Nitrogen Oxides: Vehicle Emissions and Atmospheric Chemistry

2012 ◽  
pp. 101-113 ◽  
Author(s):  
Timothy J. Wallington ◽  
John R. Barker ◽  
Lam Nguyen
Keyword(s):  
Nitrogen Oxides ◽  
Atmospheric Chemistry ◽  
Vehicle Emissions

scholarly journals Intrusion, retention, and snowpack chemical effects from exhaust emissions at Concordia Station, Antarctica

2018 ◽  
Author(s):  
Detlev Helmig ◽  
Daniel Liptzin ◽  
Jacques Hueber ◽  
Joel Savarino
Keyword(s):  
Nitrogen Oxides ◽  
Atmospheric Chemistry ◽  
Power Grid ◽  
Photochemical Reactions ◽  
Particulate Emissions ◽  
Surface Sampling ◽  
Surface Exchange ◽  
Exhaust Plumes ◽  
Clean Air ◽  
Main Station

Abstract. Continuous measurements of reactive gases in the snowpack and above the snowpack surface were conducted at Concordia Station (Dome C), Antarctica, from December 2012–January 2014. Measured species included ozone, nitrogen oxides, gaseous elemental mercury, and formaldehyde, for study of photochemical reactions, surface exchange, and the seasonal cycles and atmospheric chemistry of these gases. The experiment was installed ~ 1 km from the main station infrastructure inside the station clean air sector and within the station electrical power grid boundary. Air was sampled continuously from three inlets on a 10 m meteorological tower, as well as from two above and four below the surface sampling inlets from within the snowpack. Despite being in the clean air sector, over the course of the 1.2-year study, we observed on the order of 15 occasions when exhaust plumes from the camp, most notably from the power generation system, were transported to the study site. Highly elevated levels of nitrogen oxides (up to 1000 x background) and lowered ozone (down to ~ 50 %), most likely from titration with nitric oxide, were measured in the exhaust plumes. Within 5–15 minutes from observing elevated pollutant levels above the snow, rapidly increasing and long-lasting concentration enhancements were measured in snowpack air. While pollution events typically lasted only a few minutes to an hour above the snow surface, elevated nitrogen oxides levels were observed in the snowpack lasting from a few days to one week. These observations add important new insight to the discussion of if and how snow-photochemical experiments within reach of the power grid of polar research sites are possibly compromised by the snowpack being chemically influenced (contaminated) by gaseous and particulate emissions from the research camp activities. This question is critical for evaluating if snowpack trace chemical measurements from within the camp boundaries are representative for the vast polar ice sheets.

Major influence of BrO on the NOx and nitrate budgets in the Arctic spring, inferred from Δ17O(NO3 - ) measurements during ozone depletion events

2007 ◽  
Vol 4 (4) ◽  
pp. 238 ◽  
Author(s):  
S. Morin ◽  
J. Savarino ◽  
S. Bekki ◽  
A. Cavender ◽  
P. B. Shepson ◽  
...  
Keyword(s):  
Nitrogen Oxides ◽  
Isotopic Composition ◽  
Atmospheric Chemistry ◽  
Ozone Depletion ◽  
Lower Atmosphere ◽  
The Arctic ◽  
Major Influence ◽  
Peroxy Radicals ◽  
Bromine Oxide ◽  
Atmospheric Nitrate

Environmental context. Ozone depletion events (ODEs) in the Arctic lower atmosphere drive profound changes in the chemistry of nitrogen oxides (NOx) because of the presence of bromine oxide (BrO). These are investigated using the isotopic composition of atmospheric nitrate (NO3–), which is a ubiquitous species formed through the oxidation of nitrogen oxides. Since BrO is speculated to play a key role in the atmospheric chemistry of marine regions and in the free troposphere, our studies contribute to the improvement of the scientific knowledge on this new topic in atmospheric chemistry. Abstract. The triple oxygen isotopic composition of atmospheric inorganic nitrate was measured in samples collected in the Arctic in springtime at Alert, Nunavut and Barrow, Alaska. The isotope anomaly of nitrate (Δ17O = δ17O–0.52δ18O) was used to probe the influence of ozone (O3), bromine oxide (BrO), and peroxy radicals (RO2) in the oxidation of NO to NO2, and to identify the dominant pathway that leads to the production of atmospheric nitrate. Isotopic measurements confirm that the hydrolysis of bromine nitrate (BrONO2) is a major source of nitrate in the context of ozone depletion events (ODEs), when brominated compounds primarily originating from sea salt catalytically destroy boundary layer ozone. They also show a case when BrO is the main oxidant of NO into NO2.

scholarly journals Atmospheric nitrogen oxides (NO and NO<sub>2</sub>) at Dome C, East Antarctica, during the OPALE campaign

2015 ◽  
Vol 15 (14) ◽  
pp. 7859-7875 ◽  
Author(s):  
M. M. Frey ◽  
H. K. Roscoe ◽  
A. Kukui ◽  
J. Savarino ◽  
J. L. France ◽  
...  
Keyword(s):  
Nitrogen Oxides ◽  
Atmospheric Chemistry ◽  
Ambient Air ◽  
Skin Layer ◽  
East Antarctica ◽  
Atmospheric Nitrogen ◽  
Bromine Oxide ◽  
Diurnal Cycles ◽  
Mixing Ratios ◽  
Air Chemistry

Abstract. Mixing ratios of the atmospheric nitrogen oxides NO and NO2 were measured as part of the OPALE (Oxidant Production in Antarctic Lands &amp; Export) campaign at Dome C, East Antarctica (75.1° S, 123.3° E, 3233 m), during December 2011 to January 2012. Profiles of NOx mixing ratios of the lower 100 m of the atmosphere confirm that, in contrast to the South Pole, air chemistry at Dome C is strongly influenced by large diurnal cycles in solar irradiance and a sudden collapse of the atmospheric boundary layer in the early evening. Depth profiles of mixing ratios in firn air suggest that the upper snowpack at Dome C holds a significant reservoir of photolytically produced NO2 and is a sink of gas-phase ozone (O3). First-time observations of bromine oxide (BrO) at Dome C show that mixing ratios of BrO near the ground are low, certainly less than 5 pptv, with higher levels in the free troposphere. Assuming steady state, observed mixing ratios of BrO and RO2 radicals are too low to explain the large NO2 : NO ratios found in ambient air, possibly indicating the existence of an unknown process contributing to the atmospheric chemistry of reactive nitrogen above the Antarctic Plateau. During 2011–2012, NOx mixing ratios and flux were larger than in 2009–2010, consistent with also larger surface O3 mixing ratios resulting from increased net O3 production. Large NOx mixing ratios at Dome C arise from a combination of continuous sunlight, shallow mixing height and significant NOx emissions by surface snow (FNOx). During 23 December 2011–12 January 2012, median FNOx was twice that during the same period in 2009–2010 due to significantly larger atmospheric turbulence and a slightly stronger snowpack source. A tripling of FNOx in December 2011 was largely due to changes in snowpack source strength caused primarily by changes in NO3− concentrations in the snow skin layer, and only to a secondary order by decrease of total column O3 and associated increase in NO3− photolysis rates. A source of uncertainty in model estimates of FNOx is the quantum yield of NO3− photolysis in natural snow, which may change over time as the snow ages.

scholarly journals Modeling of the chemistry in oxidation flow reactors with high initial NO

2017 ◽  
Vol 17 (19) ◽  
pp. 11991-12010 ◽  
Author(s):  
Zhe Peng ◽  
Jose L. Jimenez
Keyword(s):  
Atmospheric Chemistry ◽  
Vehicle Emissions ◽  
High Efficiency ◽  
Input Parameter ◽  
High Water ◽  
Peroxy Radicals ◽  
Aerosol Formation ◽  
Experimental Conditions ◽  
Flow Reactors ◽  
Chemistry Research

Abstract. Oxidation flow reactors (OFRs) are increasingly employed in atmospheric chemistry research because of their high efficiency of OH radical production from low-pressure Hg lamp emissions at both 185 and 254 nm (OFR185) or 254 nm only (OFR254). OFRs have been thought to be limited to studying low-NO chemistry (in which peroxy radicals (RO2) react preferentially with HO2) because NO is very rapidly oxidized by the high concentrations of O3, HO2, and OH in OFRs. However, many groups are performing experiments by aging combustion exhaust with high NO levels or adding NO in the hopes of simulating high-NO chemistry (in which RO2 + NO dominates). This work systematically explores the chemistry in OFRs with high initial NO. Using box modeling, we investigate the interconversion of N-containing species and the uncertainties due to kinetic parameters. Simple initial injection of NO in OFR185 can result in more RO2 reacted with NO than with HO2 and minor non-tropospheric photolysis, but only under a very narrow set of conditions (high water mixing ratio, low UV intensity, low external OH reactivity (OHRext), and initial NO concentration (NOin) of tens to hundreds of ppb) that account for a very small fraction of the input parameter space. These conditions are generally far away from experimental conditions of published OFR studies with high initial NO. In particular, studies of aerosol formation from vehicle emissions in OFRs often used OHRext and NOin several orders of magnitude higher. Due to extremely high OHRext and NOin, some studies may have resulted in substantial non-tropospheric photolysis, strong delay to RO2 chemistry due to peroxynitrate formation, VOC reactions with NO3 dominating over those with OH, and faster reactions of OH–aromatic adducts with NO2 than those with O2, all of which are irrelevant to ambient VOC photooxidation chemistry. Some of the negative effects are the worst for alkene and aromatic precursors. To avoid undesired chemistry, vehicle emissions generally need to be diluted by a factor of > 100 before being injected into an OFR. However, sufficiently diluted vehicle emissions generally do not lead to high-NO chemistry in OFRs but are rather dominated by the low-NO RO2 + HO2 pathway. To ensure high-NO conditions without substantial atmospherically irrelevant chemistry in a more controlled fashion, new techniques are needed.

Significance of peroxynitric acid in atmospheric chemistry of nitrogen oxides

Nature ◽  
1977 ◽  
Vol 270 (5635) ◽  
pp. 328-329 ◽  
Author(s):  
R. A. Cox ◽  
R. G. DERWENT ◽  
A. J. L. HUTTON
Keyword(s):  
Nitrogen Oxides ◽  
Atmospheric Chemistry ◽  
Peroxynitric Acid

scholarly journals Model uncertainties affecting satellite-based inverse modeling of nitrogen oxides emissions and implications for surface ozone simulation

2012 ◽  
Vol 12 (6) ◽  
pp. 14269-14327 ◽  
Author(s):  
J.-T. Lin ◽  
Z. Liu ◽  
Q. Zhang ◽  
H. Liu ◽  
J. Mao ◽  
...  
Keyword(s):  
Nitrogen Oxides ◽  
Atmospheric Chemistry ◽  
Inverse Modeling ◽  
Positive Impact ◽  
Current Knowledge ◽  
Surface Ozone ◽  
Heterogeneous Reactions ◽  
Model Errors ◽  
Chemical Parameters ◽  
Ozone Monitoring Instrument

Abstract. Errors in chemical transport models (CTMs) interpreting the relation between space-retrieved tropospheric column densities of nitrogen dioxide (NO2) and emissions of nitrogen oxides (NOx) have important consequences on the inverse modeling. They are however difficult to quantify due to lack of adequate in situ measurements, particularly over China and other developing countries. This study proposes an alternate approach for model evaluation over East China, by analyzing the sensitivity of modeled NO2 columns to errors in meteorological and chemical parameters/processes important to the nitrogen abundance. As a demonstration, it evaluates the nested version of GEOS-Chem driven by the GEOS-5 meteorology and the INTEX-B anthropogenic emissions and used with retrievals from the Ozone Monitoring Instrument (OMI) to constrain emissions of NOx. The CTM has been used extensively for such applications. Errors are examined for a comprehensive set of meteorological and chemical parameters using measurements and/or uncertainty analysis based on current knowledge. Results are exploited then for sensitivity simulations perturbing the respective parameters, as the basis of the following post-model linearized and localized first-order modification. It is found that the model meteorology likely contains errors of various magnitudes in cloud optical depth, air temperature, water vapor, boundary layer height and many other parameters. Model errors also exist in gaseous and heterogeneous reactions, aerosol optical properties and emissions of non-nitrogen species affecting the nitrogen chemistry. Modifications accounting for quantified errors in 10 selected parameters increase the NO2 columns in most areas with an average positive impact of 22% in July and 10% in January. This suggests a possible systematic model bias such that the top-down emissions will be overestimated by the same magnitudes if the model is used for emission inversion without corrections. The modifications however cannot account for the large model underestimates in cities and other extremely polluted areas (particularly in the north) as compared to satellite retrievals, likely pointing to underestimates of the a priori emission inventory in these places with important implications for understanding of atmospheric chemistry and air quality. Post-model modifications also have large impacts on surface ozone concentrations with the peak values in July over North China decreasing by about 15 ppb. Individually, modification for the uptake of the hydroperoxyl radical on aerosols has the largest impact for both NO2 and ozone, followed by various other parameters important for some species in some seasons. Note that these modifications are simplified and should be used with caution for error apportionment.

scholarly journals Quantitative constraints on the atmospheric chemistry of nitrogen oxides: An analysis along chemical coordinates

2000 ◽  
Vol 105 (D19) ◽  
pp. 24283-24304 ◽  
Author(s):  
R. C. Cohen ◽  
K. K. Perkins ◽  
L. C. Koch ◽  
R. M. Stimpfle ◽  
P. O. Wennberg ◽  
...  
Keyword(s):  
Nitrogen Oxides ◽  
Atmospheric Chemistry

scholarly journals Photochemical environment over Southeast Asia primed for hazardous ozone levels with influx of nitrogen oxides from seasonal biomass burning

2020 ◽  
Author(s):  
Margaret R. Marvin ◽  
Paul I. Palmer ◽  
Barry G. Latter ◽  
Richard Siddans ◽  
Brian J. Kerridge ◽  
...  
Keyword(s):  
Nitrogen Oxides ◽  
Southeast Asia ◽  
Biomass Burning ◽  
Atmospheric Chemistry ◽  
Tropospheric Ozone ◽  
Transport Model ◽  
Dry Season ◽  
Ozone Exposure ◽  
Ozone Production ◽  
Ozone Levels

Abstract. Mainland and maritime Southeast Asia are home to more than 655 million people, representing nearly 10 % of the global population. The dry season in this region is typically associated with intense biomass burning activity, which leads to a significant increase in surface air pollutants that are harmful to human health, including ozone (O3). Latitude-based differences in dry season and land use distinguish two regional biomass burning regimes: (1) burning on the peninsular mainland peaking in March and (2) burning across Indonesia peaking in September. The type and amount of material burned in each regime impacts the emissions of nitrogen oxides (NOx = NO + NO2) and volatile organic compounds (VOCs), which combine to produce ozone. Here, we use the nested GEOS-Chem atmospheric chemistry transport model (horizontal resolution of 0.25° × 0.3125°), in combination with satellite observations from the Ozone Monitoring Instrument (OMI) and ground-based observations from Malaysia, to investigate ozone photochemistry over Southeast Asia in 2014. Seasonal cycles of tropospheric ozone columns from OMI and GEOS-Chem peak with biomass burning emissions. Compared to OMI, the model has a mean annual bias of −11 % but tends to overestimate tropospheric ozone near areas of seasonal fire activity. We find that outside of these burning areas, the underlying photochemical environment is generally NOx-limited, dominated by anthropogenic NOx and biogenic non-methane VOC emissions. Pyrogenic emissions of NOx play a key role in photochemistry, shifting towards more VOC-limited ozone production and contributing about 30 % of the regional ozone formation potential during both biomass burning seasons. Using the GEOS-Chem model, we find that biomass burning activity coincides with widespread ozone exposure at levels that exceed world public health guidelines, resulting in 272 premature deaths on mainland Southeast Asia in March of 2014 and another 273 deaths across Indonesia in September. Despite a positive model bias, hazardous ozone levels are confirmed by surface observations during both burning seasons.

scholarly journals Tropospheric ozone changes, radiative forcing and attribution to emissions in the Atmospheric Chemistry and Climate Model Inter-comparison Project (ACCMIP)

2012 ◽  
Vol 12 (10) ◽  
pp. 26047-26097 ◽  
Author(s):  
D. S. Stevenson ◽  
P. J. Young ◽  
V. Naik ◽  
J.-F. Lamarque ◽  
D. T. Shindell ◽  
...  
Keyword(s):  
Nitrogen Oxides ◽  
Atmospheric Chemistry ◽  
Tropospheric Ozone ◽  
Radiative Forcing ◽  
Climate Model ◽  
Lower Troposphere ◽  
Radiative Forcings ◽  
A Value ◽  
Intercomparison Project ◽  
Column Ozone

Abstract. Ozone (O3) from 17 atmospheric chemistry models taking part in the Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP) has been used to calculate tropospheric ozone radiative forcings (RFs). We calculate a~value for the pre-industrial (1750) to present-day (2010) tropospheric ozone RF of 0.40 W m−2. The model range of pre-industrial to present-day changes in O3 produces a spread (±1 standard deviation) in RFs of ±17%. Three different radiation schemes were used – we find differences in RFs between schemes (for the same ozone fields) of ±10%. Applying two different tropopause definitions gives differences in RFs of ±3%. Given additional (unquantified) uncertainties associated with emissions, climate-chemistry interactions and land-use change, we estimate an overall uncertainty of ±30% for the tropospheric ozone RF. Experiments carried out by a subset of six models attribute tropospheric ozone RF to increased emissions of methane (47%), nitrogen oxides (29%), carbon monoxide (15%) and non-methane volatile organic compounds (9%); earlier studies attributed more of the tropospheric ozone RF to methane and less to nitrogen oxides. Normalising RFs to changes in tropospheric column ozone, we find a global mean normalised RF of 0.042 W m−2 DU−1, a value similar to previous work. Using normalised RFs and future tropospheric column ozone projections we calculate future tropospheric ozone RFs (W m−2; relative to 1850 – add 0.04 W m−2 to make relative to 1750) for the Representative Concentration Pathways in 2030 (2100) of: RCP2.6: 0.31 (0.16); RCP4.5: 0.38 (0.26); RCP6.0: 0.33 (0.24); and RCP8.5: 0.42 (0.56). Models show some coherent responses of ozone to climate change: decreases in the tropical lower troposphere, associated with increases in water vapour; and increases in the sub-tropical to mid-latitude upper troposphere, associated with increases in lightning and stratosphere-to-troposphere transport.

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