Influence of natural hydrocarbons on ozone formation in an isolated power plant plume

Luria, Menachem; Tanner, Roger L.; Imhoff, Robert E.; Valente, Ralph J.; Bailey, Elizabeth M.; Mueller, Stephen F.

doi:10.1029/1999jd901018

Cited by 25 publications

(16 citation statements)

References 32 publications

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“…(3) The sensitivity analyses show that while the modeled chemical OPE appears to be relatively insensitive to the dilution rate for the present episode, it responds nonlinearly to changes in NO x and anthropogenic VOC emissions. It decreases at high NO x , increases at high VOC and vice versa, which are consistent with previous studies [ Liu et al , 1987; Lin et al , 1988; Luria et al , 2000; Daum et al , 2000; Ryerson et al , 1998, 2001]. The corresponding downwind O 3 concentrations responded in a nonlinear fashion as well.…”

Section: Discussionsupporting

confidence: 91%

“…Thus each point on the lines in this figure represents the chemical OPE predicted at the end point C 3 (indicated in Figure 4) for the corresponding scaling factor value applied to the base case emissions and initial concentrations as mentioned earlier. The figure shows that OPE decreases at high NO x concentrations as was predicted by Liu et al [1987] and observed by Ryerson et al [1998, 2001], and increases at high VOC concentrations as observed by Luria et al [2000] and Ryerson et al [2001]. However, it should be also noted that part of the increase of OPE at low is due to PAN decomposition to give back NO 2 .…”

Section: Sensitivity Analysissupporting

confidence: 64%

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Ozone production efficiency and NO_x depletion in an urban plume: Interpretation of field observations and implications for evaluating O₃‐NO_x‐VOC sensitivity

et al. 2003

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[1] Ozone production efficiency (OPE) can be defined as the number of ozone (O 3 ) molecules photochemically produced by a molecule of NO x (NO + NO 2 ) before it is lost from the NO x À O 3 cycle. Here we consider observational and modeling techniques to evaluate various operational definitions of OPEs using aircraft and surface measurements taken as part of the 1999 Southern Oxidant Study field campaign in Nashville, Tennessee. A key tool in our analysis is a Lagrangian box model, which is used to quantitatively describe the effects of emissions, dilution, dry deposition, and photochemistry in an urban air parcel as it was advected downwind. After evaluating the model using the observed downwind concentrations of several key species, we show that the modeled NO x oxidation and O 3 production rates as well as the associated instantaneous and cumulative OPEs depend on the time of day and the photochemical age of the air parcel. The observationbased OPEs are found to be consistent with the modeled values with the expected biases. A model sensitivity study suggests that downwind O 3 concentrations in the Nashville plume are more sensitive to NO x emissions than anthropogenic VOC emissions. Because the OPE exhibits a nonlinear dependence on emissions and meteorological effects, it would be difficult to rely only on observations to map out the nonlinear response of O 3 to a wide span of NO x and VOC emission changes. Properly constrained and well-evaluated models using a variety of observations are therefore necessary to reliably predict O 3 -NO x -VOC sensitivity for designing effective O 3 control strategies.

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Section: Discussionsupporting

confidence: 91%

Section: Sensitivity Analysissupporting

confidence: 64%

Ozone production efficiency and NO_x depletion in an urban plume: Interpretation of field observations and implications for evaluating O₃‐NO_x‐VOC sensitivity

et al. 2003

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“…Isoprene plays an important role in O 3 formation in rural areas [ Trainer et al , 1987], cities [ Chameides et al , 1988], and power plant plumes [ Luria et al , 2000; Ryerson et al , 2001]. It is very reactive (k OH = 9.7 × 10 −11 cm −3 s −1 ) so that even levels below ppb can dominate the overall OH‐VOC reactivity.…”

Section: Discussionmentioning

confidence: 99%

A comparative study of ozone production in five U.S. metropolitan areas

2005

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. Ozone production rates P(O 3 ) and their sensitivity to NO x and volatile organic carbons (VOCs) are calculated using observed concentrations as inputs to a steady state box model. City to city comparisons are made to illustrate common features of urban photochemistry and features that are unique to specific cities. Ozone production rates vary from nearly zero to 155 ppb h À1 . Differences in P(O 3 ) depend on precursor concentrations, namely, radical sources, NO x and VOCs. Under conditions where P(O 3 ) is greater than 25 ppb h À1 , there is a potential to produce enough same-day O 3 to transform a typical regional background into a severe O 3 episode. Six such cases were observed, in Nashville, Philadelphia, and Houston, with elevated O 3 concentrations in the afternoon (130-211 ppb) following a morning in which P(O 3 ) was 25-140 ppb h À1 . High P(O 3 ) occurs when NO x concentrations are 5-25 ppb and OH-VOC reactivity is above 5 s À1 . These conditions are infrequent, and aside from a common dependence on calm winds, reasons vary from city to city. In Nashville, high P(O 3 ) was observed during a stagnation event over downtown and under the circumstance that an air mass with a high concentration of isoprene encountered a NO x source. In Houston, NO x and light olefins are coemitted from petrochemical facilities leading to the highest P(O 3 )s of the five cities studied. High values of P(O 3 ) did not occur in Phoenix because of low radical production, caused mainly by a dry atmosphere, and a low VOC to NO x ratio. The sensitivity of P(O 3 ) to its precursors varied from NO x limited in rural samples to VOC limited near emission sources. In Philadelphia, and especially Phoenix, the highest O 3 production rates occurred under VOC-limited conditions. In Nashville, New York City, and Houston the high-P(O 3 ) samples were near the ridge line where P(O 3 ) responds somewhat to VOC reductions but is insensitive to NO x changes.

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“…Isoprene can play an important role in O 3 formation in rural areas , for cities (Chameides et al, 1988), and for power plant plumes (Luria et al, 2000;Ryerson et al, 2001). It is very reactive (kOH = 10.0 ± 1.2 × 10 −11 cm 3 molecule −1 s −1 at 294 K; Karl et al, 2006) and thus even sub-ppb levels can dominate the overall OH-VOC reactivity.…”

Section: Isoprene Oxidation Pathways: Change Frommentioning

confidence: 99%

Impact of Manaus City on the Amazon Green Ocean atmosphere: ozone production, precursor sensitivity and aerosol load

et al. 2010

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Abstract. As a contribution to the Large-Scale BiosphereAtmosphere Experiment in Amazonia -Cooperative LBA Airborne Regional Experiment (LBA-CLAIRE-2001) field campaign in the heart of the Amazon Basin, we analyzed the temporal and spatial dynamics of the urban plume of Manaus City during the wet-to-dry season transition period in July 2001. During the flights, we performed vertical stacks of crosswind transects in the urban outflow downwind of Manaus City, measuring a comprehensive set of trace constituents including O 3 , NO, NO 2 , CO, VOC, CO 2 , and H 2 O. Aerosol loads were characterized by concentrations of total aerosol number (CN) and cloud condensation nuclei (CCN), and by light scattering properties. Measurements over pristine rainforest areas during the campaign showed low levCorrespondence to: U. Kuhn (uwe.kuhn@art.admin.ch) els of pollution from biomass burning or industrial emissions, representative of wet season background conditions. The urban plume of Manaus City was found to be joined by plumes from power plants south of the city, all showing evidence of very strong photochemical ozone formation. One episode is discussed in detail, where a threefold increase in ozone mixing ratios within the atmospheric boundary layer occurred within a 100 km travel distance downwind of Manaus. Observation-based estimates of the ozone production rates in the plume reached 15 ppb h −1 .Within the plume core, aerosol concentrations were strongly enhanced, with CN/ CO ratios about one order of magnitude higher than observed in Amazon biomass burning plumes. CN/ CO ratios tended to decrease with increasing transport time, indicative of a significant reduction in particle number by coagulation, and without substantial new particle nucleation occurring within the time/space observed. While in the background atmosphere a large Published by Copernicus Publications on behalf of the European Geosciences Union. 9252 U. Kuhn et al.: Impact of Manaus City on the Amazon Green Ocean atmosphere fraction of the total particle number served as CCN (about 60-80% at 0.6% supersaturation), the CCN/CN ratios within the plume indicated that only a small fraction (16 ± 12 %) of the plume particles were CCN. The fresh plume aerosols showed relatively weak light scattering efficiency. The COnormalized CCN concentrations and light scattering coefficients increased with plume age in most cases, suggesting particle growth by condensation of soluble organic or inorganic species.We used a Single Column Chemistry and Transport Model (SCM) to infer the urban pollution emission fluxes of Manaus City, implying observed mixing ratios of CO, NO x and VOC. The model can reproduce the temporal/spatial distribution of ozone enhancements in the Manaus plume, both with and without accounting for the distinct (high NO x ) contribution by the power plants; this way examining the sensitivity of ozone production to changes in the emission rates of NO x . The VOC reactivity in the Manaus region was dominated by a high burden of biogenic isoprene from the b...

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Influence of natural hydrocarbons on ozone formation in an isolated power plant plume

Cited by 25 publications

References 32 publications

Ozone production efficiency and NO_x depletion in an urban plume: Interpretation of field observations and implications for evaluating O₃‐NO_x‐VOC sensitivity

Ozone production efficiency and NO_x depletion in an urban plume: Interpretation of field observations and implications for evaluating O₃‐NO_x‐VOC sensitivity

A comparative study of ozone production in five U.S. metropolitan areas

Impact of Manaus City on the Amazon Green Ocean atmosphere: ozone production, precursor sensitivity and aerosol load

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Influence of natural hydrocarbons on ozone formation in an isolated power plant plume

Cited by 25 publications

References 32 publications

Ozone production efficiency and NOx depletion in an urban plume: Interpretation of field observations and implications for evaluating O3‐NOx‐VOC sensitivity

Ozone production efficiency and NOx depletion in an urban plume: Interpretation of field observations and implications for evaluating O3‐NOx‐VOC sensitivity

A comparative study of ozone production in five U.S. metropolitan areas

Impact of Manaus City on the Amazon Green Ocean atmosphere: ozone production, precursor sensitivity and aerosol load

Contact Info

Product

Resources

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Ozone production efficiency and NO_x depletion in an urban plume: Interpretation of field observations and implications for evaluating O₃‐NO_x‐VOC sensitivity

Ozone production efficiency and NO_x depletion in an urban plume: Interpretation of field observations and implications for evaluating O₃‐NO_x‐VOC sensitivity