Model correlations for ozone, reactive nitrogen, and peroxides for Nashville in comparison with measurements: Implications for O3‐NOx‐hydrocarbon chemistry

Sillman, Sanford; He, Dongyang; Pippin, M. R.; Daum, P. H.; Imre, Daniel; Kleinman, Lawrence I.; Lee, Jai Hoon; Weinstein-Lloyd, J.

doi:10.1029/98jd00349

Cited by 95 publications

(120 citation statements)

References 53 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Their results show that the surface resistance is negligible in the case of H 2 O 2 and that the dry deposition of all peroxides is limited by turbulence. Sillman et al (1998) derive a dry deposition velocity of ≈5 cm/s for H 2 O 2 from correlations of O 3 , NO z and peroxides during the Middle Tennessee Ozone Study (model and measurements), again significantly higher than the value found in the present study. Junkermann and Stockwell (1999) estimate hydrogen peroxide and methyl hydroperoxide dry deposition rates of 1×10 −5 s −1 and 0.8×10 −5 s −1 above the tropical South Atlantic in October and November 1994.…”

Section: Comparison With Results From Other Studiescontrasting

confidence: 55%

“…The present study suggests a best estimate for the 24 h mean of the dry deposition velocity of hydrogen peroxide of Gao et al (1993) 2.5 above forest Heikes et al (1996) 0.88 1.4×10 −5 South Atlantic Hall and Claiborn (1997) 1-5 coniferous forest in Canada Sillman et al (1998) ≈5 Tennessee Walcek (1987) theoretically calculated a value of 1 cm/s for the H 2 O 2 dry deposition velocity over the northeast United States which is roughly in agreement with our result for the rainforest and with the mean 1-D SCM result over land. Baer and Nester (1992) assessed an average v d (H 2 O 2 )=1.5 cm/s for the region of the Upper Rhine Valley (Germany) in March 1985 with a regional mesoscale diffusion model, again relatively close to our estimate.…”

Section: Comparison With Results From Other Studiesmentioning

confidence: 99%

See 1 more Smart Citation

Chemistry, transport and dry deposition of trace gases in the boundary layer over the tropical Atlantic Ocean and the Guyanas during the GABRIEL field campaign

et al. 2007

View full text Add to dashboard Cite

Abstract. We present a comparison of different Lagrangian and chemical box model calculations with measurement data obtained during the GABRIEL campaign over the tropical Atlantic Ocean and the Amazon rainforest in the Guyanas, October 2005. Lagrangian modelling of boundary layer (BL) air constrained by measurements is used to derive a horizontal gradient (≈5.6 pmol/mol km −1 ) of CO from the ocean to the rainforest (east to west). This is significantly smaller than that derived from the measurements (16-48 pmol/mol km −1 ), indicating that photochemical production from organic precursors alone cannot explain the observed strong gradient. It appears that HCHO is overestimated by the Lagrangian and chemical box models, which include dry deposition but not exchange with the free troposphere (FT). The relatively short lifetime of HCHO implies substantial BL-FT exchange. The mixing-in of FT air affected by African and South American biomass burning at an estimated rate of 0.12 h −1 increases the CO and decreases the HCHO mixing ratios, improving agreement with measurements. A mean deposition velocity of 1.35 cm/s for H 2 O 2 over the ocean as well as over the rainforest is deduced assuming BL-FT exchange adequate to the results for CO. The measured increase of the organic peroxides from the ocean to the rainforest (≈0.66 nmol/mol d −1 ) is significantly overestimated by the Lagrangian model, even when using high values for the deposition velocity and the entrainment rate. Our results point at either heterogeneous loss of organic peroxides and/or their radical precursors, underestimated photodissociation or missing reaction paths of peroxy radicals not forming peroxides in isoprene chemistry. We calculate a mean integrated daytime net ozone production (NOP) in the Correspondence to: A. Stickler (alexander.stickler@env.ethz.ch) BL of (0.2±5.9) nmol/mol (ocean) and (2.4±2.1) nmol/mol (rainforest). The NOP strongly correlates with NO and has a positive tendency in the boundary layer over the rainforest.

show abstract

Section: Comparison With Results From Other Studiescontrasting

confidence: 55%

Section: Comparison With Results From Other Studiesmentioning

confidence: 99%

Chemistry, transport and dry deposition of trace gases in the boundary layer over the tropical Atlantic Ocean and the Guyanas during the GABRIEL field campaign

et al. 2007

View full text Add to dashboard Cite

show abstract

“…The correlation shows surface values of O 3 versus NO z for the entire model domain, which includes both Mexico City and the surrounding rural area. The figure also shows equivalent correlations from model-based studies in two different locations: Nashville (Sillman et al, 1998) and Paris (Sillman et al, 2003). The previous studies also included comparisons with measured O 3 versus NO z for the model events and generally good agreement.…”

Section: Comparison Between Mexico City Parismentioning

confidence: 90%

Reactive nitrogen in Mexico City and its relation to ozone-precursor sensitivity: results from photochemical models

Sillman

West

2009

Atmos. Chem. Phys.

View full text Add to dashboard Cite

Abstract.We use results of a 3-D photochemistry/transport model for ozone formation in Mexico City during events in 1997 to investigate ambient concentrations of reactive nitrogen in relation to ozone-precursor sensitivity. Previous results from other locations suggest that ratios such as O 3 /NO y and H 2 O 2 /HNO 3 might provide measurement-based indicators for NO x -sensitive or VOC-sensitive conditions. Mexico City presents a different environment due to its high concentrations of VOC and high level of pollutants in general. The model predicts a correlation between PAN and O 3 with relatively high PAN/O 3 (0.07), which is still lower than measured values. The model PAN is comparable with results from a model for Paris but much higher than were found in Nashville in both models and measurements. The difference is due in part to the lower temperature in Mexico City relative to Nashville. Model HNO 3 in Mexico City is unusually low for an urban area and PAN/HNO 3 is very high, probably due to the high ratio of reactivity-weighted VOC to NO x . The model predicts that VOC-sensitive chemistry in Mexico is associated with high NO x , NO y and NO x /NO y and with low O 3 /NO y and H 2 O 2 /HNO 3 , suggesting that these indicators work well for Mexico City. The relation between ozone-precursor sensitivity and either O 3 /NO z or O 3 /HNO 3 is more ambiguous. VOC-sensitive conditions are associated with higher O 3 /HNO 3 than would be found in NO x -sensitive conditions, but model O 3 /HNO 3 associated with both NO xsensitive and VOC-sensitive chemistry is higher in Mexico than in other cities. The model predicts a mixed pattern of ozone-precursor sensitivity in Mexico City, with VOCsensitive conditions in the morning and NO x -sensitive in the afternoon, in contrast to results from other models for more recent events that predicted strongly VOC-sensitive conditions throughout the day. The difference in predicted ozoneCorrespondence to: S. Sillman (sillman@umich.edu) precursor sensitivity is most likely due to different emission rates and to changes in emissions over time. The model with mixed sensitivity predicts much lower ambient NO x and NO x /NO y than the strongly VOC-sensitive model.

show abstract

“…Our analysis of the instantaneous chemistry should not be confused with modeling analysis that has been performed on the Nashville data using full scale Eulerian models driven by measured wind fields and emission inventories [e.g., Sillman et al, 1998]. Such modeling exercises have been employed to predict maximum O3 concentrations and to address the consequences of the reduction of NO,` and/or hydrocarbon emissions on maximum O3 concentrations.…”

mentioning

confidence: 99%

Analysis of the processing of Nashville urban emissions on July 3 and July 18, 1995

Daum¹,

Kleinman²,

Imre³

et al. 2000

J. Geophys. Res.

View full text Add to dashboard Cite

Abstract. This paper analyzes data obtained on July 3 and 18, 1995, during the summer 1995 Southern Oxidant Study (SOS) field campaign. In a previous paper [Nunnermacker et al., 1998] we analyzed measurements of key species that contribute to formation of O3 in the Nashville urban plume and presented a semiquantitative picture of O3 production in the plume from the point of emission to locations where no net O3 was being formed. In this paper we use a box model constrained by observed concentrations of stable species to obtain a detailed mechanistic description of the instantaneous processing of urban emissions at various times in the chemical evolution of the urban plume. Instantaneous ozone production rates and efficiencies with respect to NOx and to primary radical production are examined. At high NOx concentrations in the fresh urban plume the O3 production rate was found to be directly proportional to the hydrocarbon to NOx reactivity ratio. At lower NOx concentrations, corresponding to the mature urban plume and the background atmosphere, the O3 production rate was found to be directly proportional to the NOx concentration and independent of the hydrocarbon reactivity. NOx was found to be most efficiently used for ozone production at low NOx concentrations. In contrast, the efficiency with which the system uses primary radicals was found to be very low at low NOx concentrations and to peak at a NOx concentration of approximately 4 ppbv. A sensitivity study of the instantaneous O3 production rates to changes in NOx or hydrocarbon concentrations showed that the instantaneous 03 production rate at the center of the urban plume, when half of the urban NOx emissions had been processed, is hydrocarbon sensitive. However, 03 production becomes NOx sensitive as the plume matures.

show abstract

Model correlations for ozone, reactive nitrogen, and peroxides for Nashville in comparison with measurements: Implications for O₃‐NO_x‐hydrocarbon chemistry

Cited by 95 publications

References 53 publications

Chemistry, transport and dry deposition of trace gases in the boundary layer over the tropical Atlantic Ocean and the Guyanas during the GABRIEL field campaign

Chemistry, transport and dry deposition of trace gases in the boundary layer over the tropical Atlantic Ocean and the Guyanas during the GABRIEL field campaign

Reactive nitrogen in Mexico City and its relation to ozone-precursor sensitivity: results from photochemical models

Analysis of the processing of Nashville urban emissions on July 3 and July 18, 1995

Contact Info

Product

Resources

About