASA Astrophysics Data System (ADS)

Oltmans, S. J.; Thompson, A. M.; Cooper, O. R.; Merrill, J. T.; Tarasick, D. W.; Newchurch, M. J.

2007-05-01

Ozone in the troposphere plays a significant role as an absorber of infrared radiation (greenhouse gas), in the cleansing capacity of the atmosphere as a precursor of hydroxol radical formation, and a regulated air pollutant capable of deleterious health and ecosystem effects. Knowledge of the ozone budget in the troposphere over North America (NA) is required to properly understand the various mechanisms that contribute to the measured distribution and to develop and test models capable of simulating and predicting this key player in atmospheric chemical and physical processes. Recent field campaigns including the 2004 and 2006 INTEX Ozone Network Studies (IONS) http:croc.gsfc.nasa.gov/intexb/ions06.html that have included intensive ozone profile measurements from ozonesondes provide a unique data set for describing tropospheric ozone over a significant portion of the North American continent. These campaigns have focused on the spring and summer seasons when tropospheric ozone over NA is particularly influenced by long-range transport processes, significant photochemical ozone production resulting from both anthropogenic and natural (lightning) precursor emissions, and exchange with the stratosphere. This study uses ozone profiles measured over NA in the latitude band from approximately 12-60N, extending from the tropics to the high mid latitudes, to describe the seasonal behavior of tropospheric ozone over NA with an emphasis on the spring and summer. This includes the variability within seasons at a particular site as well as the contrasts between the seasons. Emphasis is placed on the variations among the sites including latitudinal and longitudinal gradients and how these differ through the seasons and with altitude in the troposphere. Regional differences are most pronounced during the summer season likely reflecting the influence of a wider variation in processes influencing the tropospheric ozone distribution including lightning NOX production in the upper

Measurements of upward turbulent ozone fluxes above a subalpine spruce-fir forest

Treesearch

Karl Zeller; Ted Hehn

1996-01-01

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

Extreme Value Analysis for Evaluating Ozone Control Strategies

EPA Science Inventory

Tropospheric ozone is one of six criteria pollutants regulated by the US EPA, and has been linked to respiratory and cardiovascular endpoints and adverse effects on vegetation and ecosystems. Regional photochemical models have been developed to study the impacts of emission reduc...

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.

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

PubMed

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

2011-01-01

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

Meteorological and chemical impacts on ozone formation: A case study in Hangzhou, China

NASA Astrophysics Data System (ADS)

Li, Kangwei; Chen, Linghong; Ying, Fang; White, Stephen J.; Jang, Carey; Wu, Xuecheng; Gao, Xiang; Hong, Shengmao; Shen, Jiandong; Azzi, Merched; Cen, Kefa

2017-11-01

Regional ozone pollution has become one of the most challenging problems in China, especially in the more economically developed and densely populated regions like Hangzhou. In this study, measurements of O3, CO, NOx and non-methane hydrocarbons (NMHCs), together with meteorological data, were obtained for the period July 1, 2013-August 15, 2013 at three sites in Hangzhou. These sites included an urban site (Zhaohui ;ZH;), a suburban site (Xiasha ;XS;) and a rural site (Qiandaohu ;QDH;). During the observation period, both ZH and XS had a higher ozone level than QDH, with exceeding rates of 41.3% and 47.8%, respectively. Elevated O3 levels in QDH were found at night, which could be explained by less prominent NO titration effect in rural area. Detailed statistical analysis of meteorological and chemical impacts on ozone formation was carried out for ZH, and higher ozone concentration was observed when the wind direction was from the east. This is possibly due to emissions of VOCs from XS, a typical chemical industrial park located in 30 km upwind area of ZH. A comprehensive comparison between three ozone episode periods and one non-episode period were made in ZH. It was concluded that elevated concentrations of precursors and temperatures, low relative humidity and wind speed and easterly-dominated wind direction contribute to urban ozone episodes in Hangzhou. VOCs reactivity analysis indicated that reactive alkenes like isoprene and isobutene contributed most to ozone formation. Three methods were applied to evaluate O3-VOCs-NOx sensitivity in ZH: VOCs/NOx ratio method, Smog Production Model (SPM) and Relative Incremental Reactivity (RIR). The results show that summer ozone in urban Hangzhou mostly presents VOCs-limited and transition region alternately. Our study implies that the increasing automobiles and VOCs emissions from upwind area could result in ozone pollution in urban Hangzhou, and synergistic reduction of VOCs and NOx will be more effective.

Ozone production potential following convective redistribution of biomass burning emissions

NASA Technical Reports Server (NTRS)

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

1992-01-01

The effects of deep convection on the potential for forming ozone in the free troposphere have been simulated for regions where the trace gas composition is influenced by biomass burning. Cloud photochemical and dynamic simulations based on observations in the 1980 and 1985 Brazilian campaigns form the basis of a sensitivity study of the ozone production potential under differing conditions. It is seen that there is considerably more ozone formed in the middle and upper troposphere when convection has redistributed hydrocarbons, NO(x), and CO compared to the example of no convection.

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.

Missing ozone-induced potential aerosol formation in a suburban deciduous forest

NASA Astrophysics Data System (ADS)

Nakayama, T.; Kuruma, Y.; Matsumi, Y.; Morino, Y.; Sato, K.; Tsurumaru, H.; Ramasamy, S.; Sakamoto, Y.; Kato, S.; Miyazaki, Y.; Mochizuki, T.; Kawamura, K.; Sadanaga, Y.; Nakashima, Y.; Matsuda, K.; Kajii, Y.

2017-12-01

As a new approach to investigating formation processes of secondary organic aerosol (SOA) in the atmosphere, ozone-induced potential aerosol formation was measured in summer at a suburban forest site surrounded by deciduous trees, near Tokyo, Japan. After passage through a reactor containing high concentrations of ozone, increases in total particle volume (average of 1.4 × 109 nm3/cm3, which corresponds to 17% that of pre-existing particles) were observed, especially during daytime. The observed aerosol formations were compared with the results of box model simulations using simultaneously measured concentrations of gaseous and particulate species. According to the model, the relative contributions of isoprene, monoterpene, and aromatic hydrocarbon oxidation to SOA formation in the reactor were 24, 21, and 55%, respectively. However, the model could explain, on average, only ∼40% of the observed particle formation, and large discrepancies between the observations and model were found, especially around noon and in the afternoon when the concentrations of isoprene and oxygenated volatile organic compounds were high. The results suggest a significant contribution of missing (unaccounted-for) SOA formation processes from identified and/or unidentified volatile organic compounds, especially those emitted during daytime. Further efforts should be made to explore and parameterize this missing SOA formation to assist in the improvement of atmospheric chemistry and climate models.

Formation of N-nitrosodimethylamine (NDMA) by ozonation of dyes and related compounds.

PubMed

Oya, Masami; Kosaka, Koji; Asami, Mari; Kunikane, Shoichi

2008-12-01

Formation of N-nitrosodimethylamine (NDMA) by ozonation of commercially available dyes and related compounds was investigated. Ozonation was conducted using a semi-batch type reactor, and ozone concentration in gas phase and the ozone gas flow were 10 mg L(-1) and 1.0 L min(-1), respectively. NDMA was formed by 15 min of ozonation of seven out of eight selected target compounds (0.05 mM) at pH 7. All the target compounds with N,N-dimethylamino functions were NDMA precursors in ozonation. The lowest and highest NDMA concentrations after ozonation of the target compounds were 13 ng L(-1) for N,N-dimethylformamide (DMF) and 1600 ng L(-1) for N,N-dimethyl-p-phenylenediamine (DMPD), respectively. NDMA concentrations after 15 min of ozonation of 0.05 mM methylene blue (MB) and DMPD increased with an increase in pH in its range of 6-8. The effects of coexisting compounds on NDMA concentrations after 15 min of ozonation of 0.05 mM MB and DMPD were examined at pH 7. NDMA concentrations after ozonation of MB and DMPD increased by the presence of 0.05 mM (0.7 mg L(-1) as N) nitrite (NO(2)(-)); 5000 ng L(-1) for MB and 4000 ng L(-1) for DMPD. NDMA concentration after MB ozonation decreased by the presence of 5mM tertiary butyl alcohol (TBA), a hydroxyl radical (HO.) scavenger, but that after DMPD ozonation was increased by the presence of TBA. NDMA concentrations after ozonation of MB and DMPD were not affected by the presence of 0.16 mM (5.3 mg L(-1)) hydrogen peroxide (H(2)O(2)). When 0.05 mM MB and DMPD were added to the Yodo and Tone river water samples, NDMA concentrations after 15 min of their ozonation at pH 7 increased compared with those in the case of addition to ultrapure water samples.

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.;

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.

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

Chemical Data Assimilation Estimates of Continental US Ozone and Nitrogen Budgets during INTEX-A

NASA Technical Reports Server (NTRS)

Pierce, Robert B.; Schaack, Todd K.; Al-Saadi, Jassim A.; Fairlie, T. Duncan; Kittaka, Chieko; Lingenfelser, Gretchen; Natarajan, Murali; Olson, Jennifer; Soja, Amber; Zapotocny, Tom;

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

PubMed

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

2015-10-27

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

Ozone Production and Loss Rate Measurements in the Middle Stratosphere

NASA Technical Reports Server (NTRS)

Jucks, Kenneth W.; Johnson, David G.; Chance, K. V.; Traub, Wesley A.; Salawitch, R. J.; Stachnik, R. A.

1996-01-01

The first simultaneous measurements of HO(x), NO(x), and Cl(x) radicals in the middle stratosphere show that NO(x) catalytic cycles dominate loss of ozone (O3) for altitudes between 24 and 38 km; Cl(x) catalytic cycles are measured to be less effective than previously expected; and there is no 'ozone deficit' in the photochemically dominated altitude range from 31 and 38 km, contrary to some previous theoretical studies.

Kinetic and mechanistic reactivity. Isoprene impact on ozone levels in an urban area near Tijuca Forest, Rio de Janeiro.

PubMed

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

2016-12-01

Volatile organic compounds (VOCs) play a central role in atmospheric chemistry. In this work, the kinetic and mechanistic reactivities of VOCs are analyzed, and the contribution of the organic compounds emitted by anthropogenic and natural sources is estimated. VOCs react with hydroxyl radicals and other photochemical oxidants, such as ozone and nitrate radicals, which cause the conversion of NO to NO 2 in various potential reaction paths, including photolysis, to form oxygen atoms, which generate ozone. The kinetic reactivity was evaluated based on the reaction coefficients for hydroxyl radicals with VOCs. The mechanistic reactivity was estimated using a detailed mechanism and the incremental reactivity scale that Carter proposed. Different scenarios were proposed and discussed, and a minimum set of compounds, which may describe the tropospheric reactivity in the studied area, was determined. The role of isoprene was analyzed in terms of its contribution to ozone formation.

Potential Biosignatures in Super-Earth Atmospheres II. Photochemical Responses

PubMed Central

Gebauer, S.; Godolt, M.; Palczynski, K.; Rauer, H.; Stock, J.; von Paris, P.; Lehmann, R.; Selsis, F.

2013-01-01

Abstract Spectral characterization of super-Earth atmospheres for planets orbiting in the habitable zone of M dwarf stars is a key focus in exoplanet science. A central challenge is to understand and predict the expected spectral signals of atmospheric biosignatures (species associated with life). Our work applies a global-mean radiative-convective-photochemical column model assuming a planet with an Earth-like biomass and planetary development. We investigated planets with gravities of 1g and 3g and a surface pressure of 1 bar around central stars with spectral classes from M0 to M7. The spectral signals of the calculated planetary scenarios have been presented by in an earlier work by Rauer and colleagues. The main motivation of the present work is to perform a deeper analysis of the chemical processes in the planetary atmospheres. We apply a diagnostic tool, the Pathway Analysis Program, to shed light on the photochemical pathways that form and destroy biosignature species. Ozone is a potential biosignature for complex life. An important result of our analysis is a shift in the ozone photochemistry from mainly Chapman production (which dominates in Earth's stratosphere) to smog-dominated ozone production for planets in the habitable zone of cooler (M5–M7)-class dwarf stars. This result is associated with a lower energy flux in the UVB wavelength range from the central star, hence slower planetary atmospheric photolysis of molecular oxygen, which slows the Chapman ozone production. This is important for future atmospheric characterization missions because it provides an indication of different chemical environments that can lead to very different responses of ozone, for example, cosmic rays. Nitrous oxide, a biosignature for simple bacterial life, is favored for low stratospheric UV conditions, that is, on planets orbiting cooler stars. Transport of this species from its surface source to the stratosphere where it is destroyed can also be a key process

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.

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.

Air Quality Criteria for Ozone and Other Photochemical Oxidants. External Review Draft No 1. Volume III

EPA Science Inventory

This review of the effects of photochemical oxidants on vegetation and the responses of vegetation to photochemical oxidants first discusses the general methodologies used in studies of air pollution effects to provide a basis for understanding the methods, approaches, and experi...

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

Changes in air quality and tropospheric composition due to depletion of stratospheric ozone and interactions with climate.

PubMed

Tang, X; Wilson, S R; Solomon, K R; Shao, M; Madronich, S

2011-02-01

Air pollution will be directly influenced by future changes in emissions of pollutants, climate, and stratospheric ozone, and will have significant consequences for human health and the environment. UV radiation is one of the controlling factors for the formation of photochemical smog, which includes tropospheric ozone (O(3)) and aerosols; it also initiates the production of hydroxyl radicals (˙OH), which control the amount of many climate- and ozone-relevant gases (e.g., methane and HCFCs) in the atmosphere. Numerical models predict that future changes in UV radiation and climate will modify the trends and geographic distribution of ˙OH, thus affecting the formation of photochemical smog in many urban and regional areas. Concentrations of ˙OH are predicted to decrease globally by an average of 20% by 2100, with local concentrations varying by as much as a factor of two above and below current values. However, significant differences between modelled and measured values in a limited number of case studies show that chemistry of hydroxyl radicals in the atmosphere is not fully understood. Photochemically produced tropospheric ozone is projected to increase. If emissions of anthropogenic air pollutants from combustion of fossil fuels, burning of biomass, and agricultural activities continue to increase, concentrations of tropospheric O(3) will tend to increase over the next 20-40 years in certain regions of low and middle latitudes because of interactions of emissions, chemical processes, and climate change. Climate-driven increases in temperature and humidity will also increase production of tropospheric O(3) in polluted regions, but reduce it in more pristine regions. Higher temperatures tend to increase emissions of nitrogen oxides (NO(x)) from some soils and release of biogenic volatile organic compounds (VOCs) from vegetation, leading to greater background concentrations of ozone in the troposphere. The net effects of future changes in UV radiation

40 CFR 52.2585 - Control strategy: Ozone.

Code of Federal Regulations, 2010 CFR

2010-07-01

... serious nonattainment for ozone is approved, based on Wisconsin's demonstration through photochemical grid... are 0.74 tons of volatile organic compounds (VOC) per day and 1.17 tons of oxides of nitrogen (NOX... section 182(2)(3)(A) of the Clean Air Act as amended in 1990. (s) Approval—On January 31, 2003, Wisconsin...

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.

From Mars Meteorites to Laboratory Investigations: Understanding Heterogeneous Photochemical Transformations Using Oxygen Triple Isotope Anomalies of Carbonates

NASA Astrophysics Data System (ADS)

Shaheen, R.; Smirnova, V.; Jackson, T. L.; Mang, L.; Thiemens, M. H.

2016-12-01

The planet Mars is unique in our solar system with a positive O-isotope anomaly observed in its bulk silicate and carbonates minerals ranging from 0.3 to 0.6 ‰. The carbonate isotopic signature can be used to reveal its origin, past history and atmosphere-hydrosphere-geosphere-interactions. Ozone is a powerful natural tracer of photochemical processes in Earth's atmosphere. It possess the highest enrichment in heavy isotopes δ17O ≈ δ18O (70-150‰) and oxygen isotopic anomaly (Δ17O = 30-40‰). The oxygen isotopic anomaly from ozone is transferred to other oxygen carrying molecules in the atmosphere through different mechanisms. Laboratory experiments were conducted with the JSC-Mars Simulant and iron oxide to investigate how this anomaly can be transferred to water and minerals under conditions similar to present day Mars. Three sets of laboratory experiments (O3-H2O-UV-minerals; O2-H2O-UV-minerals; O3-H2O-minerals) were performed. The oxygen triple isotopic analysis of product mineral carbonates formed from adsorbed CO2 reaction showed an oxygen isotopic anomaly (Δ17O = 0.4-3‰). The oxygen triple isotopic composition of water at photochemical equilibrium shifted towards ozone with Δ17O = 9‰ indicating reaction of ozone with water vapor via electronically excited oxygen atoms and transfer of the anomaly via hydroxyl radicals. HOx (HO, HO2) are extremely reactive and have very short life time (< μs), however, our data indicate that its signature is preserved through surficial interactions with adsorbed CO2 on mineral surfaces. Hydroxyl radicals may have played a significant role in heterogeneous photochemical transformations on mineral dust in the atmosphere of Mars and transfer of ozone anomaly to water and other oxygen bearing minerals through surficial reactions. Series of experiments were performed to constrain the amount of H2O required to preserve the oxygen isotope anomaly observed in carbonate minerals in the Martian meteorites. These

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.

Sensitivity studies and a simple ozone perturbation experiment with a truncated two-dimensional model of the stratosphere

NASA Technical Reports Server (NTRS)

Stordal, Frode; Garcia, Rolando R.

1987-01-01

The 1-1/2-D model of Holton (1986), which is actually a highly truncated two-dimensional model, describes latitudinal variations of tracer mixing ratios in terms of their projections onto second-order Legendre polynomials. The present study extends the work of Holton by including tracers with photochemical production in the stratosphere (O3 and NOy). It also includes latitudinal variations in the photochemical sources and sinks, improving slightly the calculated global mean profiles for the long-lived tracers studied by Holton and improving substantially the latitudinal behavior of ozone. Sensitivity tests of the dynamical parameters in the model are performed, showing that the response of the model to changes in vertical residual meridional winds and horizontal diffusion coefficients is similar to that of a full two-dimensional model. A simple ozone perturbation experiment shows the model's ability to reproduce large-scale latitudinal variations in total ozone column depletions as well as ozone changes in the chemically controlled upper stratosphere.

Anomalous low tropospheric column ozone over eastern India during the severe drought event of monsoon 2002: a case study.

PubMed

Ghude, Sachin D; Kulkarni, Santosh H; Kulkarni, Pavan S; Kanawade, Vijay P; Fadnavis, Suvarna; Pokhrel, Samir; Jena, Chinmay; Beig, G; Bortoli, D

2011-09-01

The present study is an attempt to examine some of the probable causes of the unusually low tropospheric column ozone observed over eastern India during the exceptional drought event in July 2002. We examined horizontal wind and omega (vertical velocity) anomalies over the Indian region to understand the large-scale dynamical processes which prevailed in July 2002. We also examined anomalies in tropospheric carbon monoxide (CO), an important ozone precursor, and observed low CO mixing ratio in the free troposphere in 2002 over eastern India. It was found that instead of a normal large-scale ascent, the air was descending in the middle and lower troposphere over a vast part of India. This configuration was apparently responsible for the less convective upwelling of precursors and likely caused less photochemical ozone formation in the free troposphere over eastern India in July 2002. The insight gained from this case study will hopefully provide a better understanding of the process controlling the distribution of the tropospheric ozone over the Indian region.

Impact of Biomass Burning Plumes on Photolysis Rates and Ozone Formation at the Mount Bachelor Observatory

NASA Astrophysics Data System (ADS)

Baylon, P.; Jaffe, D. A.; Hall, S. R.; Ullmann, K.; Alvarado, M. J.; Lefer, B. L.

2018-02-01

In this paper, we examine biomass burning (BB) events at the Mt. Bachelor Observatory (MBO) during the summer of 2015. We explored the photochemical environment in these BB plumes, which remains poorly understood. Because we are interested in understanding the effect of aerosols only (as opposed to the combined effect of aerosols and clouds), we carefully selected three cloud-free days in August and investigate the photochemistry in these plumes. At local midday (solar zenith angle (SZA) = 35°), j(NO2) values were slightly higher (0.2-1.8%) in the smoky days compared to the smoke-free day, presumably due to enhanced scattering by the smoke aerosols. At higher SZA (70°), BB aerosols decrease j(NO2) by 14-21%. We also observe a greater decrease in the actinic flux at 310-350 nm, compared to 360-420 nm, presumably due to absorption in the UV by brown carbon. We compare our measurements with results from the Tropospheric Ultraviolet-Visible v.5.2 model. As expected, we find a good agreement (to within 6%) during cloud-free conditions. Finally, we use the extended Leighton relationship and a photochemical model (Aerosol Simulation Program v.2.1) to estimate midday HO2 and RO2 concentrations and ozone production rates (P(O3)) in the fire plumes. We observe that Leighton-derived HO2 and RO2 values (49-185 pptv) and instantaneous P(O3) (2.0-3.6 ppbv/h) are higher than the results from the photochemical model.

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.

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

PubMed

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

2011-02-01

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

Indications of photochemical histories of Pacific air masses from measurements of atmospheric trace species at Point Arena, California

NASA Technical Reports Server (NTRS)

Parrish, D. D.; Hahn, C. J.; Williams, E. J.; Norton, R. B.; Fehsenfeld, F. C.; Singh, H. B.; Shetter, J. D.; Gandrud, B. W.; Ridley, B. A.

1992-01-01

Measurements were made of a suite of photochemically active trace species (including light hydrocarbons, ozone, peroxyacetyl nitrate, HNO3, NO3(-), NO(x), and NO(y)) in marine air collected during a 10-day period in April and May 1985 at Point Arena (California), a coastal inflow site. It was found that the mixing ratios of the alkanes, ozone, peroxyacetyl nitrate, and HNO3 correlated with variations in the origins of calculated air parcel trajectories and with variations in the ratios of the light alkanes. The highest levels of alkanes and the photochemical products were found in parcels that had been rapidly transported across the North Pacific Ocean from near the 600-mbar level above the east Asian coast. It is suggested that production over the continents, transport to the marine areas, and parallel removal processes account for much of the observed correlation.

Impact of Diurnal Variations of Precursors on the Prediction of Ozone

NASA Astrophysics Data System (ADS)

Hamer, P. D.; Bowman, K. W.; Henze, D. K.; Singh, K.

2009-12-01

Using a photochemical box model and its adjoint, constructed using the Kinetic Pre-Processor, we investigate the impacts of changing observational capacity, observation frequency and quality upon the ability to both understand and predict the nature of peak ozone events within a variety of polluted environments. The model consists of a chemical mechanism based on the Master Chemical Mechanism utilising 171 chemical species and 524 chemical reactions interacting with emissions, dry deposition and mixing schemes. The model was run under a variety of conditions designed to simulate a range of summertime polluted environments spanning a range of NOx and volatile organic compound regimes (VOCs). Using the forward model we were able to generate simulated atmospheric conditions representative of a particular polluted environment, which could in turn be used to generate a set of pseudo observations of key photochemical constituents. The model was then run under somewhat less polluted conditions to generate a background and then perturbed back towards the polluted trajectory using sequential data assimilation and the pseudo observations. Using a combination of the adjoint sensitivity analysis and the sequential data assimilation described here we assess the optimal time of observation and the diversity of observed chemical species required to provide acceptable forecast estimates of ozone concentrations. As the photochemical regime changes depending on NOx and VOC concentrations different observing strategies become favourable. The impact of using remote sensing based observations of the free tropospheric photochemical state are investigated to demonstrate the advantage of gaining knowledge of atmospheric trace gases away from the immediate photochemical environment.

Ozone Promotes Chloropicrin Formation by Oxidizing Amines to Nitro Compounds.

PubMed

McCurry, Daniel L; Quay, Amanda N; Mitch, William A

2016-02-02

Chloropicrin formation has been associated with ozonation followed by chlorination, but the reaction pathway and precursors have been poorly characterized. Experiments with methylamine demonstrated that ozonation converts methylamine to nitromethane at ∼100% yield. Subsequent chlorination converts nitromethane to chloropicrin at ∼50% yield under the conditions evaluated. Similarly high yields from other primary amines were limited to those with functional groups on the β-carbon (e.g., the carboxylic acid in glycine) that facilitate carbon-carbon bond cleavage to release nitromethyl anion. Secondary amines featuring these reactive primary amines as functional groups (e.g., secondary N-methylamines) formed chloropicrin at high yields, likely by facile dealkylation to release the primary nitro compound. Chloropicrin yields from tertiary amines were low. Natural water experiments, including derivatization to transform primary and secondary amines to less reactive carbamate functional groups, indicated that primary and secondary amines were the dominant chloropicrin precursors during ozonation/chlorination. Ozonation followed by chlorination of the primary amine side chain of lysine demonstrated low yields (∼0.2%) of chloropicrin, but high yields (∼17%) of dichloronitrolysine, a halonitroalkane structural analogue to chloropicrin. However, chloropicrin yields increased and dichloronitrolysine yields decreased in the absence of hydroxyl radical scavengers, suggesting that future research should characterize the potential occurrence of such halonitroalkane analogues relative to natural radical scavenger (e.g., carbonate) concentrations.

A comparison of wet and dry season ozone and CO over Brazil using in situ and satellite measurements

NASA Technical Reports Server (NTRS)

Watson, Catherine E.; Fishman, Jack; Gregory, Gerald L.; Sachse, Glen W.

1991-01-01

A comparison conducted between direct measurements of Brazilian ozone and NO concentrations and space-based measurements has indicated a strong correlation between the two environmental sensing methods and indicated the seasonality of both ozone and CO concentrations in this region. Dry season increases appear to be due to both increased local biomass burning and the transport of CO and ozone from Africa. The coincident high values of both CO and ozone suggest photochemical sources, rather than a stratospheric source, for the African and South American ozone.

Photochemistry and dynamics of the ozone layer

NASA Technical Reports Server (NTRS)

Prinn, R. G.; Alyea, F. N.; Cunnold, D. M.

1978-01-01

The paper presents a broad review of the photochemical and dynamic theories of the ozone layer. The two theories are combined into the MIT three-dimensional dynamic-chemical quasi-geostrophic model with 26 levels in the vertical spaced in logarithmic pressure coordinates between the ground and 72-km altitude. The chemical scheme incorporates the important odd nitrogen, odd hydrogen, and odd oxygen chemistry, but is simplified in the sense that it requires specification of the distributions of NO2, OH and HO2. The prognostic equations are the vorticity equation, the perturbation thermodynamic equation, and the global mean and perturbation continuity equations for ozone; diagnostic equations include the hydrostatic equation, the balance condition, and the mass continuity equation. The model is applied to the investigation of the impact of supersonic aircraft on the ozone layer.

Ozone Measurements in the Mesosphere During a Solar Proton Event

NASA Technical Reports Server (NTRS)

Lippert, W.; Felske, D.

1984-01-01

Charged particle precipitation in the Earth's atmosphere produces odd nitrogen and odd hydrogen. These species take part in catalytic reactions which destroy atmospheric ozone in the stratosphere and mesosphere. Modeling efforts regarding the impact of these ionization events on the neutral atmosphere describe ozone depletions in good agreement with observations in the stratosphere and mesosphere. The photochemical effects of the solar proton event (SPE) of August 1972 are discussed, and calculations for higher altitudes (70 to 90 km) are presented that indicate after a brief reduction during and immediately following intense particle precipitation, ozone will later reach higher concentrations than those present before the event.

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.

Long-term response of total ozone content at different latitudes of the Northern and Southern Hemispheres caused by solar activity during 1958-2006 (results of regression analysis)

NASA Astrophysics Data System (ADS)

Krivolutsky, Alexei A.; Nazarova, Margarita; Knyazeva, Galina

Solar activity influences on atmospheric photochemical system via its changebale electromag-netic flux with eleven-year period and also by energetic particles during solar proton event (SPE). Energetic particles penetrate mostly into polar regions and induce additional produc-tion of NOx and HOx chemical compounds, which can destroy ozone in photochemical catalytic cycles. Solar irradiance variations cause in-phase variability of ozone in accordance with photo-chemical theory. However, real ozone response caused by these two factors, which has different physical nature, is not so clear on long-term time scale. In order to understand the situation multiply linear regression statistical method was used. Three data series, which covered the period 1958-2006, have been used to realize such analysis: yearly averaged total ozone at dif-ferent latitudes (World Ozone Data Centre, Canada, WMO); yearly averaged proton fluxes with E¿ 10 MeV ( IMP, GOES, METEOR satellites); yearly averaged numbers of solar spots (Solar Data). Then, before the analysis, the data sets of ozone deviations from the mean values for whole period (1958-2006) at each latitudinal belt were prepared. The results of multiply regression analysis (two factors) revealed rather complicated time-dependent behavior of ozone response with clear negative peaks for the years of strong SPEs. The magnitudes of such peaks on annual mean basis are not greater than 10 DU. The unusual effect -positive response of ozone to solar proton activity near both poles-was discovered by statistical analysis. The pos-sible photochemical nature of found effect is discussed. This work was supported by Russian Science Foundation for Basic Research (grant 09-05-009949) and by the contract 1-6-08 under Russian Sub-Program "Research and Investigation of Antarctica".

Direct observation of ozone formation on SiO2 surfaces in O2 discharges

NASA Astrophysics Data System (ADS)

Marinov, D.; Guaitella, O.; Booth, J. P.; Rousseau, A.

2013-01-01

Ozone production is studied in a pulsed O2 discharge at pressures in the range 1.3-6.7 mbar. Time-resolved absolute concentrations of O3 and O are measured in the post-discharge using UV absorption spectroscopy and two-photon absorption laser-induced fluorescence. In a bare silica discharge tube ozone is formed mainly by three-body gas-phase recombination. When the tube surface is covered by a high specific surface silica catalyst heterogeneous formation becomes the main source of ozone. The efficiency of this surface process increases with O2 pressure and is favoured by the presence of OH groups and adsorbed H2O on the surface. At p = 6.7 mbar ozone production accounts for up to 25% of the atomic oxygen losses on the surface.

Contribution of long-range transport to the ozone levels recorded in the Northeast of Portugal

NASA Astrophysics Data System (ADS)

Gama, C.; Nunes, T.; Marques, M. C.; Ferreira, F.

2009-04-01

In the past four years (2004-2007), measurements carried out at Lamas de Olo, the only air quality monitoring background station in the Northeast of Portugal, showed high ozone concentrations (97,7±29,7 g.m-3). This remote site, located in the middle of Alvão Natural Park, in Portugal, 1086 m asl, plays a significant role on the total amount of exceedances registered in the national air quality network. The analysis of the data recorded at this monitoring station revealed an annual cycle of ozone concentrations similar to the ones observed in other background sites of the Northern Hemisphere (Monks, 2000; Vingarzan and Taylor, 2003). This common feature comprises a distinct maximum during spring (peaking during the month of April). Nevertheless it is during the summer that the hourly concentrations are higher, due to the typical atmospheric and meteorological conditions that promote photochemical pollution episodes. Photochemical pollution episodes can be related with production of ozone in a local scale or in a global scale due to the transportation of polluted air masses. For this reason analysing these events is crucial to fully understand the behaviour of ozone in the Northeast of Portugal, in order to adopt the correct long-term policies. With the purpose of studying the influence of long-range transport on the ozone levels recorded at Lamas de Olo, a cluster analysis was performed on 96-hour back trajectories air masses. Different trajectory clusters represent air masses with different source regions of atmospheric pollutants and the influence of these regions on the atmospheric composition at the arrival point (receptor) of the trajectories can therefore be assessed (EMPA, 2008). The back trajectories were simulated 4 times per day, using HYSPLIT model. A "bottom-up" cluster methodology was used to group trajectories into clusters according to their characteristics, for several time periods with similar ozone levels and/or distributions. Ozone average

An Extended View of Mars Ozone

NASA Technical Reports Server (NTRS)

Fast, Kelly

2011-01-01

We present an ongoing effort to characterize chemistry in Mars' atmosphere in multiple seasons on timescales longer than flight missions through coordinated efforts by GSFC's HIPWAC spectrometer and Mars Express SPICAM, archival measurements, and tests/application of photochemical models. The trace species ozone (O3) is an effective probe of atmospheric chemistry because it is destroyed by chemically active odd hydrogen species (HO(sub x)) that result from water vapor photolysis. Observed ozone abundance on Mars is a critical test for three-dimensional photochemistry coupled general circulation models (GCM) that make specific predictions for the spatial, diurnal, and seasonal behavior of ozone and related chemistry and climatological conditions. Coordinated measurements by HIPWAC and SPICAM quantitatively linked mission data to the 23-year GSFC ozone data record and also revealed unanticipated inter-decadal variability of same-season ozone abundances, a possible indicator of changing cloud activity (heterogeneous sink for HO(sub x)). A detailed study of long-term conditions is critical to characterizing the predictability of Mars' seasonal chemical behavior, particularly in light of the implications of and the lack of explanation for reported methane behavior.

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

Federal Register 2010, 2011, 2012, 2013, 2014

2013-02-15

... Photochemical Oxidants'' will be made available primarily through the Internet on the National Center for..., among other things, ``cause or contribute to air pollution which may reasonably be anticipated to... Air Act, is charged (among other things) with independent scientific review of EPA's air quality...

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 ...

Uncertainties in Episodic Ozone Modeling Stemming from Uncertainties in the Meteorological Fields.

NASA Astrophysics Data System (ADS)

Biswas, Jhumoor; Trivikrama Rao, S.

2001-02-01

This paper examines the uncertainty associated with photochemical modeling using the Variable-Grid Urban Airshed Model (UAM-V) with two different prognostic meteorological models. The meteorological fields for ozone episodes that occurred during 17-20 June, 12-15 July, and 30 July-2 August in the summer of 1995 were derived from two meteorological models, the Regional Atmospheric Modeling System (RAMS) and the Fifth-Generation Pennsylvania State University-National Center for Atmospheric Research Mesoscale Model (MM5). The simulated ozone concentrations from the two photochemical modeling systems, namely, RAMS/UAM-V and MM5/UAM-V, are compared with each other and with ozone observations from several monitoring sites in the eastern United States. The overall results indicate that neither modeling system performs significantly better than the other in reproducing the observed ozone concentrations. The results reveal that there is a significant variability, about 20% at the 95% level of confidence, in the modeled 1-h ozone concentration maxima from one modeling system to the other for a given episode. The model-to-model variability in the simulated ozone levels is for most part attributable to the unsystematic type of errors. The directionality for emission controls (i.e., NOx versus VOC sensitivity) is also evaluated with UAM-V using hypothetical emission reductions. The results reveal that not only the improvement in ozone but also the VOC-sensitive and NOx-sensitive regimes are influenced by the differences in the meteorological fields. Both modeling systems indicate that a large portion of the eastern United States is NOx limited, but there are model-to-model and episode-to-episode differences at individual grid cells regarding the efficacy of emission reductions.

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.

Impacts of Lowered Urban Air Temperatures on Precursor Emission and Ozone Air Quality.

PubMed

Taha, Haider; Konopacki, Steven; Akbari, Hashem

1998-09-01

Meteorological, photochemical, building-energy, and power plant simulations were performed to assess the possible precursor emission and ozone air quality impacts of decreased air temperatures that could result from implementing the "cool communities" concept in California's South Coast Air Basin (SoCAB). Two pathways are considered. In the direct pathway, a reduction in cooling energy use translates into reduced demand for generation capacity and, thus, reduced precursor emissions from electric utility power plants. In the indirect pathway, reduced air temperatures can slow the atmospheric production of ozone as well as precursor emission from anthropogenic and biogenic sources. The simulations suggest small impacts on emissions following implementation of cool communities in the SoCAB. In summer, for example, there can be reductions of up to 3% in NO x emissions from in-basin power plants. The photochemical simulations suggest that the air quality impacts of these direct emission reductions are small. However, the indirect atmospheric effects of cool communities can be significant. For example, ozone peak concentrations can decrease by up to 11% in summer and population-weighted exceedance exposure to ozone above the California and National Ambient Air Quality Standards can decrease by up to 11 and 17%, respectively. The modeling suggests that if these strategies are combined with others, such as mobile-source emission control, the improvements in ozone air quality can be substantial.

Airborne and ground-based observations of a weekend effect in ozone, precursors, and oxidation products in the California South Coast Air Basin

NASA Astrophysics Data System (ADS)

Pollack, I. B.; Ryerson, T. B.; Trainer, M.; Parrish, D. D.; Andrews, A. E.; Atlas, E. L.; Blake, D. R.; Brown, S. S.; Commane, R.; Daube, B. C.; Gouw, J. A.; Dubé, W. P.; Flynn, J.; Frost, G. J.; Gilman, J. B.; Grossberg, N.; Holloway, J. S.; Kofler, J.; Kort, E. A.; Kuster, W. C.; Lang, P. M.; Lefer, B.; Lueb, R. A.; Neuman, J. A.; Nowak, J. B.; Novelli, P. C.; Peischl, J.; Perring, A. E.; Roberts, J. M.; Santoni, G.; Schwarz, J. P.; Spackman, J. R.; Wagner, N. L.; Warneke, C.; Washenfelder, R. A.; Wofsy, S. C.; Xiang, B.

2011-11-01

Airborne and ground-based measurements during the CalNex (California Research at the Nexus of Air Quality and Climate Change) field study in May/June 2010 show a weekend effect in ozone in the South Coast Air Basin (SoCAB) consistent with previous observations. The well-known and much-studied weekend ozone effect has been attributed to weekend reductions in nitrogen oxide (NOx = NO + NO2) emissions, which affect ozone levels via two processes: (1) reduced ozone loss by titration and (2) enhanced photochemical production of ozone due to an increased ratio of non-methane volatile organic compounds (VOCs) to NOx. In accord with previous assessments, the 2010 airborne and ground-based data show an average decrease in NOx of 46 ± 11% and 34 ± 4%, respectively, and an average increase in VOC/NOxratio of 48 ± 8% and 43 ± 22%, respectively, on weekends. This work extends current understanding of the weekend ozone effect in the SoCAB by identifying its major causes and quantifying their relative importance from the available CalNex data. Increased weekend production of a VOC-NOxoxidation product, peroxyacetyl nitrate, compared to a radical termination product, nitric acid, indicates a significant contribution from increased photochemical production on weekends. Weekday-to-weekend differences in the products of NOx oxidation show 45 ± 13% and 42 ± 12% more extensive photochemical processing and, when compared with odd oxygen (Ox = O3 + NO2), 51 ± 14% and 22 ± 17% greater ozone production efficiency on weekends in the airborne and ground-based data, respectively, indicating that both contribute to higher weekend ozone levels in the SoCAB.

Airborne and ground-based observations of a weekend effect in ozone, precursors, and oxidation products in the California South Coast Air Basin

NASA Astrophysics Data System (ADS)

Pollack, I. B.; Ryerson, T. B.; Trainer, M.; Parrish, D. D.; Andrews, A. E.; Atlas, E. L.; Blake, D. R.; Brown, S. S.; Commane, R.; Daube, B. C.; de Gouw, J. A.; Dubé, W. P.; Flynn, J.; Frost, G. J.; Gilman, J. B.; Grossberg, N.; Holloway, J. S.; Kofler, J.; Kort, E. A.; Kuster, W. C.; Lang, P. M.; Lefer, B.; Lueb, R. A.; Neuman, J. A.; Nowak, J. B.; Novelli, P. C.; Peischl, J.; Perring, A. E.; Roberts, J. M.; Santoni, G.; Schwarz, J. P.; Spackman, J. R.; Wagner, N. L.; Warneke, C.; Washenfelder, R. A.; Wofsy, S. C.; Xiang, B.

2012-02-01

Airborne and ground-based measurements during the CalNex (California Research at the Nexus of Air Quality and Climate Change) field study in May/June 2010 show a weekend effect in ozone in the South Coast Air Basin (SoCAB) consistent with previous observations. The well-known and much-studied weekend ozone effect has been attributed to weekend reductions in nitrogen oxide (NOx = NO + NO2) emissions, which affect ozone levels via two processes: (1) reduced ozone loss by titration and (2) enhanced photochemical production of ozone due to an increased ratio of non-methane volatile organic compounds (VOCs) to NOx. In accord with previous assessments, the 2010 airborne and ground-based data show an average decrease in NOx of 46 ± 11% and 34 ± 4%, respectively, and an average increase in VOC/NOx ratio of 48 ± 8% and 43 ± 22%, respectively, on weekends. This work extends current understanding of the weekend ozone effect in the SoCAB by identifying its major causes and quantifying their relative importance from the available CalNex data. Increased weekend production of a VOC-NOx oxidation product, peroxyacetyl nitrate, compared to a radical termination product, nitric acid, indicates a significant contribution from increased photochemical production on weekends. Weekday-to-weekend differences in the products of NOx oxidation show 45 ± 13% and 42 ± 12% more extensive photochemical processing and, when compared with odd oxygen (Ox = O3 + NO2), 51 ± 14% and 22 ± 17% greater ozone production efficiency on weekends in the airborne and ground-based data, respectively, indicating that both contribute to higher weekend ozone levels in the SoCAB.

Chemical Loss of Polar Ozone: Present Understanding and Remaining Uncertainties

NASA Technical Reports Server (NTRS)

Salawitch, Ross; Canty, Tim; Cunnold, Derek; Dorf, Marcel; Frieler, Katja; Godin-Beekman, Sophie; Newchurch, Michael; Pfeilsticker, Klaus; Rex, Markus; Stimpfle, Rick;

Study of the impact of organic nitrate production on ozone production in a southeastern mixed forest environment using a 0-D photochemical model

NASA Astrophysics Data System (ADS)

Mcavey, K. M.; Groff, C. J.; Xiong, F.; Seeley, J. V.; Starn, T.; Feiner, P. A.; Zhang, L.; Brune, W. H.; Baumann, K.; Misztal, P. K.; Koss, A.; De Gouw, J. A.; Olson, K. F.; Goldstein, A. H.; Bertman, S. B.; Shepson, P. B.

2014-12-01

Organic nitrates (RONO2 + ROONO2) act as an important sink for both organic alkoxy and peroxy and NOx (NO+NO2) radicals, and thus their production can have a significant limiting impact on ozone production. However, there remains significant uncertainty on the formation yields and fates of organic nitrates in the atmosphere. This certainly applies to the biogenic volatile organic compounds (BVOCs), which can often be the dominant reaction partner for OH and thus precursors to the peroxy radicals that produce ozone. Observations of BVOCs and total isoprene and monoterpene nitrates were measured as part of the Southern Oxidant and Aerosol Study in the summer of 2013, at the SEARCH Centreville site in rural, central Alabama. A 0-D box model was constructed to observe the effect of individual and total organic nitrates on ozone production potential, to determine the relative importance of each species in organic nitrate formation. Here we examine the impact of yield uncertainty, and secondary oxidation reactions that might release NOx from the primary organic nitrates.

An investigation into the causes of stratospheric ozone loss in the southern Australasian region

NASA Astrophysics Data System (ADS)

Lehmann, P.; Karoly, D. J.; Newmann, P. A.; Clarkson, T. S.; Matthews, W. A.

1992-07-01

Measurements of total ozone at Macquarie Island (55 deg S, 159 deg E) reveal statistically significant reductions of approximately twelve percent during July to September when comparing the mean levels for 1987-90 with those in the seventies. In order to investigate the possibility that these ozone changes may not be a result of dynamic variability of the stratosphere, a simple linear model of ozone was created from statistical analysis of tropopause height and isentropic transient eddy heat flux, which were assumed representative of the dominant dynamic influences. Comparison of measured and modeled ozone indicates that the recent downward trend in ozone at Macquarie Island is not related to stratospheric dynamic variability and therefore suggests another mechanism, possibly changes in photochemical destruction of ozone.

Diagnosing ozone recovery using the O3-N2O relationship

NASA Astrophysics Data System (ADS)

Butler, A. H.; Gao, R. S.; Maycock, A.; Portmann, R. W.; Thornberry, T. D.; Rosenlof, K. H.; Fahey, D. W.

2016-12-01

The ubiquitous compact correlation between collocated values of stratospheric ozone (O3) and the tracer nitrous oxide (N2O) results from the stratospheric photochemical processes that produce ozone and destroy N2O combined with common transport and mixing processes. Changes in the correlation slope under certain circumstances reflect changes in the production and loss balance of ozone. This approach has been used extensively to diagnose and quantify ozone loss in polar spring. Using a coupled atmosphere-ocean model with interactive chemistry (CESM/WACCM), we show that this relationship can be used to diagnose ozone recovery in the lower extratropical stratosphere. We then consider in situ measurements of O3 and N2O from ATTREX, GloPac, and HIPPO as well as satellite measurements from ACE and Aura MLS to consider whether ozone recovery can be detected in observations during the period 2004-2016.

Multiscale multifractal properties between ground-level ozone and its precursors in rural area in Hong Kong.

PubMed

He, Hong-di; Qiao, Zhong-Xia; Pan, Wei; Lu, Wei-Zhen

2017-07-01

In rural area, due to the reduction of NOx and CO emitted from vehicle exhausts, the ozone photochemical reaction exhibits relatively weak effect and ozone formation presents different pattern with its precursors in contrast to urban situation. Hence, in this study, we apply detrended cross-correlation analysis to investigate the multifractal properties between ozone and its precursors in a rural area in Hong Kong. The observed databases of ozone, NO 2 , NOx and CO levels during 2005-2014 are obtained from a rural monitoring station in Hong Kong. Based on the collected database, the cross-correlation analysis is carried out firstly to examine the cross-correlation patterns and the results indicate that close interactive relations exist between them. Then the detrended cross-correlation analysis is performed for further analysis. The multifractal characters occur between ozone and its precursors. The long-term cross-correlations behaviors in winter are verified to be stronger than that in other seasons. Additionally, the method is extended on daily averaged data to explore the multifractal property on various time scales. The long-term cross-correlation behavior of ozone vs NO 2 and NOx on daily basis becomes weaker while that of ozone vs CO becomes stronger. The multifractal properties for all pairs in summer are found to be the strongest among the whole year. These findings successfully illustrate that the multifractal analysis is a useful tool for describing the temporal scaling behaviors of ozone trends in different time series in rural areas. Copyright © 2017 Elsevier Ltd. All rights reserved.

Changes in air quality and tropospheric composition due to depletion of stratospheric ozone and interactions with changing climate: implications for human and environmental health.

PubMed

Madronich, S; Shao, M; Wilson, S R; Solomon, K R; Longstreth, J D; Tang, X Y

2015-01-01

UV radiation is an essential driver for the formation of photochemical smog, which includes ground-level ozone and particulate matter (PM). Recent analyses support earlier work showing that poor outdoor air quality is a major environmental hazard as well as quantifying health effects on regional and global scales more accurately. Greater exposure to these pollutants has been linked to increased risks of cardiovascular and respiratory diseases in humans and is associated globally with several million premature deaths per year. Ozone also has adverse effects on yields of crops, leading to loss of billions of US dollars each year. These detrimental effects also may alter biological diversity and affect the function of natural ecosystems. Future air quality will depend mostly on changes in emission of pollutants and their precursors, but changes in UV radiation and climate will contribute as well. Significant reductions in emissions, mainly from the energy and transportation sectors, have already led to improved air quality in many locations. Air quality will continue to improve in those cities/states that can afford controls, and worsen where the regulatory infrastructure is not available. Future changes in UV radiation and climate will alter the rates of formation of ground-level ozone and photochemically-generated particulate matter and must be considered in predictions of air quality. The decrease in UV radiation associated with recovery of stratospheric ozone will, according to recent global atmospheric model simulations, lead to increases in ground-level ozone at most locations. If correct, this will add significantly to future ground-level ozone trends. However, the spatial resolution of these global models is insufficient to inform policy at this time, especially for urban areas. UV radiation affects the atmospheric concentration of hydroxyl radicals, ˙OH, which are responsible for the self-cleaning of the atmosphere. Recent measurements confirm that, on a

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

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…

Chemical kinetic and photochemical data for use in stratospheric modeling evaluation number 4: NASA panel for data evaluation

NASA Technical Reports Server (NTRS)

1981-01-01

Evaluated sets of rate constants and photochemical cross sections compiled by the Panel are presented. The primary application of the data is in the modelling of stratospheric processes, with particular emphasis on the ozone layer and its possible perturbation by anthropogenic and natural phenomena.

Ozone chemical equilibrium in the extended mesopause under the nighttime conditions

NASA Astrophysics Data System (ADS)

Belikovich, M. V.; Kulikov, M. Yu.; Grygalashvyly, M.; Sonnemann, G. R.; Ermakova, T. S.; Nechaev, A. A.; Feigin, A. M.

2018-01-01

For retrieval of atomic oxygen and atomic hydrogen via ozone observations in the extended mesopause region (∼70-100 km) under nighttime conditions, an assumption on photochemical equilibrium of ozone is often used in research. In this work, an assumption on chemical equilibrium of ozone near mesopause region during nighttime is proofed. We examine 3D chemistry-transport model (CTM) annual calculations and determine the ratio between the correct (modeled) distributions of the O3 density and its equilibrium values depending on the altitude, latitude, and season. The results show that the retrieval of atomic oxygen and atomic hydrogen distributions using an assumption on ozone chemical equilibrium may lead to large errors below ∼81-87 km. We give simple and clear semi-empirical criterion for practical utilization of the lower boundary of the area with ozone's chemical equilibrium near mesopause.

Derived Emission Rates and Photochemical Production Rates of Volatile Organic Compounds (VOCs) Associated with Oil and Natural Gas Operations in the Uintah Basin, UT During a Wintertime Ozone Formation Event

NASA Astrophysics Data System (ADS)

Koss, A.; De Gouw, J. A.; Warneke, C.; Gilman, J.; Lerner, B. M.; Graus, M.; Yuan, B.; Edwards, P. M.; Brown, S. S.; Wild, R. J.; Roberts, J. M.; Bates, T. S.; Quinn, P.

2014-12-01

The Uintah Basin, an oil and natural gas extraction field in Utah, experienced extremely high levels of volatile organic compounds (VOCs) and ozone during the winter of 2013 - up to 100 ppmv carbon and 150 ppbv O3. Here we interpret VOCs measured during an ozone formation event from 31 Jan 2013 to 8 Feb 2013. Ratios of VOCs show strong diurnal cycles and week-long trends. A simple analysis was applied to ratios of aromatic VOCs measured by proton transfer reaction mass spectrometer (PTR-MS) to explain these trends and to estimate emission rates of aromatic VOCs from oil and natural gas extraction, VOC emission ratios relative to benzene, and ambient [OH]. The analysis incorporates the following assumptions: (1) the source composition of emitted VOCs and their emission rates were temporally and spatially constant, and (2) the removal of VOCs was governed by reaction with OH, diurnal profile of which is constrained by measured photolysis rates. The main findings are (1) the emission rate of methane, extrapolated from the emission rate of benzene, is on the same order as an independent estimate from aircraft measurements of methane in 2012, (2) the derived aromatic emission ratios are consistent with source contributions from both oil and gas producing wells, and (3) calculated daily OH concentrations are low, peaking at 1x106 molecules cm-3. The analysis was extended to investigate secondary production of oxygenated VOCs measured by PTR-MS. The analysis is able to explain daytime production, but it does not adequately explain nighttime behavior, which may be affected by complex deposition to snow and ice surfaces. The relative carbon mass of primary and secondary compounds was calculated and compared to observations. At the end of the ozone formation event (day 6), our analysis predicts that secondary (oxidized) VOCs should comprise about 40% of total carbon mass. However, only 12% of these compounds are accounted for by measured oxygenated VOCs and organic aerosol

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

PubMed

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

2013-02-01

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

Path-integral method for the source apportionment of photochemical pollutants

NASA Astrophysics Data System (ADS)

Dunker, A. M.

2015-06-01

A new, path-integral method is presented for apportioning the concentrations of pollutants predicted by a photochemical model to emissions from different sources. A novel feature of the method is that it can apportion the difference in a species concentration between two simulations. For example, the anthropogenic ozone increment, which is the difference between a simulation with all emissions present and another simulation with only the background (e.g., biogenic) emissions included, can be allocated to the anthropogenic emission sources. The method is based on an existing, exact mathematical equation. This equation is applied to relate the concentration difference between simulations to line or path integrals of first-order sensitivity coefficients. The sensitivities describe the effects of changing the emissions and are accurately calculated by the decoupled direct method. The path represents a continuous variation of emissions between the two simulations, and each path can be viewed as a separate emission-control strategy. The method does not require auxiliary assumptions, e.g., whether ozone formation is limited by the availability of volatile organic compounds (VOCs) or nitrogen oxides (NOx), and can be used for all the species predicted by the model. A simplified configuration of the Comprehensive Air Quality Model with Extensions (CAMx) is used to evaluate the accuracy of different numerical integration procedures and the dependence of the source contributions on the path. A Gauss-Legendre formula using three or four points along the path gives good accuracy for apportioning the anthropogenic increments of ozone, nitrogen dioxide, formaldehyde, and nitric acid. Source contributions to these increments were obtained for paths representing proportional control of all anthropogenic emissions together, control of NOx emissions before VOC emissions, and control of VOC emissions before NOx emissions. There are similarities in the source contributions from the

Path-integral method for the source apportionment of photochemical pollutants

NASA Astrophysics Data System (ADS)

Dunker, A. M.

2014-12-01

A new, path-integral method is presented for apportioning the concentrations of pollutants predicted by a photochemical model to emissions from different sources. A novel feature of the method is that it can apportion the difference in a species concentration between two simulations. For example, the anthropogenic ozone increment, which is the difference between a simulation with all emissions present and another simulation with only the background (e.g., biogenic) emissions included, can be allocated to the anthropogenic emission sources. The method is based on an existing, exact mathematical equation. This equation is applied to relate the concentration difference between simulations to line or path integrals of first-order sensitivity coefficients. The sensitivities describe the effects of changing the emissions and are accurately calculated by the decoupled direct method. The path represents a continuous variation of emissions between the two simulations, and each path can be viewed as a separate emission-control strategy. The method does not require auxiliary assumptions, e.g., whether ozone formation is limited by the availability of volatile organic compounds (VOC's) or nitrogen oxides (NOx), and can be used for all the species predicted by the model. A simplified configuration of the Comprehensive Air Quality Model with Extensions is used to evaluate the accuracy of different numerical integration procedures and the dependence of the source contributions on the path. A Gauss-Legendre formula using 3 or 4 points along the path gives good accuracy for apportioning the anthropogenic increments of ozone, nitrogen dioxide, formaldehyde, and nitric acid. Source contributions to these increments were obtained for paths representing proportional control of all anthropogenic emissions together, control of NOx emissions before VOC emissions, and control of VOC emissions before NOx emissions. There are similarities in the source contributions from the three paths but

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.

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

PubMed

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

2015-04-01

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

Future-year ozone prediction for the United States using updated models and inputs.

PubMed

Collet, Susan; Kidokoro, Toru; Karamchandani, Prakash; Shah, Tejas; Jung, Jaegun

2017-08-01

The relationship between emission reductions and changes in ozone can be studied using photochemical grid models. These models are updated with new information as it becomes available. The primary objective of this study was to update the previous Collet et al. studies by using the most up-to-date (at the time the study was done) modeling emission tools, inventories, and meteorology available to conduct ozone source attribution and sensitivity studies. Results show future-year, 2030, design values for 8-hr ozone concentrations were lower than base-year values, 2011. The ozone source attribution results for selected cities showed that boundary conditions were the dominant contributors to ozone concentrations at the western U.S. locations, and were important for many of the eastern U.S. Point sources were generally more important in the eastern United States than in the western United States. The contributions of on-road mobile emissions were less than 5 ppb at a majority of the cities selected for analysis. The higher-order decoupled direct method (HDDM) results showed that in most of the locations selected for analysis, NOx emission reductions were more effective than VOC emission reductions in reducing ozone levels. The source attribution results from this study provide useful information on the important source categories and provide some initial guidance on future emission reduction strategies. The relationship between emission reductions and changes in ozone can be studied using photochemical grid models, which are updated with new available information. This study was to update the previous Collet et al. studies by using the most current, at the time the study was done, models and inventory to conduct ozone source attribution and sensitivity studies. The source attribution results from this study provide useful information on the important source categories and provide some initial guidance on future emission reduction strategies.

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.

Sulfate aerosols and polar stratospheric cloud formation

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

Tolbert, M.A.

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

Exploring ozone pollution in Chengdu, southwestern China: A case study from radical chemistry to O3-VOC-NOx sensitivity.

PubMed

Tan, Zhaofeng; Lu, Keding; Jiang, Meiqing; Su, Rong; Dong, Huabin; Zeng, Limin; Xie, Shaodong; Tan, Qinwen; Zhang, Yuanhang

2018-09-15

We present the in-situ measurements in Chengdu, a major city in south west of China, in September 2016. The concentrations of ozone and its precursor were measured at four sites. Although the campaign was conducted in early autumn, up to 100 ppbv (parts per billion by volume) daily maximum ozone was often observed at all sites. The observed ozone concentrations showed good agreement at all sites, which implied that ozone pollution is a regional issue in Chengdu. To better understand the ozone formation in Chengdu, an observation based model is used in this study to calculate the RO x radical concentrations (RO x  = OH + HO 2  + RO 2 ) and ozone production rate (P(O 3 )). The model predicts OH daily maximum is in the range of 4-8 × 10 6  molecules cm -3 , and HO 2 and RO 2 are in the range of 3-6 × 10 8  molecules cm -3 . The modelled radical concentrations show a distinct difference between ozone pollution and attainment period. The relative incremental reactivity (RIR) results demonstrate that anthropogenic VOCs reduction is the most efficient way to mitigate ozone pollution at all sites, of which alkenes dominate >50% of the ozone production. Empirical kinetic modelling approach shows that three out of four sites are under the VOC-limited regime, while Pengzhou is in a transition regime due to the local petrochemical industry. The ozone budget analysis showed that the local ozone production driven by the photochemical process is important to the accumulation of ozone concentrations. Copyright © 2018 Elsevier B.V. All rights reserved.

A numerical study of tropospheric ozone in the springtime in East Asia

NASA Astrophysics Data System (ADS)

Zhang, Meigen; Xu, Yongfu; Itsushi, Uno; Hajime, Akimoto

2004-04-01

The Models-3 Community Multi-scale Air Quality modeling system (CMAQ) coupled with the Regional Atmospheric Modeling System (RAMS) is applied to East Asia to study the transport and photochemical transformation of tropospheric ozone in March 1998. The calculated mixing ratios of ozone and carbon monoxide are compared with ground level observations at three remote sites in Japan and it is found that the model reproduces the observed features very well. Examination of several high episodes of ozone and carbon monoxide indicates that these elevated levels are found in association with continental outflow, demonstrating the critical role of the rapid transport of carbon monoxide and other ozone precursors from the continental boundary layer. In comparison with available ozonesonde data, it is found that the model-calculated ozone concentrations are generally in good agreement with the measurements, and the stratospheric contribution to surface ozone mixing ratios is quite limited.

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

PubMed

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

2008-05-15

We developed a first- and second-order sensitivity analysis approach with the decoupled direct method to examine spatial and temporal variations of ozone-limiting reagents and the importance of local vs upwind emission sources in the San Joaquin Valley of central California for a 5 day ozone episode (Jul 29th to Aug 3rd, 2000). Despite considerable spatial variations, nitrogen oxides (NO(x)) emission reductions are overall more effective than volatile organic compound (VOC) control for attaining the 8 h ozone standard in this region for this episode, in contrast to the VOC control that works better for attaining the prior 1 h ozone standard. Interbasin source contributions of NO(x) emissions are limited to the northern part of the SJV, while anthropogenic VOC (AVOC) emissions, especially those emitted at night, influence ozone formation in the SJV further downwind. Among model input parameters studied here, uncertainties in emissions of NO(x) and AVOC, and the rate coefficient of the OH + NO2 termination reaction, have the greatest effect on first-order ozone responses to changes in NO(x) emissions. Uncertainties in biogenic VOC emissions only have a modest effect because they are generally not collocated with anthropogenic sources in this region.

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

NASA Astrophysics Data System (ADS)

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

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

Global variations of zonal mean ozone during stratospheric warming events

NASA Technical Reports Server (NTRS)

Randel, William J.

1993-01-01

Eight years of Solar Backscatter Ultraviolet (SBUV) ozone data are examined to study zonal mean variations associated with stratospheric planetary wave (warming) events. These fluctuations are found to be nearly global in extent, with relatively large variations in the tropics, and coherent signatures reaching up to 50 deg in the opposite (summer) hemisphere. These ozone variations are a manifestation of the global circulation cells associated with stratospheric warming events; the ozone responds dynamically in the lower stratosphere to transport, and photochemically in the upper stratosphere to the circulation-induced temperature changes. The observed ozone variations in the tropics are of particular interest because transport is dominated by zonal-mean vertical motions (eddy flux divergences and mean meridional transports are negligible), and hence, substantial simplifications to the governing equations occur. The response of the atmosphere to these impulsive circulation changes provides a situation for robust estimates of the ozone-temperature sensitivity in the upper stratosphere.

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.

Fate of Chloromethanes in the Atmospheric Environment: Implications for Human Health, Ozone Formation and Depletion, and Global Warming Impacts.

PubMed

Tsai, Wen-Tien

2017-09-21

Among the halogenated hydrocarbons, chloromethanes (i.e., methyl chloride, CH₃Cl; methylene chloride, CH₂Cl₂; chloroform, CHCl₃; and carbon tetrachloride, CCl₄) play a vital role due to their extensive uses as solvents and chemical intermediates. This article aims to review their main chemical/physical properties and commercial/industrial uses, as well as the environment and health hazards posed by them and their toxic decomposition products. The environmental properties (including atmospheric lifetime, radiative efficiency, ozone depletion potential, global warming potential, photochemical ozone creation potential, and surface mixing ratio) of these chlorinated methanes are also reviewed. In addition, this paper further discusses their atmospheric fates and human health implications because they are apt to reside in the lower atmosphere when released into the environment. According to the atmospheric degradation mechanism, their toxic degradation products in the troposphere include hydrogen chloride (HCl), carbon monoxide (CO), chlorine (Cl₂), formyl chloride (HCOCl), carbonyl chloride (COCl₂), and hydrogen peroxide (H₂O₂). Among them, COCl₂ (also called phosgene) is a powerful irritating gas, which is easily hydrolyzed or thermally decomposed to form hydrogen chloride.

Effect of Pre-ozonation on Haloacetic Acids Formation in Ganga River Water at Kanpur, India

NASA Astrophysics Data System (ADS)

Naladala, Nagasrinivasa Rao; Singh, Rambabu; Katiyar, Kumud Lata Devi; Bose, Purnendu; Dutta, Venkatesh

2017-11-01

Almost all natural water bodies which are considered to be sustainable sources of drinking water contain organic matter in dissolved form and pathogens. This dissolved organic matter and pathogens cannot be removed effectively through traditional filtering processes in drinking water treatment plants. Chlorination of such water for disinfection results in large amounts of disinfection by-products (DBPs), mainly trihalomethanes and haloacetic acids (HAAs), which showed many health effects like cancer and reproductive problems in lab animals and in human beings as well. Complete removal of dissolved organic carbon (DOC), which is a precursor compound for HAAs formation, is impossible from a practical point of view; hence, it will be better if DOC activity towards DBPs formation can be reduced via some process. The present article describes the process of pre-ozonating post-coagulated Ganga River water at Kanpur in a continuous flow mode and its effect on HAAs formation. Nearly 58% reduction in HAAs formation was observed during this study at higher doses of ozone.

Environmental effects of ozone depletion and its interactions with climate change: progress report, 2008.

PubMed

Andrady, Anthony; Aucamp, Pieter J; Bais, Alkiviadis; Ballaré, Carlos L; Björn, Lars Olof; Bornman, Janet F; Caldwell, Martyn; Cullen, Anthony P; Erickson, David J; de Gruijl, Frank R; Häder, Donat-P; Ilyas, Mohammad; Kulandaivelu, G; Kumar, H D; Longstreth, Janice; McKenzie, Richard L; Norval, Mary; Paul, Nigel; Redhwi, Halim Hamid; Smith, Raymond C; Solomon, Keith R; Sulzberger, Barbara; Takizawa, Yukio; Tang, Xiaoyan; Teramura, Alan H; Torikai, Ayako; van der Leun, Jan C; Wilson, Stephen R; Worrest, Robert C; Zepp, Richard G

2009-01-01

After the enthusiastic celebration of the 20th Anniversary of the Montreal Protocol on Substances that Deplete the Ozone Layer in 2007, the work for the protection of the ozone layer continues. The Environmental Effects Assessment Panel is one of the three expert panels within the Montreal Protocol. This EEAP deals with the increase of the UV irradiance on the Earth's surface and its effects on human health, animals, plants, biogeochemistry, air quality and materials. For the past few years, interactions of ozone depletion with climate change have also been considered. It has become clear that the environmental problems will be long-lasting. In spite of the fact that the worldwide production of ozone depleting chemicals has already been reduced by 95%, the environmental disturbances are expected to persist for about the next half a century, even if the protective work is actively continued, and completed. The latest full report was published in Photochem. Photobiol. Sci., 2007, 6, 201-332, and the last progress report in Photochem. Photobiol. Sci., 2008, 7, 15-27. The next full report on environmental effects is scheduled for the year 2010. The present progress report 2008 is one of the short interim reports, appearing annually.

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

NASA Astrophysics Data System (ADS)

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

2018-04-01

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

Source Attribution of Tropospheric Ozone using a Global Model

NASA Astrophysics Data System (ADS)

Coates, J.; Lupascu, A.; Butler, T. M.; Zhu, S.

2016-12-01

Tropospheric ozone is both a short-lived climate forcing pollutant and a radiatively active greenhouse gas. Ozone is not directly emitted into the troposphere but photochemically produced from chemical reactions involving nitrogen oxides (NOx) and volatile organic compounds (VOCs). Emissions of ozone precursors (NOx and VOCs) have both natural and anthropogenic sources and may be transported away from their sources to produce ozone downwind. Also, transport of ozone from the stratosphere into the troposphere also influences tropospheric ozone levels in some regions. Attributing ozone concentrations to the contributions from different sources would indicate the effects of locally emitted or transported precursors on ozone levels in specific regions. This information could be used to inform the emission reduction strategies of ozone precursors by indicating which emission sources could be targeted for effective reductions thus reducing the burden of ozone pollution. We use a "tagging" approach within the CESM global model to attribute ozone levels to their source emissions. We use different tags to quantify the impact from natural (soils, lightning, stratospheric transport) and anthropogenic (aircraft, biomass burning) sources of NOx and VOCs (including methane) on ozone levels. These source sectors of different global regions are assigned based on the global emissions specified by HTAPv2.2. Using these results, we develop a transboundary source-receptor relationship of ozone concentration to its precursor emission regions. Additionally, the transport of ozone precursors from regional anthropogenic sources is analysed to illustrate the extent to which mitigation strategies of regional emissions aid in mitigating global ozone levels.

Attribution of Recovery in Lower-Stratospheric Ozone

NASA Technical Reports Server (NTRS)

Yang, Eun-Su; Cunnold, Derek M.; Salawitch, Ross J.; McCormick, M. Patrick; Russell, James, III; Zawodny, Joseph M.; Oltmans, Samuel; Newchurch, Michael J.

2005-01-01

Multiple satellite and ground-based observations provide consistent evidence that the thickness of Earth's protective ozone layer has stopped declining since 1997, close to the time of peak stratospheric halogen loading. Regression analyses with Effective Equivalent Stratospheric Chlorine (EESC) in conjunction with further analyses using more sophisticated photochemical model calculations constrained by satellite data demonstrate that the cessation of ozone depletion between 18-25 km altitude is consistent with a leveling off of stratospheric abundances of chlorine and bromine, due to the Montreal Protocol and its amendments. However, ozone increases in the lowest part of the stratosphere, from the tropopause to 18 km, account for about half of the improvement in total column ozone during the past 9 years at northern hemisphere mid-latitudes. The increase in ozone for altitudes below 18 km is most likely driven by changes in transport, rather than driven by declining chlorine and bromine. Even with this evidence that the Montreal Protocol and its amendments are having the desired, positive effect on ozone above 18 km, total column ozone is recovering faster than expected due to the apparent transport driven changes at lower altitudes. Accurate prediction of future levels of stratospheric ozone will require comprehensive understanding of the factors that drive temporal changes at various altitudes, and partitioning of the recent transport-driven increases between natural variability and changes in atmospheric structure perhaps related to anthropogenic climate change.

Attribution of Recovery in Lower-stratospheric Ozone

NASA Technical Reports Server (NTRS)

Yang, Eun-Su; Cunnold, Derek M.; Salawitch, Ross J.; McCormick, M. Patrick; Russell, James, III; Zawodny, Joseph M.; Oltmans, Samuel; Newchurch, Michael J.

2006-01-01

Multiple satellite and ground-based observations provide consistent evidence that the thickness of Earth's protective ozone layer has stopped declining since 1997, close to the time of peak stratospheric halogen loading. Regression analyses with Effective Equivalent Stratospheric Chlorine (EESC) in conjunction with further analyses using more sophisticated photochemical model calculations constrained by satellite data demonstrate that the cessation of ozone depletion between 18-25 km altitude is consistent with a leveling off of stratospheric abundances of chlorine and bromine, due to the Montreal Protocol and its amendments. However, ozone increases in the lowest part of the stratosphere, from the tropopause to 18 km, account for about half of the improvement in total column ozone during the past 9 years at northern hemisphere mid-latitudes. The increase in ozone for altitudes below 18 km is most likely driven by changes in transport, rather than driven by declining chlorine and bromine. Even with this evidence that the Montreal Protocol and its amendments are having the desired, positive effect on ozone above 18 km, total column ozone is recovering faster than expected due to the apparent transport driven changes at lower altitudes. Accurate prediction of future levels of stratospheric ozone will require comprehensive understanding of the factors that drive temporal changes at various altitudes, and partitioning of the recent transport-driven increases between natural variability and changes in atmospheric structure perhaps related to anthropogenic climate change.

Sources and sinks of ozone in savanna and forest areas during EXPRESSO: Airborne turbulent flux measurements

NASA Astrophysics Data System (ADS)

Cros, B.; Delon, C.; Affre, C.; Marion, T.; Druilhet, A.; Perros, P. E.; Lopez, A.

2000-12-01

An airborne study of ozone concentrations and fluxes in the lower layers of the atmosphere was conducted over the Central African Republic (CAR) and northern Congo in November/December 1996, within the framework of the Experiment of Regional Sources and Sinks of Oxidants (EXPRESSO). The first 4 km of the atmosphere above savanna, rain forest, and the transitional area between them, were investigated with the French research aircraft Avion de Recherche Atmosphérique et de Télédétection (ARAT). Turbulent fluxes and deposition velocities of ozone were determined using the Eddy Correlation (EC) method. A specific methodology was developed to obtain accurate airborne turbulent flux measurements. This methodology is linked to the turbulence stationarity. The average values of ozone fluxes and ozone deposition velocities in the Atmospheric Boundary Layer (ABL) increase appreciably from savanna to forest. Near the ground, the ozone fluxes range between -0.115 +/-0.073 ppbv m/s above savanna and -0.350 +/-0.115 ppbv m/s above forest; for the deposition, the ranges are 0.0042 +/-0.0018 m/s and 0.015 +/-0.004 m/s. A simple empirical relationship between deposition velocity and Leaf Area Index (LAI) is proposed, giving an estimation of the deposition velocity for a whole latitudinal band. Vertical inputs of ozone to the ABL are estimated according to entrainment fluxes. The role of advection is neglected for horizontal transport of ozone in the ABL. The photochemical ozone production is deduced from the photo-stationary state deviation, and compared to the net ozone increase in the ABL during the flights performed above the forest. A tentative ozone budget based on the aircraft measurements is proposed in the ABL of the rain forest. Around noon, the photochemical production dominates with a net production of about 10 ppbv/h.

Chemical Evolution of Ozone and Its Precursors in Asian Pacific Rim Outflow During TRACE-P

NASA Astrophysics Data System (ADS)

Hamlin, A.; Crawford, J.; Olson, J.; Pippin, M.; Avery, M.; Sachse, G.; Barrick, J.; Blake, D.; Tan, D.; Sandholm, S.; Kondo, Y.; Singh, H.; Eisele, F.; Zondlo, M.; Flocke, F.; Talbot, R.

2002-12-01

During NASA's GTE/TRACE-P (Transport and Chemical Evolution over the Pacific) mission, a widespread stagnant pollution layer was observed between 2 and 4 km over the central Pacific. In this region, high levels of O3 (70~ppbv), CO (210~ppbv), and NOx (130~pptv) were observed. Back trajectories suggest this airmass had been rapidly transported from the Asian coast near the Yellow Sea to the central Pacific where it underwent subsidence. The chemical evolution of ozone and its precursors for this airmass is examined using lagrangian photochemical box model calculations. Simulations are conducted along trajectories which intersect the flight path where predicted mixing ratios are compared to measurements. An analysis of the photochemical processes controlling the cycling of nitrogen oxides and ozone production and destruction during transport will be presented.

Impact Assessment of Global Temperature Perturbations on Urban and Regional Ozone Levels in South Texas

NASA Astrophysics Data System (ADS)

Biswas, Jhumoor; John, Kuruvilla; Farooqui, Zuber

The recent Intergovernmental Panel on Climate Change report predicts significant temperature increases over the century which constitutes the pulse of climate variability in a region. A modeling study was performed to identify the potential impact of temperature perturbations on tropospheric ozone concentrations in South Texas. A future case modeling scenario which incorporates appropriate emission reduction strategies without accounting for climatic inconsistencies was used in this study. The photochemical modeling was undertaken for a high ozone episode of 13-20 September 1999, and a future modeling scenario was projected for ozone episode days in 2007 utilizing the meteorological conditions prevalent in the base year. The temperatures were increased uniformly throughout the simulation domain and through the vertical layers by 2°C, 3°C, 4°C, 5°C, and 6°C, respectively in the future year modeling case. These temperature perturbations represented the outcome of extreme climate change within the study region. Significantly large changes in peak ozone concentrations were predicted by the photochemical model. For the 6°C temperature perturbation, the greatest amplification in the maximum 8-h ozone concentrations within urban areas of the modeling domain was approximately 12 ppb. In addition, transboundary flux from major industrialized urban areas played a major role in supplementing the high ozone concentrations during the perturbed temperature scenarios. The Unites States Environmental Protection Agency (USEPA) is currently proposing stricter 8-h ozone standards. The effect of temperature perturbations on ozone exceedances based on current and potential stringent future National Ambient Air Quality Standards (NAAQS) was also studied. Temperatures had an appreciable spatial impact on the 8-h ozone exceedances with a considerable increase in spatial area exceeding the NAAQS for the 8-h ozone levels within the study region for each successive augmentation in

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

PubMed

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

2018-01-01

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

Photochemical aging of volatile organic compounds associated with oil and natural gas extraction in the Uintah Basin, UT, during a wintertime ozone formation event

NASA Astrophysics Data System (ADS)

Koss, A. R.; de Gouw, J.; Warneke, C.; Gilman, J. B.; Lerner, B. M.; Graus, M.; Yuan, B.; Edwards, P.; Brown, S. S.; Wild, R.; Roberts, J. M.; Bates, T. S.; Quinn, P. K.

2015-05-01

High concentrations of volatile organic compounds (VOCs) associated with oil and natural gas extraction were measured during a strong temperature inversion in the winter of 2013 at a rural site in the Uintah Basin, Utah. During this period, photochemistry enhanced by the stagnant meteorological conditions and concentrated VOCs led to high ozone mixing ratios (150 ppbv). A simple analysis of aromatic VOCs measured by proton-transfer-reaction mass-spectrometry (PTR-MS) is used to estimate (1) VOC emission ratios (the ratio of two VOCs at the time of emission) relative to benzene, (2) aromatic VOC emission rates, and (3) ambient OH radical concentrations. These quantities are determined from a best fit to VOC : benzene ratios as a function of time. The main findings are that (1) emission ratios are consistent with contributions from both oil and gas producing wells; (2) the emission rate of methane (27-57 x 103 kg methane h-1), extrapolated from the emission rate of benzene (4.1 ± 0.4 x 105 molecules cm-3 s-1), agrees with an independent estimate of methane emissions from aircraft measurements in 2012; and (3) calculated daily OH concentrations are low, peaking at 1 x 106 molecules cm-3, and are consistent with Master Chemical Mechanism (MCM) modeling. The analysis is extended to photochemical production of oxygenated VOCs measured by PTR-MS and is able to explain daytime variability of these species. It is not able to completely reproduce nighttime behavior, possibly due to surface deposition. Using results from this analysis, the carbon mass of secondary compounds expected to have formed by the sixth day of the stagnation event was calculated, then compared to the measured mass of primary and secondary compounds. Only 17% of the expected secondary carbon mass is accounted for by gas phase, aerosol, and snow organic carbon measurements. The disparity is likely due to substantial amounts of unquantified oxygenated products.

Photochemical aging of volatile organic compounds associated with oil and natural gas extraction in the Uintah Basin, UT, during a wintertime ozone formation event

NASA Astrophysics Data System (ADS)

Koss, A. R.; de Gouw, J.; Warneke, C.; Gilman, J. B.; Lerner, B. M.; Graus, M.; Yuan, B.; Edwards, P.; Brown, S. S.; Wild, R.; Roberts, J. M.; Bates, T. S.; Quinn, P. K.

2015-03-01

High concentrations of volatile organic compounds (VOCs) associated with oil and natural gas extraction were measured during a strong temperature inversion in winter of 2013 at a rural site in the Uintah Basin, Utah. During this period, photochemistry enhanced by the stagnant meteorological conditions and concentrated VOCs led to high ozone mixing ratios (150 ppbv). A simple analysis of aromatic VOCs measured by proton-transfer-reaction mass-spectrometry (PTR-MS) is used to estimate (1) VOC emission ratios (the ratio of two VOCs at the time of emission) relative to benzene, (2) aromatic VOC emission rates, and (3) ambient OH radical concentrations. These quantities are determined from a best fit to VOC : benzene ratios as a function of time. The main findings are that (1) emission ratios are consistent with contributions from both oil and gas producing wells, (2) the emission rate of methane (27-57 × 103 kg methane h-1), extrapolated from the emission rate of benzene (4.1 ± 0.4 × 105 molecules cm-3 s-1), agrees with an independent estimate of methane emissions from aircraft measurements in 2012, and (3) calculated daily OH concentrations are low, peaking at 1× 106 molecules cm-3, and are consistent with Master Chemical Mechanism (MCM) modeling. The analysis is extended to photochemical production of oxygenated VOCs measured by PTRMS and is able to explain daytime variability of these species. It is not able to completely reproduce nighttime behavior, possibly due to surface deposition. Using results from this analysis, the carbon mass of secondary compounds expected to have formed by the sixth day of the stagnation event was calculated, then compared to the measured mass of primary and secondary compounds. Only 17% of the expected secondary carbon mass is accounted for by gas phase, aerosol, and snow organic carbon measurements. The disparity is likely due to substantial amounts of unquantified oxygenated products.

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

PubMed

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

2016-06-01

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

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. Copyright © 2011 Elsevier B.V. All rights reserved.

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.

Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies: Evaluation Number 18

NASA Technical Reports Server (NTRS)

Burkholder, J. B.; Sander, S. P.; Abbatt, J. P. D.; Barker, J. R.; Huie, R. E.; Kolb, C. E.; Kurylo, M. J.; Orkin, V. L.; Wilmouth, D. M.; Wine, P. H.

2015-01-01

This is the eighteenth in a series of evaluated sets of rate constants, photochemical cross sections, heterogeneous parameters, and thermochemical parameters compiled by the NASA Panel for Data Evaluation. The data are used primarily to model stratospheric and upper tropospheric processes, with particular emphasis on the ozone layer and its possible perturbation by anthropogenic and natural phenomena. The evaluation is available in electronic form from the following Internet URL: http://jpldataeval.jpl.nasa.gov/

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.

OZONE PRODUCTION EFFICIENCY AND NOX DEPLETION IN AN URBAN PLUME: INTERPRETATION OF FIELD OBSERVATIONS AND IMPLICATIONS FOR EVALUATING O3-NOX-VOC SENSITIVITY

EPA Science Inventory

Ozone production efficiency (OPE) can be defined as the number of ozone (O3) molecules photochemically produced by a molecule of NOx (NO + NO2) before it is lost from the NOx - O3 cycle. Here, we consider observational and modeling techniques to evaluate various operational defi...

An Analytical Investigation of Ozone Episodes in Bangu, Rio de Janeiro.

PubMed

Geraldino, Claudio Gabriel Pinheiro; Martins, Eduardo Monteiro; da Silva, Cleyton Martins; Arbilla, Graciela

2017-05-01

This study investigated the potential factors that contribute to frequent high levels of ozone as well as ozone episodes in Bangu, one of the most critical areas in the city of Rio de Janeiro regarding ozone levels. For 74 days in a two-year period (10.3%), the national air quality standard was exceeded. For the same period, a total of 378 days (51.8%) had ozone concentrations that were between 80 and 160 µg m -3 . A statistical analysis of pollutant concentrations and meteorological data as well as a kinetic and mechanistic analysis of VOC reactivity showed that the high ozone concentrations did not seem to be closely related to local emissions but, rather, were related to pollutant transport and triggered by photochemical activity. The mountains in the southern and northern part of the district contribute to the increase of surface temperatures and the accumulation of pollutants. The VOC/NO x ratios corresponded to a VOC-limited process.

Intercontinental Transport of Tropical Ozone from Biomass Burning: Views from Satellite and SHADOZ (Southern Hemisphere Additional Ozonesondes)

NASA Technical Reports Server (NTRS)

Thompson, A. M.; Witte, J. C.; Chatfield, R. B.; Guam, H.

2003-01-01

There has been interest in the connection between tropical fires and ozone since about 1980. Photochemically reactive gases released by fires (e.g. NO, CO, volatile organic carbon) interact as they do in an urban environment to form ozone. Interacting with chemical sources, tropical meteorology plays a part in tropospheric ozone distributions in the tropics, through large-scale circulation, deep convection, and regional phenomena like the West African and Asian monsoons. An overview of observations, taken from satellite and from ozone soundings, illustrates regional influences and intercontinental- range ozone transport in the tropics. One of the most striking findings is evidence for impacts of Indian Ocean pollution on the south Atlantic ozone maximum referred to as the "ozone paradox" [Thompson et al., GRL, 2000; JGR, 2003; Chatfield et al., GRL, 20031.

Isoprene and its degradation products as strong ozone precursors in Insubria, Northern Italy

NASA Astrophysics Data System (ADS)

Duane, M.; Poma, B.; Rembges, D.; Astorga, C.; Larsen, B. R.

Frequent smog episodes occur during spring, summer, and autumn in Insubria, Northern Italy. On a test site in this area the atmospheric concentration of the photo-oxidants ozone and peroxyacetyl nitrate has been monitored over a year (2000) together with ozone precursors listed in the European Union Air Quality Directive 2002/3/EC, such as nitrous oxides (NO X) and volatile organic compounds (VOC) including hydrocarbons and carbonyls. The results of this study revealed a strong impact of biogenic isoprene on the air quality. In winter isoprene was detected at the ppt level and correlated with anthropogenic VOC. However, during the growing season isoprene exhibited a distinct diurnal variation with maximum concentrations late in the afternoon reaching up 70 ppbC attributed to strong emissions from the abundant vegetation of broad-leaf deciduous trees in this area. A new HPLC-MS method was developed for the determination of isoprene's primary atmospheric oxidation products methacrolein as its 2,4-dinitrophenylhydrazone and methyl vinyl ketone as an unusual double derivative with 2,4-dinitrophenylhydrazine. Methacrolein and methyl vinyl ketone followed the same diurnal and annual trends as isoprene. The average monthly concentration of isoprene and these products ranged from around 10 ppbC in June, July and September to 20 ppbC in August, which constitutes 15-30% of C 3-C 9 VOCs. The contribution from isoprene photo-oxidation to the ambient air formaldehyde concentrations was also found to be high during this period ranging from 30% to 60% in May, June, July and August. From the atmospheric VOC and NO X concentrations the local photochemical ozone formation was estimated by the incremental reactivity approach. The calculations showed that in summer isoprene's contribution to the local ozone formation was as high as 50-75%.

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

Provisional assessment of recent studies on health and ecological effects of ozone exposure

EPA Science Inventory

A reconsideration of the national ambient air quality standards (NAAQS) for O₃ is currently underway. The last Air Quality Criteria Document for Ozone and Related Photochemical Oxidants (O_...

Economic damages of ozone air pollution to crops using combined air quality and GIS modelling

NASA Astrophysics Data System (ADS)

Vlachokostas, Ch.; Nastis, S. A.; Achillas, Ch.; Kalogeropoulos, K.; Karmiris, I.; Moussiopoulos, N.; Chourdakis, E.; Banias, G.; Limperi, N.

2010-09-01

This study aims at presenting a combined air quality and GIS modelling methodological approach in order to estimate crop damages from photochemical air pollution, depict their spatial resolution and assess the order of magnitude regarding the corresponding economic damages. The analysis is conducted within the Greater Thessaloniki Area, Greece, a Mediterranean territory which is characterised by high levels of photochemical air pollution and considerable agricultural activity. Ozone concentration fields for 2002 and for specific emission reduction scenarios for the year 2010 were estimated with the Ozone Fine Structure model in the area under consideration. Total economic damage to crops turns out to be significant and estimated to be approximately 43 M€ for the reference year. Production of cotton presents the highest economic loss, which is over 16 M€, followed by table tomato (9 M€), rice (4.2 M€), wheat (4 M€) and oilseed rape (2.8 M€) cultivations. Losses are not spread uniformly among farmers and the major losses occur in areas with valuable ozone-sensitive crops. The results are very useful for highlighting the magnitude of the total economic impacts of photochemical air pollution to the area's agricultural sector and can potentially be used for comparison with studies worldwide. Furthermore, spatial analysis of the economic damage could be of importance for governmental authorities and decision makers since it provides an indicative insight, especially if the economic instruments such as financial incentives or state subsidies to farmers are considered.

Effects of ozone and ozone/peroxide on trace organic contaminants and NDMA in drinking water and water reuse applications.

PubMed

Pisarenko, Aleksey N; Stanford, Benjamin D; Yan, Dongxu; Gerrity, Daniel; Snyder, Shane A

2012-02-01

An ozone and ozone/peroxide oxidation process was evaluated at pilot scale for trace organic contaminant (TOrC) mitigation and NDMA formation in both drinking water and water reuse applications. A reverse osmosis (RO) pilot was also evaluated as part of the water reuse treatment train. Ozone/peroxide showed lower electrical energy per order of removal (EEO) values for TOrCs in surface water treatment, but the addition of hydrogen peroxide increased EEO values during wastewater treatment. TOrC oxidation was correlated to changes in UV(254) absorbance and fluorescence offering a surrogate model for predicting contaminant removal. A decrease in N-nitrosodimethylamine (NDMA) formation potential (after chloramination) was observed after treatment with ozone and ozone/peroxide. However, during spiking experiments with surface water, ozone/peroxide achieved limited destruction of NDMA, while in wastewaters net direct formation of NDMA of 6-33 ng/L was observed after either ozone or ozone/peroxide treatment. Once formed during ozonation, NDMA passed through the subsequent RO membranes, which highlights the significance of the potential for direct NDMA formation during oxidation in reuse applications. Copyright © 2011 Elsevier Ltd. All rights reserved.

Simulating ozone concentrations using precursor emission inventories in Delhi - National Capital Region of India

NASA Astrophysics Data System (ADS)

Sharma, Sumit; Khare, Mukesh

2017-02-01

This study simulates ground level ozone concentrations in a heavily populated and polluted National Capital Region (NCR- Delhi) in India. Multi-sectoral emission inventories of ozone precursors are prepared at a high resolution of 4 × 4 km2 for the whole region covering the capital city of Delhi along with other surrounding towns and rural regions in NCR. Emission inventories show that transport sector accounts for 55% of the total NOx emissions, followed by power plants (23%) and diesel generator sets (7%). In NMVOC inventories, transport sector again accounts for 33%, followed by evaporative emissions released from solvent use and fuel handling activities (30%), and agricultural residue burning (28%). Refuse burning contributes to 73% of CO emissions mainly due to incomplete combustion, followed by agricultural residue burning (14%). These emissions are spatially and temporally distributed across the study domain and are fed into the WRF-CMAQ models to predict ozone concentrations for the year 2012. Model validations are carried out with the observed values at different monitoring stations in Delhi. The performance of the models over various metrics used for evaluation was found to be satisfactory. Summers and post-monsoon seasons were better simulated than monsoon and winter seasons. Simulations have shown higher concentrations of ozone formation during summers and lesser during winters and monsoon seasons, mainly due to varying solar radiation affecting photo-chemical activities. Ozone concentrations are observed lower at those locations where NOx emissions are higher, and concentrations increase close to the boundary of study domain when compared to the center of Delhi city. Downwind regions to Delhi are influenced by the ozone formed due to plume of precursor emissions released from Delhi. Considering significant background contributions, regional scale controls are required for reducing ozone in NCR.

Ozone Quenching Properties of Isoprene and Its Antioxidant Role in Leaves1

PubMed Central

Loreto, Francesco; Mannozzi, Michela; Maris, Christophe; Nascetti, Pamela; Ferranti, Francesco; Pasqualini, Stefania

2001-01-01

Isoprene is formed in and emitted by plants and the reason for this apparent carbon waste is still unclear. It has been proposed that isoprene stabilizes cell and particularly chloroplast thylakoid membranes. We tested if membrane stabilization or isoprene reactivity with ozone induces protection against acute ozone exposures. The reduction of visible, physiological, anatomical, and ultrastructural (chloroplast) damage shows that clones of plants sensitive to ozone and unable to emit isoprene become resistant to acute and short exposure to ozone if they are fumigated with exogenous isoprene, and that isoprene-emitting plants that are sensitive to ozone do not suffer damage when exposed to ozone. Isoprene-induced ozone resistance is associated with the maintenance of photochemical efficiency and with a low energy dissipation, as indicated by fluorescence quenching. This suggests that isoprene effectively stabilizes thylakoid membranes. However, when isoprene reacts with ozone within the leaves or in a humid atmosphere, it quenches the ozone concentration to levels that are less or non-toxic for plants. Thus, protection from ozone in plants fumigated with isoprene may be due to a direct ozone quenching rather than to an induced resistance at membrane level. Irrespective of the mechanism, isoprene is one of the most effective antioxidants in plants. PMID:11457950

Microphysical Modelling of the 1999-2000 Arctic Winter. 2; Chlorine Activation and Ozone Depletion

NASA Technical Reports Server (NTRS)

Drdla, K.; Schoeberl, M. R.; Gore, Warren J. (Technical Monitor)

2001-01-01

The effect of a range of assumptions about polar stratospheric clouds (PSCs) on ozone depletion has been assessed using at couple microphysical/photochemical model. The composition of the PSCs was varied (ternary solutions, nitric acid trihydrate, nitric acid dehydrate, or ice), as were parameters that affected the levels of denitrification and dehydration. Ozone depletion was affected by assumptions about PSC freezing because of the variability in resultant nitrification chlorine activation in all scenarios was similar despite the range of assumed PSC compositions. Vortex-average ozone loss exceeded 40% in the lower stratosphere for simulations without nitrification an additional ozone loss of 15-20% was possible in scenarios where vortex-average nitrification reached 60%. Ozone loss intensifies non-linearly with enhanced nitrification in air parcels with 90% nitrification 40% ozone loss in mid-April can be attributed to nitrification alone. However, these effects are sensitive to the stability of the vortex in springtime: nitrification only began to influence ozone depletion in mid-March.

[The two ozone problems: too much in the troposphere, too little in the stratosphere].

PubMed

Staehelin, J

1992-03-10

Trends analysis based on the long-term Swiss ozone measurements from Arosa and Payerne operationally performed by the Swiss Meteorological Institute are presented. These measurement include stratospheric ozone (approximately 90% of total ozone) and tropospheric ozone. The total ozone measurements from Arosa, the world longest series started at 1926, indicate, that total ozone has declined since about 1970 by approximately 5%. The ozone balloon soundings, operationally performed at Payerne since 1969 (2-3 ascents per week) show, that stratospheric ozone has decreased strongly in the last 20 years, whereas tropospheric ozone, remarkably has increased during this period. The relative change was strongest in the troposphere (more than 10% per decade, 3-4% increase per year during 1982-1988). However, on an absolute scale, changes in the stratosphere were strongest (relative decrease: 6 to 7% per decade at 20-22 km). The present scientific theories of the two ozone problems are reviewed: stratospheric ozone decrease was caused by the anthropogenic emissions of fluorochlorocarbons and other compounds mainly released from the earth surface. Tropospheric ozone has increased due to photochemical production of mainly anthropogenically emitted nitrogen oxides, volatile organic compounds and CO.

Ozone budget over the Amazon - Regional effects from biomass-burning emissions

NASA Technical Reports Server (NTRS)

Richardson, Jennifer L.; Fishman, Jack; Gregory, Gerald L.

1991-01-01

Data from the NASA dry-season Amazon boundary layer experiment (ABLE2A) is used with a 1D tropospheric photochemical model to analyze the atmospheric chemistry in the region and determine the impact of the long-range transport of biomass-burning emissions. Inputs of surface sources and the deposition of various species measured during ABLE2A are employed to simulate the background atmosphere, and haze characteristics are introduced for a 12-hr simulation. The in situ ozone production rate doubles during the period of haze when hydrocarbons are present. The model predicts that the production of ozone is enhanced during the dry season, and that increased ozone during the southern tropical burning season is related to the regional transport of haze.

Comparison of scientific findings from major ozone field studies in North America and Europe

NASA Astrophysics Data System (ADS)

Solomon, Paul; Cowling, Ellis; Hidy, George; Furiness, Cari

During the past decade, nearly 600 million dollars were invested in more than 30 major field studies in North America and Europe examining tropospheric ozone chemistry, meteorology, precursor emissions, and modeling. Most of these studies were undertaken to provide new or refined knowledge about ozone accumulation and to assist in the development of economical and effective emissions management practices for ozone. In this paper, we describe a selection of field research programs conducted under a wide range of geographical and climatological conditions in North America and Europe. The designs of these studies were generally similar, employing a combination of ground-based observation networks, upper-air sampling, and meteorological observations. Analysis and interpretation of the resulting data were combined with improved inventories of ozone precursor emissions and air quality modeling to develop new or enhanced knowledge about photochemical processes under various tropospheric conditions. The scientific results from these studies contained few surprises; in fact, they generally affirmed the conclusions in the review by the US National Research Council (NRC, 1999). Key findings include: (1) reaffirmation that tropospheric ozone is a multi-scale phenomenon extending to continental boundaries; (2) aerometric conditions aloft are important to ground-level ozone; (3) biogenic sources make important contributions to VOC and NO x emissions in parts of eastern North America and southern Europe; (4) emissions estimates are among the more uncertain components of predictive models for ozone; (5) recirculating flow over complex terrain and large water bodies are universally important factors affecting accumulation of ozone at the ground; (6) nonlinearities in ozone response to precursor changes create important degrees of freedom in management strategies - VOC and NO x sensitivities vary extensively in urban and rural areas, making decisions about emissions management

Ozone from Wildfires: Peering through the Smog

NASA Astrophysics Data System (ADS)

Jaffe, D. A.; Baylon, P.; Wigder, N. L.; Collier, S.; Zhou, S.; Zhang, Q.; Alvarado, M. J.

2014-12-01

In the western US, many areas are near the current air quality standard for O3. Yet there is substantial inter-annual variability (IAV) in the number of days that exceed the O3 air quality threshold (currently 75 ppbv for an 8-hour average). We propose that wildfires are the dominant cause for this IAV. However there are large uncertainties around O3 production from wildfires due to numerous complicating factors. Ozone formation in wildfire plumes differs substantially from urban O3 production in several ways: substantial variations in the emissions, much larger aerosol loadings, a much greater variety of reactive and oxygenated VOCs, rapid and substantial formation of PAN and very different sources of HOx in the plume. These factors make it challenging to model wildfire impacts on photochemistry in the usual way. In this presentation we will show examples of three common situations based on data from the Mt. Bachelor Observatory: Rapid O3 formation (within one day) in a wildfire plume. Slow, but substantial, O3 formation (over days to a week) in a wildfire plume. No detectable O3 formation in a wildfire plume. We will interpret these results with respect to the observed NOy mixing ratios, the photochemical environment, the combustion efficiency, the plume transport and other factors and suggest some key experiments and modeling studies that can help further our understanding of wildfire O3 production.

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.

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...

Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies Evaluation Number 15

NASA Technical Reports Server (NTRS)

Sander, S. P.; Friedl, R. R.; Golden, D. M.; Kurylo, M. J.; Moortgat, G. K.; Wine, P. H.; Ravishankara, A. R.; Kolb, C. E.; Molina, M. J.; Finlayson-Pitts, B. J.;

Chemical kinetics and photochemical data for use in stratospheric modeling evaluation Number 8

NASA Technical Reports Server (NTRS)

Demore, W. B.; Molina, M. J.; Sander, S. P.; Golden, D. M.; Hampson, R. F.; Kurylo, M. J.; Howard, C. J.; Ravishankara, A. R.

1987-01-01

This is the eighth 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 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, Documentation Section, 111-116B, California Institute of Technology, Pasadena, California, 91109.

Ozone production during an urban air stagnation episode over Nashville, Tennessee

NASA Astrophysics Data System (ADS)

Valente, R. J.; Imhoff, R. E.; Tanner, R. L.; Meagher, J. F.; Daum, P. H.; Hardesty, R. M.; Banta, R. M.; Alvarez, R. J.; McNider, R. T.; Gillani, N. V.

1998-09-01

The highest O3 levels observed during the 1995 Southern Oxidants Study in middle Tennessee occurred during a period of air stagnation from July 11 through July 15. Extensive airborne (two fixed wing and one helicopter) and ground-based measurements of the chemistry and meteorology of this episode near Nashville, Tennessee, are presented. In situ airborne measurements include O3, NOy, NO, NO2, SO2, CO, nitrate, hydrocarbons, and aldehydes. Airborne LIDAR O3 measurements are also utilized to map the vertical and horizontal extent of the urban plume. The use of multiple instrumented research aircraft permitted highly detailed mapping of the plume chemistry in the vertical and horizontal dimensions. Interactions between the urban Nashville plume (primarily a NOx and hydrocarbon source) and the Gallatin coal-fired power plant plume (primarily a NOx and SO2 source) are also documented, and comparisons of ozone formation in the isolated and mixed urban and power plant plume are presented. The data suggest that during this episode the background air and the edges of the urban plume are NOx sensitive and the core of the urban plume is hydrocarbon sensitive. Under these worst case meteorological conditions, ambient O3 levels well over the level of the new National Ambient Air Quality Standard (NAAQS) for ozone (80 ppb) were observed over and just downwind of Nashville. For example, on July 12, the boundary layer air upwind of Nashville showed 60 to 70 ppb O3, while just downwind of the city the urban plume maximum was over 140 ppb O3. With a revised ozone standard set at 80 ppb (8 hour average) and upwind levels already within 10 or 20 ppb of the standard, only a slight increase in ozone from the urban area will cause difficulty in attaining the standard at monitors near the core of the urban plume during this type of episode. The helicopter mapping and LIDAR aircraft data clearly illustrate that high O3 levels can occur during stagnation episodes within a few kilometers of

A global analysis of the ozone deficit in the upper stratosphere and lower mesosphere

NASA Technical Reports Server (NTRS)

Eluszkiewicz, Janusz; Allen, Mark

1993-01-01

The global measurements of temperature, ozone, water vapor, and nitrogen dioxide acquired by the Limb Infrared Monitor of the Stratosphere (LIMS), supplemented by a precomputed distribution of chlorine monoxide, are used to test the balance between odd oxygen production and loss in the upper stratosphere and lower mesosphere. An efficient photochemical equilibrium model, whose validity is ascertained by comparison with the results from a fully time-dependent one-dimensional model at selected latitudes, is used in the calculations. The computed ozone abundances are systematically lower than observations for May 1-7, 1979, which suggests, contrary to the conclusions of other recent studies, a real problem in model simulations of stratospheric ozone.

Mesospheric effects of solar ultraviolet variations - Further analysis of SME IR ozone and Nimbus 7 SAMS temperature data

NASA Astrophysics Data System (ADS)

Hood, L. L.; Huang, Z.; Bougher, S. W.

1991-07-01

In order to improve the constraints on models of the mesospheric response to solar UV variations, an analysis is conducted of the Solar Mesosphere Explorer (SME) IR ozone data and Nimbus 7 stratosphere and mesosphere sounder (SAMS) temperature data. Maximum low-altitude ozone and temperature-response amplitudes occur at about the same altitude, where a strong coupling between photochemical and thermal components of the mesospheric response is suggested by the simultaneous positive temperature and negative ozone response maxima. Increased Lyman-alpha dissociation of water vapor and temperature feedback are theorized to account for the negative ozone response. HO(x) chemical heating can increase as ozone destruction increases, and can therefore account for the positive temperature response.

Mesospheric effects of solar ultraviolet variations - Further analysis of SME IR ozone and Nimbus 7 SAMS temperature data

NASA Technical Reports Server (NTRS)

Hood, L. L.; Huang, Z.; Bougher, S. W.

1991-01-01

In order to improve the constraints on models of the mesospheric response to solar UV variations, an analysis is conducted of the Solar Mesosphere Explorer (SME) IR ozone data and Nimbus 7 stratosphere and mesosphere sounder (SAMS) temperature data. Maximum low-altitude ozone and temperature-response amplitudes occur at about the same altitude, where a strong coupling between photochemical and thermal components of the mesospheric response is suggested by the simultaneous positive temperature and negative ozone response maxima. Increased Lyman-alpha dissociation of water vapor and temperature feedback are theorized to account for the negative ozone response. HO(x) chemical heating can increase as ozone destruction increases, and can therefore account for the positive temperature response.

Intercontinental Transport of Tropical Ozone from Biomass Burning: Views from Satellite and SHADOZ (Southern Hemisphere Additional Ozonesondes) Soundings

NASA Technical Reports Server (NTRS)

Thompson, Anne M.

2003-01-01

The atmospheric impacts of tropical fires came to attention in the 1970's and there has been interest in the connection between these fires and ozone since about 1980. Photochemically reactive gases released by fires (e.g. NO, CO, volatile organic carbon) interact as they do in an urban environment to form ozone. Tropical meteorology also plays a part in tropospheric ozone distributions in the tropics - through large-scale circulation, deep convection, regional phenomena (West African and Asian monsoon) - and variations associated with El-Nino and the Quasi- biennial Oscillation have been reported. This Poster is an overview of observations, taken from satellite and from ozone soundings, that illustrate regional influences and intercontinental-range ozone transport in the tropics.

Fate of Chloromethanes in the Atmospheric Environment: Implications for Human Health, Ozone Formation and Depletion, and Global Warming Impacts

PubMed Central

Tsai, Wen-Tien

2017-01-01

Among the halogenated hydrocarbons, chloromethanes (i.e., methyl chloride, CH3Cl; methylene chloride, CH2Cl2; chloroform, CHCl3; and carbon tetrachloride, CCl4) play a vital role due to their extensive uses as solvents and chemical intermediates. This article aims to review their main chemical/physical properties and commercial/industrial uses, as well as the environment and health hazards posed by them and their toxic decomposition products. The environmental properties (including atmospheric lifetime, radiative efficiency, ozone depletion potential, global warming potential, photochemical ozone creation potential, and surface mixing ratio) of these chlorinated methanes are also reviewed. In addition, this paper further discusses their atmospheric fates and human health implications because they are apt to reside in the lower atmosphere when released into the environment. According to the atmospheric degradation mechanism, their toxic degradation products in the troposphere include hydrogen chloride (HCl), carbon monoxide (CO), chlorine (Cl2), formyl chloride (HCOCl), carbonyl chloride (COCl2), and hydrogen peroxide (H2O2). Among them, COCl2 (also called phosgene) is a powerful irritating gas, which is easily hydrolyzed or thermally decomposed to form hydrogen chloride. PMID:29051455

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

NASA Astrophysics Data System (ADS)

Li, Yongxian

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

The Anatomy of High Levels of Wintertime Photochemical Ozone Production in the Uintah Basin, Utah, 2013

NASA Astrophysics Data System (ADS)

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

2013-12-01

The Uintah Basin, Utah is ~ 5,000 km2 in size with lower elevations of ~1400 m msl ringed by mountains rising to ~3,000 m. Within this basin are 6,000 gas wells that produced 10 billion m3 of natural gas and 4,000 oil wells that produced ~22 million barrels of oil in 2012. In winter, the confined geography in the basin traps effluents from these fossil fuel extraction activities into a shallow layer (a few 100 meters deep) beneath strong temperature inversions, especially when ample snow cover is present throughout the basin. The temperature inversions isolate the basin from upper level winds that allow for stagnant conditions that may last for a week or more before a frontal system may flush the basin out. The highly reflective snow provides for enhanced photolysis rates that in February are comparable to those in June. In 2013 December snowfall in the Uintah Basin persisted until early March with exceptionally elevated ozone production occurring in four distinct, 10-day periods separated by 2-3 days of near background values following frontal induced washouts of the basins. In one well studied ozone event, background ozone levels of 55 ppb in the basin were measured from the surface to the lower troposphere on January 30, 2013. By February 1, ozone concentrations from the surface to the top of the 180 m deep temperature inversion averaged 100 ppb. By February 6 ozone concentrations were 165 ppb throughout the same layer. From aircraft measurements these ozone concentrations were observed to be fairly well mixed throughout the basin although there were some notable hotspots. Clean-out of ozone and ozone precursors in the Uintah Basin was observed to occur within 4 hours or less as basin air was replaced with air coming in from the west coast and mixing to the surface.

A Global Ozone Climatology from Ozone Soundings via Trajectory Mapping: A Stratospheric Perspective

NASA Technical Reports Server (NTRS)

Liu, J. J.; Tarasick, D. W.; Fioletov, V. E.; McLinden, C.; Zhao, T.; Gong, S.; Sioris, G.; Jin, J. J.; Liu, G.; Moeini, O.

2013-01-01

as the spring ozone maximum over the Canadian Arctic. It also covers higher latitudes than current satellite data. The climatology shows clearly the depletion of ozone from the 1970s to the mid 1990s and ozone recovery in the 2000s. When this climatology is used as the upper boundary condition in an Environment Canada operational chemical forecast model, the forecast is improved in the vicinity of the upper tropospherelower stratosphere region. As this ozone climatology is neither dependent on a priori data or photochemical modeling, it provides independent information and insight that can supplement satellite data and model simulations and enhance our understanding of stratospheric ozone.

Ozone Production and Its Sensitivity to NOx and VOCs: Results from the DISCOVER-AQ Field Experiment, Houston 2013

NASA Astrophysics Data System (ADS)

Ren, X.; Mazzuca, G.; Loughner, C.; Estes, M. J.; Crawford, J. H.; Weinheimer, A. J.; Pickering, K. E.; Dickerson, R. R.

2016-12-01

An observation-constrained box model based on the Carbon Bond mechanism, Version 5 (CB05), was used to study photochemical processes along the NASA P-3B flight track and spirals over eight surface sites during the September 2013 Houston, Texas deployment of the NASA DISCOVER-AQ campaign. Data from this campaign provided an opportunity to examine and improve our understanding of atmospheric photochemical oxidation processes related to the formation of secondary air pollutants such as ozone (O3). O3 production and its sensitivity to NOx and VOCs were calculated at different locations and times of day. Ozone production efficiency (OPE), defined as the ratio of the ozone production rate to the NOx oxidation rate, was calculated using the observations and the simulation results of the box and Community Multiscale Air Quality (CMAQ) models. Correlation of these results with other parameters, such as radical sources and NOx mixing ratio, was also evaluated. It was generally found that O3 production tends to be more VOC sensitive in the morning along with high ozone production rates, suggesting that control of VOCs may be an effective way to control O3 in Houston. In the afternoon, O3 production was found to be mainly NOx sensitive with some exceptions. O3 production at near major emissions sources such as Deer Park was mostly VOC sensitive for the entire day, other urban areas near Moody Tower and Channelview were VOC sensitive or in the transition regime, and areas farther from downtown Houston such as Smith Point and Conroe were mostly NOx sensitive for the entire day. It was also found that the control of NOx emissions has reduced O3 concentrations over Houston, but led to larger OPE values. The results from this work strengthen our understanding of O3 production; they indicate that controlling NOx emissions will provide air quality benefits over the greater Houston metropolitan area in the long run, but in selected areas controlling VOC emissions will also be

On the Complex Coupling Between the Production of Ozone and Secondary Organic Aerosol in Polluted Urban Regions

NASA Astrophysics Data System (ADS)

Stewart, D. R.; Stockwell, W. R.; Morris, V. R.; Fitzgerald, R. M.

2016-12-01

The major photochemical processes that produce ozone and aerosols are coupled together strongly in the polluted urban atmosphere. Aerosols are either directly emitted or formed through the same kind of chemistry that leads to the production of ozone. The aerosols produced through atmospheric chemistry are known as secondary aerosols and they may be composed of inorganic (nitrates, sulfates) or organic compounds. Wind blown dust and soot are two examples of primary aerosols. The component of secondary inorganic aerosols includes compounds such as ammonium nitrate, ammonium bisulfate and ammonium sulfate. Secondary organic aerosols are a very important component of PM with strong implications for health. The formation of secondary organic aerosol is linked with ozone photochemistry through the reactions of volatile organic compounds (VOC). The oxidation of VOC produces radicals that convert nitric oxide to nitrogen dioxide that photolyze to produce ozone. Larger VOC (those with more carbon atoms) undergo a number of oxidation cycles that add oxygen atoms to large organic molecules. The vapor pressure of many of these highly oxidized compounds is sufficiently low that they condense to produce secondary organic aerosols. The Community Multi-scale Air Quality model (CMAQ) and other chemical simulations have been made to quantify the relationship between varying emissions of VOC and NOx and the production of inorganic and secondary organic aerosols. The results from this analysis will be presented.

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...

Formation of Ozonic Compound and Used as Therapeutic Agent in Medicine

NASA Astrophysics Data System (ADS)

Zhu, Lei; Ye, Chunyong; Min, Xinmin

2018-03-01

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

Surface ozone measurements in the southwest of the Iberian Peninsula (Huelva, Spain).

PubMed

Carnero, Jose A Adame; Bolívar, Juan P; de la Morena, Benito A

2010-02-01

Photochemical ozone pollution of the lower troposphere (LT) is a very complex process involving meteorological, topographic emissions and chemical parameters. Ozone is considered the most important air pollutant in rural, suburban and industrial areas of many sites in the world since it strongly affects human health, vegetation and forest ecosystems, and its increase during the last decades has been significant. In addition, ozone is a greenhouse gas that contributes to climate change. For these reasons, it is necessary to carry out investigations that determine the behaviour of ozone at different locations. The aim of this work is to understand the levels and temporal variations of surface ozone in an industrial-urban region of the Southwest Iberian Peninsula. The study is based on ozone hourly data recorded during a 6-year period, 2000 to 2005 at four stations and meteorological data from a coastal station. The stations used were El Arenosillo and Cartaya--both coastal stations, Huelva--an urban site and Valverde--an inland station 50 km away from the coastline. The general characteristics of the ozone series, seasonal and daily ozone cycles as well as number of exceedances of the threshold established in the European Ozone Directive have been calculated and analysed. Analysis of the meteorological data shows that winter-autumn seasons are governed by the movement of synoptic weather systems; however, in the spring-summer seasons, both synoptic and mesoescale conditions exist. Average hourly ozone concentrations range from 78.5 +/- 0.1 microg m(-3) at Valverde to 57.8 +/- 0.2 microg m(-3) at Huelva. Ozone concentrations present a seasonal variability with higher values in summer months, while in wintertime, lower values are recorded. A seasonal daily evolution has also been found with minimum levels around 08:00 UTC, which occurs approximately 1-1.5 h after sunrise, whereas the maximum is reached at about 16:00 UTC. Furthermore, during summer, the maximum value

DAILY SIMULATION OF OZONE AND FINE PARTICULATES OVER NEW YORK STATE: FINDINGS AND CHALLENGES

EPA Science Inventory

This study investigates the potential utility of the application of a photochemical modeling system in providing simultaneous forecasts of ozone (O₃) and fine particulate matter (PM_2.5) over New York State. To this end, daily simulations from the Community M...

Application of a photochemical grid model to milan metropolitan area

NASA Astrophysics Data System (ADS)

Silibello, C.; Calori, G.; Brusasca, G.; Catenacci, G.; Finzi, G.

High ozone levels are regularly reached during summer period in South-European urban areas, calling for careful design of primary pollutants emission reduction strategies. In this perspective the CALGRID modelling system has been applied to Milan metropolitan area, located in the Po Valley, the most industrialised and populated area in Italy. For the first modelling exercise, a simulation domain of 100×100 km 2 has been considered and a summer period, characterised by high photochemical activity, has been selected. Hourly emissions have been derived by spatially and temporally disaggregating national inventories data, while standard upper-air and ground-based meteorological data have been used as input to the CALMET pre-processor. A careful analysis of simulation results versus local network monitoring data has revealed some critical points, related to both modelling assumptions and practical data availability. A satisfactory reproduction of daytime ozone behaviour has been, in fact, accomplished, both in urban and suburban sites, while nighttime primary pollutants accumulations and consequent ozone consumption simulated by the model have not found correspondence in the measurements. Nitrogen dioxide has been also successfully modelled, mostly in city surroundings, whereas higher discrepancies have been found in some urban stations. Possible explanations of these facts are discussed in the paper, giving an insight for further work.

Long-term tropospheric and lower stratospheric ozone variations from ozonesonde observations

NASA Technical Reports Server (NTRS)

London, J.; Liu, S. C.

1992-01-01

An analysis is presented of the long-term mean pressure-latitude seasonal distribution of tropospheric and lower stratospheric ozone for the four seasons covering, in part, over 20 years of ozonesonde data. The observed patterns show minimum ozone mixing ratios in the equatorial and tropical troposphere except in regions where net photochemical production is dominant. In the middle and upper troposphere, and low stratosphere to 50 mb, ozone increases from the tropics to subpolar latitudes of both hemispheres. In mid stratosphere, the ozone mixing ratio is a maximum over the tropics. The observed vertical ozone gradient is small in the troposphere but increases rapidly above the tropopause. The amplitude of the annual variation increases from a minimum in the tropics to a maximum in polar regions. Also, the amplitude increases with height at all latitudes up to about 30 mb where the phase of the annual variation changes abruptly. The phase of the annual variation is during spring in the boundary layer, summer in mid troposphere, and spring in the upper troposhere and lower stratosphere.

Chemical composition and photochemical reactivity of exhaust from aircraft turbine engines

NASA Astrophysics Data System (ADS)

Spicer, C. W.; Holdren, M. W.; Riggin, R. M.; Lyon, T. F.

1994-10-01

Assessment of the environmental impact of aircraft emissions is required by planners and policy makers. Seveal areas of concern are: 1. exposure of airport workers and urban residents to toxic chemicals emitted when the engines operate at low power (idle and taxi) on the ground; 2. contributions to urban photochemical air pollution of aircraft volatile organic and nitrogen oxides emissions from operations around airports; and 3. emissions of nitrogen oxides and particles during high-altitude operation. The environmental impact of chemicals emitted from jet aircraft turbine engines has not been firmly established due to lack of data regarding emission rates and identities of the compounds emitted. This paper describes an experimental study of two different aircraft turbine engines designed to determine detailed organic emissions, as well as emissions of inorganic gases. Emissions were measured at several engine power settings. Measurements were made of detailed organic composition from C1 through C17, CO, CO2, NO, NOx, and polycyclic aromatic hydrocarbons. Measurements were made using a multi-port sampling pro be positioned directly behind the engine in the exhaust exit plane. The emission measurements have been used to determine the organic distribution by carbon number and the distribution by compound class at each engine power level. The sum of the organic species was compared with an independent measurement of total organic carbon to assess the carbon mass balance. A portion of the exhaust was captured and irradiated in outdoor smog chambers to assess the photochemical reactivity of the emissions with respect to ozone formation. The reactivity of emissions from the two engines was apportioned by chemical compound class.

Transport and Chemical Production of Ozone in the East Asian Pacific Rim Region: -Modeling Study Based on Observation-

NASA Astrophysics Data System (ADS)

Akimoto, H.; Li, J.; Wang, Z.; Yamaji, K.; Pochanart, P.; Ohara, T.; Uno, I.; Gao, C.; Wang, X.; Tanimoto, H.; Kurokawa, J.

2007-12-01

Form satellite observational data, east-central China covering the North China Plain (NCP) and Yanzi Delta (YZD) has been identified as the most widely spread source area of air pollutants in the East Asian Pacific region. In order to quantify transport and chemical production of ozone in this region, both of observational and modeling studies in both of source and outflow region are necessary. In the present study, we investigated the budgets of ozone over East Asia by using regional chemical transport models (NAQPMS and CMAQ) based on observations at newly founded three mountain sites (Mt. Tai, Hua and Huang) in east-central China, and several sites from EANET and regional WMO/GAW. The observations show that a striking pattern of two sharp high ozone peaks in May-June and September-October at the three mountain sites. The budget analysis by the model confirms that maximum of net photochemical ozone production reaches 31.8, 15.1 and 11.4 ppb/day at Mt. Tai, Hua and Huang, respectively. The net chemical production dominates the formation of ozone maximum at Mt. Tai and Hua in June, and the importing transport also plays a comparable importance at Mt. Huang. In the outflow region at Oki, Japan, transport of ozone produced by East Asian emissions accounts up to 21 ppb in summer but less than 3 ppb in winter agreeing with the model analysis. The contribution of ozone due to East Asian emission is the largest (53.6%) in July-August, and somewhat smaller in May-June (34.0%) and September-October (30.7%) on the transect between Japan and the Asian continent.

Photochemical oxidation: A solution for the mixed waste dilemma

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

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 disposedmore » 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.« less

Gas-Phase Formation Rates of Nitric Acid and Its Isomers Under Urban Conditions

NASA Technical Reports Server (NTRS)

Okumura, M.; Mollner, A. K.; Fry, J. L.; Feng, L.

2005-01-01

Ozone formation in urban smog is controlled by a complex set of reactions which includes radical production from photochemical processes, catalytic cycles which convert NO to NO2, and termination steps that tie up reactive intermediates in long-lived reservoirs. The reaction OH + NO2 + M -4 HONO2 + M (la) is a key termination step because it transforms two short-lived reactive intermediates, OH and NO2, into relatively long-lived nitric acid. Under certain conditions (low VOC/NOx), ozone production in polluted urban airsheds can be highly sensitive to this reaction, but the rate parameters are not well constrained. This report summarizes the results of new laboratory studies of the OH + NO2 + M reaction including direct determination of the overall rate constant and branching ratio for the two reaction channels under atmospherically relevant conditions.

Trends in Surface Level Ozone Observations from Human-health Relevant Metrics: Results from the Tropospheric Ozone Assessment Report (TOAR)

NASA Astrophysics Data System (ADS)

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

2017-12-01

Ozone is an air pollutant formed in the atmosphere from precursor species (NOx, VOCs, CH4, CO) that is detrimental to human health and ecosystems. The global Tropospheric Ozone Assessment Report (TOAR) initiative has assembled a global database of surface ozone observations and generated ozone exposure metrics at thousands of measurement sites around the world. This talk will present results from the assessment focused on those indicators most relevant to human health. Specifically, the trends in ozone, comparing different time periods and patterns across regions and among metrics will be addressed. In addition, the fraction of population exposed to high ozone levels and how this has changed between 2000 and 2014 will also be discussed. The core time period analyzed for trends was 2000-2014, selected to include a greater number of sites in East Asia. Negative trends were most commonly observed at many US and some European sites, whereas many sites in East Asia showed positive trends, while sites in Japan showed more of a mix of positive and negative trends. More than half of the sites showed a common direction and significance in the trends for all five human-health relevant metrics. The peak ozone metrics indicate a reduction in exposure to peak levels of ozone related to photochemical episodes in Europe and the US. A considerable number of European countries and states within the US have shown a decrease in population-weighted ozone over time. The 2000-2014 results will be augmented and compared to the trend analysis for additional time periods that cover a greater number of years, but by necessity are based on fewer sites. Trends are found to be statistically significant at a larger fraction of sites with longer time series, compared to the shorter (2000-2014) time series.

DO3SE modelling of soil moisture to determine ozone flux to forest trees

Treesearch

P. Büker; T. Morrissey; A. Briolat; R. Falk; D. Simpson; J.-P. Tuovinen; R. Alonso; S. Barth; M. Baumgarten; N. Grulke; P.E. Karlsson; J. King; F. Lagergren; R. Matyssek; A. Nunn; R. Ogaya; J. Peñuelas; L. Rhea; M. Schaub; J. Uddling; W. Werner; L.D. Emberson

2012-01-01

The DO3SE (Deposition of O3 for Stomatal Exchange) model is an established tool for estimating ozone (O3) deposition, stomatal flux and impacts to a variety of vegetation types across Europe. It has been embedded within the EMEP (European Monitoring and Evaluation Programme) photochemical model to...

Consideration of air quality standards for vegetation with respect to ozone

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

Heggestad, H.E.

1969-06-01

Present evidence suggests that ozone is the most damaging of all air pollutants affecting vegetation. It is the principal oxidant in the photochemical smog complex. Concentrations of ozone have exceeded 0.5 part per million (ppm) in the Los Angeles area. One-tenth of this level for 8 hours is known to injure very sensitive tobacco varieties. Many plant species are visibly affected after a few hours exposure at concentrations much lower than 0.5 ppm. There is also some evidence that ozone reduces plant growth. Many factors must be taken into account when considering standards to protect vegetation from ozone damage. Thesemore » include ozone concentration and methods of measurement, time of exposure, possible additive effects of other pollutants, sensitivity of plant species, their economic value, and the extent of injury which can be tolerated. The response of a species to the pollutant is conditioned by genetic factors and environmental conditions. Lack of specific routine methods for measuring ozone in ambient air is a handicap. California and Colorado established standards for oxidants at 0.15 and 0.10 ppm, respectively, for 1 hour. How these standards relate to the ozone dosage causing acute and chronic injury to various plant species is discussed.« less

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

PubMed

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

2010-04-01

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

Subclinical and Overt Adverse Cardiac Effects with Ozone Inhalation in Rats: Potentially Dire Implications of Low Exposures

EPA Science Inventory

Ozone is a ubiquitous smog-associated photochemical oxidant with deleterious health effects. While most of the adverse effects described to date involve the respiratory system (i.e, decrements in lung function, airway injury and inflammation, exacerbation of asthma, and compromis...

Comprehensive Analyzer for Biogenic Volatile Organic Compounds Detected as Total Ozone Reactivity

NASA Astrophysics Data System (ADS)

Matsumoto, J.

2011-12-01

Volatile organic compounds, VOCs, are emitted from various sources into the atmosphere. Through the reactions of VOCs with atmospheric radicals (eg. daytime OH, nighttime NO3, and all-day O3), formation of photochemical oxidants and secondary organic aerosols, SOA, are important. To investigate the mechanisms of reactions in the atmosphere and to control such secondary products effectively, it is essential to capture the behavior of VOC emission with the radical reactivity of VOCs considered. Recently, in addition to OH reactions of anthropogenic VOCs, SOA formation due to ozonolysis of biogenic VOCs (BVOCs) is one of the hottest topics in the atmospheric chemistry. It is difficult to analyze all the species individually due to the great number of VOCs. In this study, a comprehensive tool for capturing the total reactivity of BVOCs with ozone is realized utilizing a chemiluminescence ozone analyzer. A sensitive and fast-response ozone analyzer was developed based on an existing chemiluminescent NO analyzer (CLD). The CLD-O3 analyzer was used to monitor the fast variation of O3 in the sample of the VOC + O3 experiment. When O3 was added to the VOC sample, the reduction of O3 due to VOC was monitored and the O3 reactivity RO3 was determined with the reaction time considered. Dependence of the response of analyzer on the reaction time and the reactivity of sample was examined and confirmed as reasonable. As a result, VOCs can be detected at the level of ppbv (as limonene, S/N = 3). The detection limit of RO3 was 0.0002 s-1. For the test of ozone reactivity measurement of BVOCs emitted from the real vegetation, variation of ozone reactivity was significantly observed after the nursery was put into a closed chamber. In addition, just after the leaves of the plant were physically stimulated, observed reactivity increased. It was experimentally confirmed that stimulus to the leaves of the plant resulted in the increase of total BVOC emission. Consequently, it was

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

NASA Astrophysics Data System (ADS)

Stone, B.

2003-12-01

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

Air Quality Criteria for Ozone and Related Photochemical Oxidants Volume I of III (Final Report, 1996)

EPA Science Inventory

The U.S. Environmental Protection Agency (EPA) promulgates the National Ambient Air Quality Standards (NAAQS) on the basis of scientific information contained in air quality criteria documents. The previous ozone (O3) criteria document, Air Quality Criteria for Ozone and Other Ph...

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

EPA Science Inventory

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

Ecological issues related to ozone: agricultural issues.

PubMed

Fuhrer, Jürg; Booker, Fitzgerald

2003-06-01

Research on the effects of ozone on agricultural crops and agro-ecosystems is needed for the development of regional emission reduction strategies, to underpin practical recommendations aiming to increase the sustainability of agricultural land management in a changing environment, and to secure food supply in regions with rapidly growing populations. Major limitations in current knowledge exist in several areas: (1) Modelling of ozone transfer and specifically stomatal ozone uptake under variable environmental conditions, using robust and well-validated dynamic models that can be linked to large-scale photochemical models lack coverage. (2) Processes involved in the initial reactions of ozone with extracellular and cellular components after entry through the stomata, and identification of key chemical species and their role in detoxification require additional study. (3) Scaling the effects from the level of individual cells to the whole-plant requires, for instance, a better understanding of the effects of ozone on carbon transport within the plant. (4) Implications of long-term ozone effects on community and whole-ecosystem level processes, with an emphasis on crop quality, element cycling and carbon sequestration, and biodiversity of pastures and rangelands require renewed efforts. The UNECE Convention on Long Range Trans-boundary Air Pollution shows, for example, that policy decisions may require the use of integrated assessment models. These models depend on quantitative exposure-response information to link quantitative effects at each level of organization to an effective ozone dose (i.e., the balance between the rate of ozone uptake by the foliage and the rate of ozone detoxification). In order to be effective in a policy, or technological context, results from future research must be funnelled into an appropriate knowledge transfer scheme. This requires data synthesis, up-scaling, and spatial aggregation. At the research level, interactions must be

Impact of Ozone Radiative Feedbacks on Global Weather Forecasting

NASA Astrophysics Data System (ADS)

Ivanova, I.; de Grandpré, J.; Rochon, Y. J.; Sitwell, M.

2017-12-01

ratio, air temperature and overhead column ozone) used for the calculation of the linearized photochemical production and loss of ozone. Furthermore the radiative budget in the tropopause region is strongly affected by water vapor cooling, which impact requires further evaluation for the use in chemically coupled operational NWP systems.

Airborne lidar mapping of vertical ozone distributions in support of the 1990 Clean Air Act Amendments

NASA Technical Reports Server (NTRS)

Uthe, Edward E.; Nielsen, Norman B.; Livingston, John M.

1992-01-01

The 1990 Clean Air Act Amendments mandated attainment of the ozone standard established by the U.S. Environmental Protection Agency. Improved photochemical models validated by experimental data are needed to develop strategies for reducing near surface ozone concentrations downwind of urban and industrial centers. For more than 10 years, lidar has been used on large aircraft to provide unique information on ozone distributions in the atmosphere. However, compact airborne lidar systems are needed for operation on small aircraft of the type typically used on regional air quality investigations to collect data with which to develop and validate air quality models. Data presented in this paper will consist of a comparison between airborne differential absorption lidar (DIAL) and airborne in-situ ozone measurements. Also discussed are future plans to improve the airborne ultraviolet-DIAL for ozone and other gas observations and addition of a Fourier Transform Infrared (FTIR) emission spectrometer to investigate the effects of other gas species on vertical ozone distribution.

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

NASA Astrophysics Data System (ADS)

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

2009-12-01

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

Transboundary Contributions To Surface Ozone In California's Central Valley

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

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.

Arctic chlorine monoxide observations during spring 1993 over Thule, Greenland, and implications for ozone depletion

NASA Technical Reports Server (NTRS)

Shindell, D. T.; Reeves, J. M.; Emmons, L. K.; De Zafra, R. L.

1994-01-01

We have determined the vertical distribution of chlorine monoxide (ClO), from measurements of pressure-broadened molecular-emission spectra made over Thule, Greenland, during the 1993 Arctic spring. The measurements show a weak lower stratospheric layer of chlorine monoxide inside the vortex in late February, which was, however, significantly greater in mixing ratio than that seen in observations we made in the spring of 1992. ClO was also observed in much smaller quantities in early to mid-March 1993 when Thule was outside the vortex. The amount of ClO within the vortex was severely reduced by the time it returned over Thule in late March. This reduction occurred several weeks earlier relative to the winter solstice than the decline of ClO inside the Antarctic vortex in 1993. The enhanced Arctic lower stratospheric layer seen in late February 1993 at a nearly equivalent photochemical period, and beyond. We have calculated daily ozone loss rates, due primarily to the dimer chlorine catalytic cycle, from both sets of measurements. The vertical integral of the Arctic daily percentage ozone loss when the largest ClO levels were present, at the end of February, is found to be approximately one quarter of that in the Antarctic at a photochemical period only 1 week later. The relative weakness of daily ozone depletion, combined with the early disappearance of ClO in the Arctic, suggests that hemispheric dilution by ozone-poor air from within the Arctic vortex is unlikely to be sufficient to explain the historically extreme loss of midlatitude northern hemisphere ozone which began in 1992 and persisted throughout 1993.

Ozone kinetics in low-pressure discharges

NASA Astrophysics Data System (ADS)

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

2012-10-01

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

Oxidation of N-nitrosodimethylamine (NDMA) precursors with ozone and chlorine dioxide: kinetics and effect on NDMA formation potential.

PubMed

Lee, Changha; Schmidt, Carsten; Yoon, Jeyong; von Gunten, Urs

2007-03-15

The oxidation of N-nitrosodimethylamine (NDMA) precursors chlorine dioxide (ClO2). Second-order rate constants for the reactions of model NDMA precursors (dimethylamine (DMA) and 7 tertiary amines) with ozone (kapp at pH 7 = 2.4 x 10(-1) to 2.3 x 10(9) M(-1) s(-1)), ClO2 (kapp at pH 7 = 6.7 x 10(-3) to 3.0 x 10(7) M(-1) s(-1)), and hydroxyl radical (*OH) (kapp at pH 7 = 6.2 x 10(7) to 1.4 x 10(10) M(-1) s(-1)) were determined, which showed that the selected NDMA precursors, with the exception of dimethylformamide (DMFA) can be completely transformed via their direct reaction with ozone. During ozonation, DMFA may be partially transformed through oxidation by the secondary oxidant *OH. ClO2 was also shown to effectively transform most of the precursors, with the exceptions of DMA and DMFA. In the second part of the study, the NDMA formation potentials (NDMA-FP) in synthetic and natural waters were measured with and without pre-oxidation with ozone and ClO2. A significant reduction in the NDMA-FPs was observed after complete transformation of the model NDMA precursors. Ozonation generally led to more effective reduction of the NDMA-FP than ClO2. For most of the precursors, the formation of DMA could account for the NDMA-FPs remaining after complete transformation of the model NDMA precursors. In contrast, dimethylethanolamine and dimethyldithiocarbamate yielded other NDMA precursors (not DMA) as their oxidation products. Pre-oxidation by ozone and ClO2 of several natural waters showed behavior similar to that of the oxidation of model NDMA precursors with a reduction of the NDMA-FP by 32-94% for various natural water sources.

Ozone precursors and ozone photochemistry over eastern North Pacific during the spring of 1984 based on the NASA GTE/CITE 1 airborne observations

NASA Technical Reports Server (NTRS)

Chameides, W. L.; Davis, D. D.; Gregory, G. L.; Sachse, G.; Torres, A. L.

1989-01-01

Simultaneous high-resolution measurements of O3, NO, CO, dew point temperature, and UV flux obtained during the NASA Global Tropospheric Experiment Chemical Instrumentation Test and Evaluation (GTE/CITE 1) spring 1984 airborne field exercise over the eastern North Pacific Ocean are analyzed. Mid-tropospheric CO, O3, and NO mixing ratios averaged about 120 parts per billion by volume (ppbv), 50 ppbv, and 10 parts per trillion by volume (pptv), respectively. Statistical analysis of the high-resolution data indicates the existence of two ozone sources, one related to the downward transport of ozone-rich air from the upper troposphere and stratosphere, and the other to the transport of ozone-rich air from the continents. Modeling calculations based on these average levels imply that, from the surface to about 8 km, photochemical reactions probably supplied a net sink of ozone to the region overlying the eastern North Pacific Ocean during the sampling period. However, because the NO levels measured during the flights were frequently at or near the detection limit of the instruments and because the results are very sensitive to the absolute NO levels and their temporal variability, the conclusion must be considered provisional.

Recent Changes in Tropospheric Ozone in the Tropics

NASA Technical Reports Server (NTRS)

Chandra, S.; Ziemke, J. R.; Einaudi, Franco (Technical Monitor)

2000-01-01

This paper presents a detailed characterization of tropical tropospheric column ozone variability on time scales varying from a few days to a solar cycle. The study is based on more than 20 years (1979 to the present) of tropospheric column ozone time series derived from the convective cloud differential (CCD) method using total ozone mapping spectrometer (TOMS) data. Results indicate three distinct regions in the tropics with distinctly three different zonal characteristics related to seasonal, interannual and solar variabilities. These three regions are the eastern Pacific, Atlantic, and western Pacific. Tropospheric column ozone in the Atlantic region peaks at about the same time (September-October) from 20 N to 20 S. The amplitude of the annual cycle, however, varies from about 3 to 6 Dobson unit (DU) from north to south of the equator. In comparison, the annual cycle in both the eastern and western Pacific is generally week and the phase varies from peak values in March and April in the northern hemisphere to September and October in the southern hemisphere. The interannual pattern in the three regions are also very different. The Atlantic region indicates a quasi biennial oscillation in the tropospheric column ozone which is out of phase with the stratospheric ozone. This is consistent with the photochemical control of this region caused by high pollution and high concentration of ozone producing precursors. The observed pattern, however, does not seem to be related to the interannual variability in ozone precursors related to biomass burning. Instead, it appears to be a manifestation of the UV modulation of upper tropospheric chemistry on a QBO time scale caused by stratospheric ozone. During El Nino events, there is anomalously low ozone in the eastern Pacific and high values in the western Pacific indicating the effects of convectively driven transport. The observed increase of 10-20 DU in tropospheric column ozone in the Indonesian region in the western

EMISSION OF OZONE IN THE VALE DO PARAÍBA REGION, IN SOUTHEASTERN BRAZIL, FOR THE YEAR 2007

NASA Astrophysics Data System (ADS)

Dos Santos Zepka, A.; Sales, A. B.; Alvalá, P. C.

2009-12-01

The city of São José dos Campos (São Paulo, Brazil) in recent years has shown strong growth and current increase in industrial economy, leading to a sharp urban development and consequent problems of air pollution. The ozone is a major greenhouse gas, present in the troposphere by photochemical reactions in natural emissions of anthropogenic and biogenic hydrocarbons such as volatile organic compounds and nitrogen oxides, which can come from lightning and soil. Due to the fact that this gas is considered the main pollutant responsible for poor air quality, the objective of this study was to characterize the behavior of the emission of ozone in the Vale do Paraíba region, in Southeastern Brazil, in association with meteorological parameters. Researches in this area are essential, because of the need for better knowledge on air quality at regional and global. The motivation for this study was based on the fact that the ozone near the surface can be considered a gas harmful to human and animal health, crops and forests as well of urban areas in general, besides being used as a major indicators of air quality by agencies of monitoring environment, such as the IPCC (Intergovernmental Panel on Climate Change), for example. This study is an initial analysis that will lead to a better understanding of chemical and physical processes that occur in the atmosphere of the city and region. Ozone and meteorological data were obtained from two locations in the city, known as INPE (23°12,04'S; 45°51,06'W) and UNIVAP (23°12,05'S; 45°57,02'W) during the year 2007. The ozone data were obtained every 15 minutes and converted in hourly and daily averages. In addition, were collected the maximum and minimum measure daily. The ozone showed similar behavior to temperature and irradiance for the period studied. In spring and summer there was an increase of ozone mixing ratio, which was produced photochemically during the increase of solar irradiance. Moreover, the periods of autumn

Model/data comparisons of ozone in the upper stratosphere and mesosphere

NASA Technical Reports Server (NTRS)

Siskind, David E.; Remsberg, Ellis E.; Eckman, Richard S.; Connor, Brian J.; Tsou, J. J.; Parrish, Alan

1994-01-01

We compare ground-based microwave observations of ozone in the upper stratosphere and mesosphere with daytime observations made from the SME (Solar Mesosphere Explorer) satellite, with nighttime data from the LIMS instrument, and with a diurnal photochemical model. The results suggest that the data are all in reasonable agreement and that the model-data discrepancy is much less than previously thought, particularly in the mesosphere. This appears to be due to the fact that the latest data are lower than earlier reports and the updated model predicts more ozone than older versions. The model and the data agree to within a factor of 1.5 at all altitudes and typically are within 20 percent.

The role of symmetry in the mass independent isotope effect in ozone

PubMed Central

Michalski, Greg; Bhattacharya, S. K.

2009-01-01

Understanding the internal distribution of “anomalous” isotope enrichments has important implications for validating theoretical postulates on the origin of these enrichments in molecules such as ozone and for understanding the transfer of these enrichments to other compounds in the atmosphere via mass transfer. Here, we present an approach, using the reaction NO2− + O3, for assessing the internal distribution of the Δ17O anomaly and the δ18O enrichment in ozone produced by electric discharge. The Δ17O results strongly support the symmetry mechanism for generating mass independent fractionations, and the δ18O results are consistent with published data. Positional Δ17O and δ18O enrichments in ozone can now be more effectively used in photochemical models that use mass balance oxygen atom transfer mechanisms to infer atmospheric oxidation chemistry. PMID:19307571

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.

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.

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...

Development of an instrument for direct ozone production rate measurements: measurement reliability and current limitations

NASA Astrophysics Data System (ADS)

Sklaveniti, Sofia; Locoge, Nadine; Stevens, Philip S.; Wood, Ezra; Kundu, Shuvashish; Dusanter, Sébastien

2018-02-01

Ground-level ozone (O3) is an important pollutant that affects both global climate change and regional air quality, with the latter linked to detrimental effects on both human health and ecosystems. Ozone is not directly emitted in the atmosphere but is formed from chemical reactions involving volatile organic compounds (VOCs), nitrogen oxides (NOx = NO + NO2) and sunlight. The photochemical nature of ozone makes the implementation of reduction strategies challenging and a good understanding of its formation chemistry is fundamental in order to develop efficient strategies of ozone reduction from mitigation measures of primary VOCs and NOx emissions. An instrument for direct measurements of ozone production rates (OPRs) was developed and deployed in the field as part of the IRRONIC (Indiana Radical, Reactivity and Ozone Production Intercomparison) field campaign. The OPR instrument is based on the principle of the previously published MOPS instrument (Measurement of Ozone Production Sensor) but using a different sampling design made of quartz flow tubes and a different Ox (O3 and NO2) conversion-detection scheme composed of an O3-to-NO2 conversion unit and a cavity attenuated phase shift spectroscopy (CAPS) NO2 monitor. Tests performed in the laboratory and in the field, together with model simulations of the radical chemistry occurring inside the flow tubes, were used to assess (i) the reliability of the measurement principle and (ii) potential biases associated with OPR measurements. This publication reports the first field measurements made using this instrument to illustrate its performance. The results showed that a photo-enhanced loss of ozone inside the sampling flow tubes disturbs the measurements. This issue needs to be solved to be able to perform accurate ambient measurements of ozone production rates with the instrument described in this study. However, an attempt was made to investigate the OPR sensitivity to NOx by adding NO inside the instrument

Impact of biogenic very short-lived bromine on the Antarctic ozone hole during the 21st century

NASA Astrophysics Data System (ADS)

Fernandez, Rafael Pedro; Kinnison, Douglas E.; Lamarque, Jean-Francois; Tilmes, Simone; Saiz-Lopez, Alfonso

2017-04-01

Active bromine released from the photochemical decomposition of biogenic very short-lived bromocarbons (VSLBr) enhances stratospheric ozone depletion. Based on a dual set of 1960-2100 coupled chemistry-climate simulations (i.e. with and without VSLBr), we show that the maximum Antarctic ozone hole depletion increases by up to 14% when natural VSLBr are considered, in better agreement with ozone observations. The impact of the additional 5 pptv VSLBr on Antarctic ozone is most evident in the periphery of the ozone hole, producing an expansion of the ozone hole area of 5 million km2, which is equivalent in magnitude to the recently estimated Antarctic ozone healing due to the implementation of the Montreal Protocol. We find that the inclusion of VSLBr in CAM-Chem does not introduce a significant delay of the modelled ozone return date to 1980 October levels, but instead affect the depth and duration of the simulated ozone hole. Our analysis further shows that total bromine-catalysed ozone destruction in the lower stratosphere surpasses that of chlorine by year 2070, and indicates that natural VSLBr chemistry would dominate Antarctic ozone seasonality before the end of the 21st century. This work suggests a large influence of biogenic bromine on the future Antarctic ozone layer.

On the variability of tropospheric ozone in the Tropical Eastern Pacific and its impact on the oxidizing capacity

NASA Astrophysics Data System (ADS)

Saiz-Lopez, A.; Gomez Martin, J.; Hay, T.; Mahajan, A.; Ordoñez, C.; Parrondo Sempere, M.; Gil, M. J.; Agama Reyes, M.; Paredes Mora, J.; Voemel, H.

2012-12-01

Observations of surface ozone, NOx and meteorological variables were made during two ground based field campaigns in the Eastern Pacific marine boundary layer (MBL). The first study was PIQUERO (Primera Investigación de la Química, Evolución y Reparto de Ozono), running from September 2000 to July 2001 in parallel to the Southern Hemisphere ADditional OZonesondes (SHADOZ) in the Galápagos Islands. The second study is the Climate and HAlogen Reactivity tropicaL EXperiment (CHARLEX), running from September 2010 to present. These long-term, high frequency, measurements enable a detailed description of the daily, monthly, seasonal and interannual variability of ozone and help to constrain the MBL and lower free troposphere (FT) ozone budget. In the Equatorial Eastern Pacific "cold season" (August - October), net ozone photochemical destruction of ~ 2 ppb day-1 occurs in the MBL (~30% due to halogens, and the rest to HOx). Ozone recovers by entrainment from aloft at night. The monthly baseline is set by the tropical instability waves (TIW), which also impact the ozone concentration in the lower FT. In the cold phase of the TIWs the MBL is stratified and, apart from higher surface ozone, it may also contain an upper drier layer with higher ozone between ~ 500 m and the main inversion at ~1 km. In the warm phase the buoyant MBL expands upwards (as much as 500 m) and poor ozone air reaches the FT. As the system shifts to the warm season (February- April), the TIWs stop and the sea becomes warmer, increasing evaporation and reducing ozone. The inversion is pushed upwards and finally disappears or becomes very weak. Surface ozone is so low that even at the low background NOx levels observed ozone production balances photochemical destruction, so the daily profile is flat (observed local effects in the populated areas of Galapagos are discussed). In February Galapagos is almost in the doldrums because the Inter-Tropical Convergence Zone (ITCZ) shifts south. In this

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

PubMed

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

2009-09-15

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

Photochemical Dimerization of Dibenzylideneacetone: A Convenient Exercise in [2+2] Cycloaddition Using Chemical Ionization Mass Spectrometry

ERIC Educational Resources Information Center

Rao, G. Nageswara; Janardhana, Chelli; Ramanathan, V.; Rajesh, T.; Kumar, P. Harish

2006-01-01

Chemical reactions induced by light have been utilized for synthesizing highly strained, thermodynamically unstable compounds, which are inaccessible through non-photochemical methods. Photochemical cycloaddition reactions, especially those leading to the formation of four-membered rings, constitute a convenient route to compounds that are…

Stratospheric Ozone Loss Over the US in Summer: Recent Advances in Observations of Temperatures, Convective Injection of Condensed Phase Water, and Analyses of Volcanic Injections That are Used to Inform Model Calculations of Catalytic Mechanisms that Control the Response of O3.

NASA Astrophysics Data System (ADS)

Anderson, J. G.

2016-12-01

In the context of changes to the structure of the Earth's climate, consequences to stratospheric ozone over the US in summer are considered. Key advances in observations directly related to the catalytic loss of ozone in the lower stratosphere include: Analysis of high resolution temperature observations over the central US in July and August from both SEAC4RS in situ observations and radio occultation (RO) observations, Inclusion of gravity wave observations from both SEAC4RS and RO measurements, Climatology of NEXRAD weather radar mapping of the 3D convective injection of condensed phase water over the central US in summer, Analysis of the impact on ozone in the lower stratosphere over the US in summer using the AER 2D model calculations of the key rate limiting radicals and rate limiting catalytic loss rates as a function of water vapor, temperature and sulfate loading in the lower stratosphere, Analysis of the impact on ozone in summer over the US under conditions of volcanic injection, overt sulfate addition for solar radiation management, and/or convective injection of water vapor, Emphasis in the analysis is placed specifically on the geographic region over the Great Plains of the US in summer because of the confluence of temperatures and water vapor concentrations that initiate the heterogeneous catalytic conversion of inorganic chlorine, primarily HCl and ClONO2, to free radical form, ClO. The ClO radical in turn engages gas phase catalytic cycles that remove ozone via the photochemical reaction mechanisms virtually identical to the catalytic photochemical processes that remove ozone over the Arctic each year in late spring. In situ observations, in the lower stratosphere of the Arctic, of the principal reaction networks that establish the relationship between observed ozone loss and the threshold in temperature, water vapor and sulfate loading is used to establish the photochemical coordinate system required to analyze ozone loss in the lower stratosphere

Photochemical Approaches to Complex Chemotypes: Applications in Natural Product Synthesis

PubMed Central

2016-01-01

The use of photochemical transformations is a powerful strategy that allows for the formation of a high degree of molecular complexity from relatively simple building blocks in a single step. A central feature of all light-promoted transformations is the involvement of electronically excited states, generated upon absorption of photons. This produces transient reactive intermediates and significantly alters the reactivity of a chemical compound. The input of energy provided by light thus offers a means to produce strained and unique target compounds that cannot be assembled using thermal protocols. This review aims at highlighting photochemical transformations as a tool for rapidly accessing structurally and stereochemically diverse scaffolds. Synthetic designs based on photochemical transformations have the potential to afford complex polycyclic carbon skeletons with impressive efficiency, which are of high value in total synthesis. PMID:27120289

Photochemical Approaches to Complex Chemotypes: Applications in Natural Product Synthesis.

PubMed

Kärkäs, Markus D; Porco, John A; Stephenson, Corey R J

2016-09-14

The use of photochemical transformations is a powerful strategy that allows for the formation of a high degree of molecular complexity from relatively simple building blocks in a single step. A central feature of all light-promoted transformations is the involvement of electronically excited states, generated upon absorption of photons. This produces transient reactive intermediates and significantly alters the reactivity of a chemical compound. The input of energy provided by light thus offers a means to produce strained and unique target compounds that cannot be assembled using thermal protocols. This review aims at highlighting photochemical transformations as a tool for rapidly accessing structurally and stereochemically diverse scaffolds. Synthetic designs based on photochemical transformations have the potential to afford complex polycyclic carbon skeletons with impressive efficiency, which are of high value in total synthesis.

Passive ozone network of Dallas: a modeling opportunity with community involvement. 2.

PubMed

Sather, M E; Varns, J L; Mulik, J D; Glen, G; Smith, L; Stallings, C

2001-11-15

Attaining the current lower tropospheric U.S. ozone standards continues to be a difficult task for many areas in the U.S. Concentrations of ozone above the standards negatively affects human health, agricultural crops, forests, and other ecosystem elements. This paper describes year two (1999) of a regional networking of passive and continuous ozone monitoring sites in the Dallas-Fort Worth (DFW) Metroplex region. The objectives of the second year of study were to (1) validate conclusions of the 1998 Passive Ozone Network of Dallas (POND) I study, (2) define the value of taking 12-h diurnal samples in addition to 24-h samples, and (3) add to the scientific knowledge base of rural/urban ozone comparison studies. Results of the POND II (1999) study demonstrated that ozone concentrations exceeding the new 8-h ozone standard could be recorded at least 130 km, or 80 miles, from the DFW Metroplex core in more rural areas. In addition, results of the POND II study indicated that ozone concentrations exceeding the 8-h standard probably occurred in areas recording a 12-h daytime ozone concentration above 60 parts per billion (ppb). The 12-h passive ozone data from POND II also suggests the relative magnitude of anthropogenic pollution influence could be assessed for rural passive ozone sites. The data from the POND II study provide modelers a rich database for future photochemical subgrid development for the DFW ozone nonattainment area. Indeed, the POND database provides a great amount of additional ozone ambient data covering 26 8-h and 13 1-h ozone standard exceedance days over an approximate 25000 km2 region. These data should help decrease uncertainties derived from future DFW ozone model exercises.

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

NASA Technical Reports Server (NTRS)

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

2017-01-01

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

Ozone production and its sensitivity to NOx and VOCs: results from the DISCOVER-AQ field experiment, Houston 2013

NASA Astrophysics Data System (ADS)

Mazzuca, Gina M.; Ren, Xinrong; Loughner, Christopher P.; Estes, Mark; Crawford, James H.; Pickering, Kenneth E.; Weinheimer, Andrew J.; Dickerson, Russell R.

2016-11-01

An observation-constrained box model based on the Carbon Bond mechanism, version 5 (CB05), was used to study photochemical processes along the NASA P-3B flight track and spirals over eight surface sites during the September 2013 Houston, Texas deployment of the NASA Deriving Information on Surface Conditions from COlumn and VERtically Resolved Observations Relevant to Air Quality (DISCOVER-AQ) campaign. Data from this campaign provided an opportunity to examine and improve our understanding of atmospheric photochemical oxidation processes related to the formation of secondary air pollutants such as ozone (O3). O3 production and its sensitivity to NOx and volatile organic compounds (VOCs) were calculated at different locations and times of day. Ozone production efficiency (OPE), defined as the ratio of the ozone production rate to the NOx oxidation rate, was calculated using the observations and the simulation results of the box and Community Multiscale Air Quality (CMAQ) models. Correlations of these results with other parameters, such as radical sources and NOx mixing ratio, were also evaluated. It was generally found that O3 production tends to be more VOC-sensitive in the morning along with high ozone production rates, suggesting that control of VOCs may be an effective way to control O3 in Houston. In the afternoon, O3 production was found to be mainly NOx-sensitive with some exceptions. O3 production near major emissions sources such as Deer Park was mostly VOC-sensitive for the entire day, other urban areas near Moody Tower and Channelview were VOC-sensitive or in the transition regime, and areas farther from downtown Houston such as Smith Point and Conroe were mostly NOx-sensitive for the entire day. It was also found that the control of NOx emissions has reduced O3 concentrations over Houston but has led to larger OPE values. The results from this work strengthen our understanding of O3 production; they indicate that controlling NOx emissions will provide

Gas-phase chemiluminescent reactions of ozone with monoterpenes

NASA Astrophysics Data System (ADS)

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

1983-08-01

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

Extensive halogen-mediated ozone destruction over the tropical Atlantic Ocean.

PubMed

Read, Katie A; Mahajan, Anoop S; Carpenter, Lucy J; Evans, Mathew J; Faria, Bruno V E; Heard, Dwayne E; Hopkins, James R; Lee, James D; Moller, Sarah J; Lewis, Alastair C; Mendes, Luis; McQuaid, James B; Oetjen, Hilke; Saiz-Lopez, Alfonso; Pilling, Michael J; Plane, John M C

2008-06-26

Increasing tropospheric ozone levels over the past 150 years have led to a significant climate perturbation; the prediction of future trends in tropospheric ozone will require a full understanding of both its precursor emissions and its destruction processes. A large proportion of tropospheric ozone loss occurs in the tropical marine boundary layer and is thought to be driven primarily by high ozone photolysis rates in the presence of high concentrations of water vapour. A further reduction in the tropospheric ozone burden through bromine and iodine emitted from open-ocean marine sources has been postulated by numerical models, but thus far has not been verified by observations. Here we report eight months of spectroscopic measurements at the Cape Verde Observatory indicative of the ubiquitous daytime presence of bromine monoxide and iodine monoxide in the tropical marine boundary layer. A year-round data set of co-located in situ surface trace gas measurements made in conjunction with low-level aircraft observations shows that the mean daily observed ozone loss is approximately 50 per cent greater than that simulated by a global chemistry model using a classical photochemistry scheme that excludes halogen chemistry. We perform box model calculations that indicate that the observed halogen concentrations induce the extra ozone loss required for the models to match observations. Our results show that halogen chemistry has a significant and extensive influence on photochemical ozone loss in the tropical Atlantic Ocean boundary layer. The omission of halogen sources and their chemistry in atmospheric models may lead to significant errors in calculations of global ozone budgets, tropospheric oxidizing capacity and methane oxidation rates, both historically and in the future.

Mapping of Ozone on Mars at Infrared Wavelengths Using Crires at VLT

NASA Astrophysics Data System (ADS)

Radeva, Y. L.; Mumma, M. J.; Villanueva, G.; Novak, R.; Hartogh, P.; Encrenaz, T.; Kaufl, H.; Smette, A.

2010-12-01

We present spatially resolved maps of ozone and water on Mars, acquired on 21 August 2009 using the ultra-high resolution infrared spectrometer CRIRES at ESO’s VLT (Paranal, Chile). On Mars, the season was mid-summer in the South (Ls = 325) and the latitudinal resolution was 10 degrees FWHM at disk center. Ozone is produced by recombination of photochemically produced O and O2. It is destroyed by UV photolysis (with O2 (a1Dg) as a principal product) but also by reaction with odd hydrogen species (especially, H - a product of H2O vapor photolysis). Thus, simultaneous measurements of water and ozone can test this relationship. We quantified ozone using spectral lines (near 1.27 mm) of O2 (a1Dg). The emission from O2 (a1Dg) serves as a tracer for O3 above 20 km, since at lower altitudes collisions with CO2 quench the excited O2 (a1Dg) molecules. We confirmed the vertical location of the O2 (a1Dg) emission by extracting rotational temperatures from line-by-line ratios, and comparing them with standard vertical temperature profiles for this season and location(s). On the same night, we also obtained 2-D (lat-long) maps of Martian water from multiple H2O lines detected in the 3.3 mm region. We compare our retrieved distributions for ozone (latitude and altitude) with predictions of Lefevre et al. [I] based on their comprehensive 3-D circulation and photochemical model for the Martian atmosphere. Acknowledgements: This work was funded by NASA’s R&A Programs in Astrobiology (344-53-51), Planetary Astronomy (344-32-51-96), and Planetary Atmospheres (NNX09AB65G). We gratefully acknowledge the Director and staff of the European Southern Observatory, for supporting these observations. References: [I] Lefevre et al. (2004), J. of Geophys. Res. 109, E07004

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).

Kinetics of p-hydroxybenzoic acid photodecomposition and ozonation in a batch reactor.

PubMed

Benitez, F J; Beltran-Heredia, J; Peres, J A; Dominguez, J R

2000-04-03

The decomposition of p-hydroxybenzoic acid, an important pollutant present in the wastewaters of the olive oil industry, has been carried out by a direct photolysis provided by a polychromatic UV radiation source, and by ozone. In both processes, the conversions obtained as a function of the operating variables (temperature, pH and ozone partial pressure in the ozonation process) are reported. In order to evaluate the radiation flow rate absorbed by the solutions in the photochemical process, the Line Source Spherical Emission Model is used. The application of this model to the experimental results provides the determination of the reaction quantum yields which values ranged between 8.62 and 81.43 l/einstein. In the ozonation process, the film theory allows to establish that the absorption process takes place in the fast and pseudo-first-order regime and the reaction is overall second-order, first-order with respect to both reactants, ozone and p-hydroxybenzoic acid. The rate constants are evaluated and vary between 0.18x10(5) and 29.9x10(5) l/mol s depending on the temperature and pH.

Ozone and nitrogen oxides in surface air in Russia: TROICA experiments.

NASA Astrophysics Data System (ADS)

Pankratova, N.; Elansky, N.; Belikov, I.; Shumskiy, R.

2009-04-01

The results of measurements of surface ozone and nitrogen oxides concentrations over the continental regions of Russia are discussed. The measurements were done during 10 TROICA experiments (Transcontinental Observations Into the Chemistry of the Atmosphere). The TROICA experiment started in 1995. By the present moment ten expeditions along the Trans-Siberian railroad from Moscow to Vladivostok (around 9300 km) are carried out. We separate data sets into unpolluted and polluted areas to study temporal and spatial features. Moreover we analyzed cities (more then 100 cities). About 50% of all data corresponds to unpolluted conditions. The data collected are used in an analysis of the physical and chemical processes occurring over continental Russia. In this work the estimations of seasonal and daily ozone and NOx distribution were made. The seasonal distribution of ozone for TROICA experiments concentration considerably differs from ozone distribution at Mace Head (Ireland) and Hohenpeissenberg (Germany) stations and well agrees with the ozone distribution at Zotino (Russia, East Siberia). The same concerns also a daily variability. The ozone concentration gradient is presented. Ozone concentration gradually increases in the eastward direction. Its result of the air transport from polluted regions of Europe and ozone depletions, oxidations of CH4 in Siberia, forest fires in Siberia and around Baikal Lake, regional transport of burning products from Northern China. Significant factor of ozone increasing is stratospheric-tropospheric exchange. It appears in TROICA-3 experiment. During several hours ozone concentration was more then 60 ppbv. The areas of photochemical ozone generation in polluted air are also detected. We estimate anthropogenic and natural factors, which are responsible for sharp ozone concentration increasing. Acknowledgments. The work was supported by International Science and Technology Center (ISTC) under contract No. 2770 and by Russian Basic

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

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

NASA Astrophysics Data System (ADS)

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

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

Photochemical and Meteorological Conditions during the MCMA-2003 Field Measurement Campaign

NASA Astrophysics Data System (ADS)

Molina, L. T.; de Foy, B.; Molina, M. J.; Caetano, E.; Magana, V.; Zitacuaro, A.; Ramos, R.; Retama, A.; Cardenas, B.; Martinez, A.; Reyes, R.; Sosa, G.

2004-12-01

MCMA-2003 was a major field campaign of the atmospheric chemistry taking place in the Mexico City Metropolitan Area (MCMA) in April of 2003. April is in the transition from the dry to the wet season with predominant westerly synoptic winds and intense radiation heating leading to strong thermal mountain flows. Three basic types of meteorological conditions were identified: "Cold Surge", "O3-North" and "O3-South", corresponding to cloudy days associated with "Norte" events, peak ozone in the north of the city, and peak ozone in the south. The circulation associated with these is described both at the regional and local level, as high concentrations of both ozone and primary pollutants for each category make them equally relevant to chemical analyses of the basin. Modified wind roses (time roses) based on time of day categories instead of wind speed categories are used to identify shifts in wind directions associated with slope flows inside the basin and sea breeze flows outside of it. The photochemical episodes are compared with historical data from the RAMA monitoring network to assess the representativeness of MCMA-2003. The analysis of the episodes during the campaign shows the existence of one-day episodes where no build-up of pollutants is needed in order to attain very highly localized concentrations but where multi-day events lead to peaks covering a much larger geographic area.

Simulated changes in biogenic VOC emissions and ozone formation from habitat expansion of Acer Rubrum (red maple)

DOE PAGES

Drewniak, Beth A.; Snyder, Peter K.; Steiner, Allison L.; ...

2014-01-17

A new vegetation trend is emerging in northeastern forests of the United States, characterized by an expansion of red maple at the expense of oak. This has changed emissions of biogenic volatile organic compounds (BVOCs), primarily isoprene and monoterpenes. Oaks strongly emit isoprene while red maple emits a negligible amount. This species shift may impact nearby urban centers because the interaction of isoprene with anthropogenic nitrogen oxides can lead to tropospheric ozone formation and monoterpenes can lead to the formation of particulate matter. Here in this study the Global Biosphere Emissions and Interactions System was used to estimate the spatialmore » changes in BVOC emission fluxes resulting from a shift in forest composition between oak and maple. A 70% reduction in isoprene emissions occurred when oak was replaced with maple. Ozone simulations with a chemical box model at two rural and two urban sites showed modest reductions in ozone concentrations of up to 5–6 ppb resulting from a transition from oak to red maple, thus suggesting that the observed change in forest composition may benefit urban air quality. This study illustrates the importance of monitoring and representing changes in forest composition and the impacts to human health indirectly through changes in BVOCs.« less

Simulated changes in biogenic VOC emissions and ozone formation from habitat expansion of Acer Rubrum (red maple)

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

Drewniak, Beth A.; Snyder, Peter K.; Steiner, Allison L.

A new vegetation trend is emerging in northeastern forests of the United States, characterized by an expansion of red maple at the expense of oak. This has changed emissions of biogenic volatile organic compounds (BVOCs), primarily isoprene and monoterpenes. Oaks strongly emit isoprene while red maple emits a negligible amount. This species shift may impact nearby urban centers because the interaction of isoprene with anthropogenic nitrogen oxides can lead to tropospheric ozone formation and monoterpenes can lead to the formation of particulate matter. Here in this study the Global Biosphere Emissions and Interactions System was used to estimate the spatialmore » changes in BVOC emission fluxes resulting from a shift in forest composition between oak and maple. A 70% reduction in isoprene emissions occurred when oak was replaced with maple. Ozone simulations with a chemical box model at two rural and two urban sites showed modest reductions in ozone concentrations of up to 5–6 ppb resulting from a transition from oak to red maple, thus suggesting that the observed change in forest composition may benefit urban air quality. This study illustrates the importance of monitoring and representing changes in forest composition and the impacts to human health indirectly through changes in BVOCs.« less

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.

Ozone's Threat Hits Back Mexico City

NASA Astrophysics Data System (ADS)

Velasco, E.; Retama, A.; Guzman, D.

2016-12-01

Last March the Mexican authorities activated after 13 years the environmental alarm when ozone (O3) reached 210 ppb. The emergency measures created confusion among the public, who had lost memory of previous air quality crisis. Despite Mexico City has experienced a significant progress towards achieving cleaner air during the last 20 years, a recent relaxation in traffic regulations and meteorology favorable for photochemical activity triggered this new episode. All criteria pollutants of primary origin have been controlled and are in compliance with the Mexican Air Quality Standards. However, O3 and fine particles still exceed the standard threshold concentrations. For instance, 49-64% of the days have exceeded the 1-hour O3 standard of 95 ppb during the last 5 years. The current control policies, which responded to the integration of air quality information by authorities and scientists, have apparently started to lose effectiveness. Although precursor gases, such as alkanes and aromatics have shown an important decrease, reactive olefins have gained importance. The increase of motor-vehicles in recent years seems to fuel again the atmosphere's reactivity. This paper analyses the effectiveness of the emergency measures during the crisis based on the knowledge obtained from previous large field studies and the comprehensive data collected by the local air quality monitoring network. It is 10 years from MILAGRO, the last interdisciplinary study that examined the air pollution of the most populous city in North America. We call for a new collaborative research initiative based on a major field measurement campaign with the target of revealing new insights into the meteorology, emission of primary pollutants and precursor gases, photochemical production and formation of secondary particles in the atmosphere of Mexico City to improve its air quality, as well as of similar cities in the developing world.

A Global Climatology of Tropospheric and Stratospheric Ozone Derived from Aura OMI and MLS Measurements

NASA Technical Reports Server (NTRS)

Ziemke, J.R.; Chandra, S.; Labow, G.; Bhartia, P. K.; Froidevaux, L.; Witte, J. C.

2011-01-01

A global climatology of tropospheric and stratospheric column ozone is derived by combining six years of Aura Ozone Monitoring Instrument (OMI) and Microwave Limb Sounder (MLS) ozone measurements for the period October 2004 through December 2010. The OMI/MLS tropospheric ozone climatology exhibits large temporal and spatial variability which includes ozone accumulation zones in the tropical south Atlantic year-round and in the subtropical Mediterranean! Asia region in summer months. High levels of tropospheric ozone in the northern hemisphere also persist in mid-latitudes over the eastern North American and Asian continents extending eastward over the Pacific Ocean. For stratospheric ozone climatology from MLS, largest ozone abundance lies in the northern hemisphere in the latitude range 70degN-80degN in February-April and in the southern hemisphere around 40degS-50degS during months August-October. The largest stratospheric ozone abundances in the northern hemisphere lie over North America and eastern Asia extending eastward across the Pacific Ocean and in the southern hemisphere south of Australia extending eastward across the dateline. With the advent of many newly developing 3D chemistry and transport models it is advantageous to have such a dataset for evaluating the performance of the models in relation to dynamical and photochemical processes controlling the ozone distributions in the troposphere and stratosphere.

Issues and progress in determining background ozone and particle concentrations

NASA Astrophysics Data System (ADS)

Pinto, J. P.

2011-12-01

Exposure to ambient ozone is associated with a variety of health outcomes ranging from mild breathing discomfort to mortality. For the purpose of health risk and policy assessments EPA evaluates the anthropogenic increase in ozone above background concentrations and has defined the North American (NA) background concentration of O3 as that which would occur in the U.S. in the absence of anthropogenic emissions of precursors in the U.S., Canada, and Mexico. Monthly average NA background ozone has been used to evaluate health risks, but EPA and state air quality managers must also estimate day specific ozone background levels for high ozone episodes as part of urban scale photochemical modeling efforts to support ozone regulatory programs. The background concentration of O3 is of more concern than other air pollutants because it typically represents a much larger fraction of observed O3 than do the backgrounds of other criteria pollutants (particulate matter (PM), CO, NO2, SO2). NA background cannot be determined directly from ambient monitoring data because of the influence of NA precursor emissions on formation of ozone within NA. Instead, estimates of NA background O3 have been based on GEOS-Chem using simulations in which NA anthropogenic precursor emissions are zeroed out. Thus, modeled NA background O3 includes contributions from natural sources of precursors (including CH4, NMVOCs, NOx, and CO) everywhere in the world, anthropogenic sources of precursors outside of NA, and downward transport of O3 from the stratosphere. Although monitoring data cannot determine NA background directly, measurements by satellites, aircraft, ozonesondes and surface monitors have proved to be highly useful for identifying sources of background O3 and for evaluating the performance of the GEOS-Chem model. Model simulated NA background concentrations are strong functions of location and season with large inter-day variability and with values increasing with elevation and higher in

Influence of isentropic transport on seasonal ozone variations in the lower stratosphere and subtropical upper troposphere

NASA Technical Reports Server (NTRS)

Jing, P.; Cunnold, D. M.; Yang, E.-S.; Wang, H.-J.

2005-01-01

The isentropic cross-tropopause ozone transport has been estimated in both hemispheres in 1999 based on the potential vorticity mapping of Stratospheric Aerosol and Gas Experiment 11 ozone measurements and contour advection calculations using the NASA Goddard Space Flight Center Global and Modeling Assimilation Office analysis. The estimated net isentropic stratosphere-to-troposphere ozone flux is approx.118 +/- 61 x 10(exp9)kg/yr globally within the layer between 330 and 370 K in 1999; 60% of it is found in the Northern Hemisphere, and 40% is found in the Southern Hemisphere. The monthly average ozone fluxes are strongest in summer and weakest in winter in both hemispheres. The seasonal variations of ozone in the lower stratosphere (LS) and upper troposphere (UT) have been analyzed using ozonesonde observations from ozonesonde stations in the extratropics and subtropics, respectively. It is shown that observed ozone levels increase in the UT over subtropical ozonesonde stations and decrease in the LS over extratropical stations in late spring/early summer and that the ozone increases in the summertime subtropical UT are unlikely to be explained by photochemical ozone production and diabatic transport alone. We conclude that isentropic transport is a significant contributor to ozone levels in the subtropical upper troposphere, especially in summer.

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

PubMed

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

2000-06-01

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

Characterizing ozone pollution in a petrochemical industrial area in Beijing, China: a case study using a chemical reaction model.

PubMed

Wei, Wei; Lv, Zhaofeng; Cheng, Shuiyuan; Wang, Lili; Ji, Dongsheng; Zhou, Ying; Han, Lihui; Wang, Litao

2015-06-01

This study selected a petrochemical industrial complex in Beijing, China, to understand the characteristics of surface ozone (O3) in this industrial area through the on-site measurement campaign during the July-August of 2010 and 2011, and to reveal the response of local O3 to its precursors' emissions through the NCAR-Master Mechanism model (NCAR-MM) simulation. Measurement results showed that the O3 concentration in this industrial area was significantly higher, with the mean daily average of 124.6 μg/m(3) and mean daily maximum of 236.8 μg/m(3), which are, respectively, 90.9 and 50.6 % higher than those in Beijing urban area. Moreover, the diurnal O3 peak generally started up early in 11:00-12:00 and usually remained for 5-6 h, greatly different with the normal diurnal pattern of urban O3. Then, we used NCAR-MM to simulate the average diurnal variation of photochemical O3 in sunny days of August 2010 in both industrial and urban areas. A good agreement in O3 diurnal variation pattern and in O3 relative level was obtained for both areas. For example of O3 daily maximum, the calculated value in the industrial area was about 51 % higher than in the urban area, while measured value in the industrial area was approximately 60 % higher than in the urban area. Finally, the sensitivity analysis of photochemical O3 to its precursors was conducted based on a set of VOCs/NOx emissions cases. Simulation results implied that in the industrial area, the response of O3 to VOCs was negative and to NOx was positive under the current conditions, with the sensitivity coefficients of -0.16~-0.43 and +0.04~+0.06, respectively. By contrast, the urban area was within the VOCs-limitation regime, where ozone enhancement in response to increasing VOCs emissions and to decreasing NOx emission. So, we think that the VOCs emissions control for this petrochemical industrial complex will increase the potential risk of local ozone pollution aggravation, but will be helpful to inhibit the

Simulation of summer ozone episodes in Southeast Louisiana during 2006-2015

NASA Astrophysics Data System (ADS)

Guo, H.; Zhang, H.

2017-12-01

Southeast Louisiana experiences high ozone (O3) events due to immense emissions from industrial and urban sources and unique meteorology conditions of high temperatures, intensive solar radiation and land-sea breeze circulation. The Community Multi-scale Air Quality (CMAQ) model with modified photochemical mechanism is used to investigate the contributions of regional transport to ozone (O3) and its precursors to Southeast Louisiana in summer months from 2006 to 2015. The meteorological and CMAQ model performance are validated. Spatial and temporal variations of O3 are investigated during summer episodes in 10 years. Contributions of different source types and regions to 1 hour O3 are also quantified. Changes in the contributions of different source types and regions are also obtained to help design intelligent control measures.

Highly sensitive and simple SERS substrate based on photochemically generated carbon nanotubes-gold nanorods hybrids.

PubMed

Caires, A J; Vaz, R P; Fantini, C; Ladeira, L O

2015-10-01

We report a simple and easy formation of hybrids between multi-wall carbon nanotubes and gold nanorods by one-pot in situ photochemical synthesis. Measurements of surface-enhanced Raman scattering (SERS) through the effect "coffee ring" in visible and near infrared (NIR) show high sensitivity with detection of nanomolar concentrations of aromatic dyes. The formation of nanocomposites between carbon nanotubes and gold nanorods without chemical binders simplifies the preparation. Photochemical synthesis is an advance over the techniques previously published. Copyright © 2015 Elsevier Inc. All rights reserved.

The use of satellite data to determine the distribution of ozone in the troposphere