scholarly journals Observations of the temperature dependent response of ozone to NO<sub>x</sub> reductions in the Sacramento, CA urban plume

2011 ◽  
Vol 11 (14) ◽  
pp. 6945-6960 ◽  
Author(s):  
B. W. LaFranchi ◽  
A. H. Goldstein ◽  
R. C. Cohen

Abstract. Observations of NOx in the Sacramento, CA region show that mixing ratios decreased by 30 % between 2001 and 2008. Here we use an observation-based method to quantify net ozone (O3) production rates in the outflow from the Sacramento metropolitan region and examine the O3 decrease resulting from reductions in NOx emissions. This observational method does not rely on assumptions about detailed chemistry of ozone production, rather it is an independent means to verify and test these assumptions. We use an instantaneous steady-state model as well as a detailed 1-D plume model to aid in interpretation of the ozone production inferred from observations. In agreement with the models, the observations show that early in the plume, the NOx dependence for Ox (Ox = O3 + NO2) production is strongly coupled with temperature, suggesting that temperature-dependent biogenic VOC emissions and other temperature-related effects can drive Ox production between NOx-limited and NOx-suppressed regimes. As a result, NOx reductions were found to be most effective at higher temperatures over the 7 year period. We show that violations of the California 1-h O3 standard (90 ppb) in the region have been decreasing linearly with decreases in NOx (at a given temperature) and predict that reductions of NOx concentrations (and presumably emissions) by an additional 30 % (relative to 2007 levels) will eliminate violations of the state 1 h standard in the region. If current trends continue, a 30 % decrease in NOx is expected by 2012, and an end to violations of the 1 h standard in the Sacramento region appears to be imminent.

2011 ◽  
Vol 11 (2) ◽  
pp. 6259-6299 ◽  
Author(s):  
B. W. LaFranchi ◽  
A. H. Goldstein ◽  
R. C. Cohen

Abstract. Observations of NOx in the Sacramento, CA region show that mixing ratios decreased by 30% between 2001 and 2008. Here we use an observation-based method to quantify net ozone production rates in the outflow from the Sacramento metropolitan region and examine the O3 decrease resulting from reductions in NOx emissions. This observational method does not rely on assumptions about detailed chemistry of ozone production, rather it is an independent means to verify and test these assumptions. We use an instantaneous steady-state model as well as a detailed 1-D plume model to aid in interpretation of the ozone production inferred from observations. In agreement with the models, the observations show that early in the plume, the NOx dependence for Ox (Ox = O3 + NO2) production is strongly coupled with temperature, suggesting that temperature-dependent biogenic VOC emissions can drive Ox production between NOx-limited and NOx-suppressed regimes. As a result, NOx reductions were found to be most effective at higher temperatures over the 7 year period. We show that violations of the California 1-hour O3 standard (90 ppb) in the region have been decreasing linearly with decreases in NOx (at a given temperature) and predict that reductions of NOx concentrations (and presumably emissions) by an additional 30% (relative to 2007 levels) will eliminate violations of the state 1 h standard in the region. If current trends continue, a 30% decrease in NOx is expected by 2012, and an end to violations of the 1 h standard in the Sacramento region appears to be imminent.


2017 ◽  
Vol 17 (11) ◽  
pp. 6517-6529 ◽  
Author(s):  
Andrew J. Abeleira ◽  
Delphine K. Farmer

Abstract. Contrary to most regions in the US, ozone in the northern Front Range metropolitan area (NFRMA) of Colorado was either stagnant or increasing between 2000 and 2015, despite substantial reductions in NOx emissions. We used available long-term ozone and NOx data in the NFRMA to investigate these trends. Ozone increased from weekdays to weekends for a number of sites in the NFRMA with weekend reductions in NO2 at two sites in downtown Denver, indicating that the region was in a NOx-saturated ozone production regime. The stagnation and increases in ozone in the NFRMA are likely due to a combination of decreasing NOx emissions in a NOx-saturated environment and increased anthropogenic volatile organic compound (VOC) emissions in the NFRMA. Further investigation of the weekend–weekday effect showed that the region outside of the most heavily trafficked Denver area was transitioning to peak ozone production towards NOx-limited chemistry. This transition implies that continued NOx decreases will result in ozone being less sensitive to changes in either anthropogenic or biogenic VOC reactivity in the NFRMA. In contrast to anthropogenic VOCs, biogenic VOCs are unlikely to have increased in the NFRMA between 2000 and 2015, but are temperature dependent and likely vary by drought year. Ozone in the NFRMA has a temperature dependence, albeit smaller than many other US locations, consistent with biogenic VOC contributions to ozone production in the region. We show that while ozone increased with temperature in the NFRMA, which is consistent with a NOx-saturated regime coupled to temperature-dependent VOCs, this relationship is suppressed in drought years. We attribute this drought year suppression to decreased biogenic isoprene emissions due to long-term drought stress. Thus, while anthropogenic NOx and VOCs likely dominate ozone production regimes in the NFRMA, biogenic VOCs may also impact regional ozone and its temperature dependence.


2010 ◽  
Vol 10 (19) ◽  
pp. 9251-9282 ◽  
Author(s):  
U. Kuhn ◽  
L. Ganzeveld ◽  
A. Thielmann ◽  
T. Dindorf ◽  
G. Schebeske ◽  
...  

Abstract. As a contribution to the Large-Scale Biosphere-Atmosphere 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 O3, NO, NO2, CO, VOC, CO2, and H2O. 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 levels 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 ΔCN/ΔCO ratios about one order of magnitude higher than observed in Amazon biomass burning plumes. ΔCN/ΔCO 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 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 CO-normalized 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, NOx 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 NOx) contribution by the power plants; this way examining the sensitivity of ozone production to changes in the emission rates of NOx. The VOC reactivity in the Manaus region was dominated by a high burden of biogenic isoprene from the background rainforest atmosphere, and therefore NOx control is assumed to be the most effective ozone abatement strategy. Both observations and models show that the agglomeration of NOx emission sources, like power plants, in a well-arranged area can decrease the ozone production efficiency in the near field of the urban populated cores. But on the other hand remote areas downwind of the city then bear the brunt, being exposed to increased ozone production and N-deposition. The simulated maximum stomatal ozone uptake fluxes were 4 nmol m−2 s−1 close to Manaus, and decreased only to about 2 nmol m−2 s−1 within a travel distance >1500 km downwind from Manaus, clearly exceeding the critical threshold level for broadleaf trees. Likewise, the simulated N deposition close to Manaus was ~70 kg N ha−1 a−1 decreasing only to about 30 kg N ha−1 a−1 after three days of simulation.


2010 ◽  
Vol 10 (5) ◽  
pp. 13091-13178 ◽  
Author(s):  
U. Kuhn ◽  
L. Ganzeveld ◽  
A. Thielmann ◽  
T. Dindorf ◽  
G. Schebeske ◽  
...  

Abstract. As a contribution to the Large-Scale Biosphere-Atmosphere 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 O3, NO, NO2, CO, VOC, CO2, and H2O. Aerosol loads were characterized by total aerosol number concentration (CN) and cloud condensation nuclei (CCN) concentrations, and light scattering properties. Measurements over pristine rainforest areas during the campaign showed low levels 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 in 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 ΔCN/ΔCO ratios about one order of magnitude higher than observed in Amazon biomass burning plumes. ΔCN/ΔCO 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 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 CO-normalized 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, NOx 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 NOx) contribution by the power plants; this way examining the sensitivity of ozone production to changes in the emission rates of NOx. The VOC reactivity in the Manaus region was dominated by a high burden of biogenic isoprene from the background rainforest atmosphere, and therefore NOx control is assumed to be the most effective ozone abatement strategy. Both observations and models show that the agglomeration of NOx emission sources, like power plants, in a well-arranged area can decrease the ozone production efficiency in the near field of the urban populated cores. But on the other hand remote areas downwind of the city then bear the brunt, being exposed to increased ozone production and N-deposition. The simulated maximum stomatal ozone uptake fluxes were 4 nmol m−2 s−1 close to Manaus, and decreased only to about 2 nmol m−2 s−1 within a travel distance >1500 km downwind from Manaus, clearly exceeding the critical threshold level for broadleaf trees. Likewise, the simulated N deposition close to Manaus was ~70 kg N ha−1 a−1 decreasing only to about 30 kg N ha−1 a−1 after three days of simulation.


2020 ◽  
Vol 6 (9) ◽  
pp. eaay4213 ◽  
Author(s):  
Yang Hu ◽  
Fred Florio ◽  
Zhizhong Chen ◽  
W. Adam Phelan ◽  
Maxime A. Siegler ◽  
...  

Spin and valley degrees of freedom in materials without inversion symmetry promise previously unknown device functionalities, such as spin-valleytronics. Control of material symmetry with electric fields (ferroelectricity), while breaking additional symmetries, including mirror symmetry, could yield phenomena where chirality, spin, valley, and crystal potential are strongly coupled. Here we report the synthesis of a halide perovskite semiconductor that is simultaneously photoferroelectricity switchable and chiral. Spectroscopic and structural analysis, and first-principles calculations, determine the material to be a previously unknown low-dimensional hybrid perovskite (R)-(−)-1-cyclohexylethylammonium/(S)-(+)-1 cyclohexylethylammonium) PbI3. Optical and electrical measurements characterize its semiconducting, ferroelectric, switchable pyroelectricity and switchable photoferroelectric properties. Temperature dependent structural, dielectric and transport measurements reveal a ferroelectric-paraelectric phase transition. Circular dichroism spectroscopy confirms its chirality. The development of a material with such a combination of these properties will facilitate the exploration of phenomena such as electric field and chiral enantiomer–dependent Rashba-Dresselhaus splitting and circular photogalvanic effects.


2019 ◽  
Vol 116 (14) ◽  
pp. 6641-6646 ◽  
Author(s):  
Havala O. T. Pye ◽  
Emma L. D’Ambro ◽  
Ben H. Lee ◽  
Siegfried Schobesberger ◽  
Masayuki Takeuchi ◽  
...  

Atmospheric oxidation of natural and anthropogenic volatile organic compounds (VOCs) leads to secondary organic aerosol (SOA), which constitutes a major and often dominant component of atmospheric fine particulate matter (PM2.5). Recent work demonstrates that rapid autoxidation of organic peroxy radicals (RO2) formed during VOC oxidation results in highly oxygenated organic molecules (HOM) that efficiently form SOA. As NOxemissions decrease, the chemical regime of the atmosphere changes to one in which RO2autoxidation becomes increasingly important, potentially increasing PM2.5, while oxidant availability driving RO2formation rates simultaneously declines, possibly slowing regional PM2.5formation. Using a suite of in situ aircraft observations and laboratory studies of HOM, together with a detailed molecular mechanism, we show that although autoxidation in an archetypal biogenic VOC system becomes more competitive as NOxdecreases, absolute HOM production rates decrease due to oxidant reductions, leading to an overall positive coupling between anthropogenic NOxand localized biogenic SOA from autoxidation. This effect is observed in the Atlanta, Georgia, urban plume where HOM is enhanced in the presence of elevated NO, and predictions for Guangzhou, China, where increasing HOM-RO2production coincides with increases in NO from 1990 to 2010. These results suggest added benefits to PM2.5abatement strategies come with NOxemission reductions and have implications for aerosol–climate interactions due to changes in global SOA resulting from NOxinteractions since the preindustrial era.


2012 ◽  
Vol 12 (5) ◽  
pp. 2567-2585 ◽  
Author(s):  
Y. Kanaya ◽  
A. Hofzumahaus ◽  
H.-P. Dorn ◽  
T. Brauers ◽  
H. Fuchs ◽  
...  

Abstract. A photochemical box model constrained by ancillary observations was used to simulate OH and HO2 concentrations for three days of ambient observations during the HOxComp field campaign held in Jülich, Germany in July 2005. Daytime OH levels observed by four instruments were fairly well reproduced to within 33% by a base model run (Regional Atmospheric Chemistry Mechanism with updated isoprene chemistry adapted from Master Chemical Mechanism ver. 3.1) with high R2 values (0.72–0.97) over a range of isoprene (0.3–2 ppb) and NO (0.1–10 ppb) mixing ratios. Daytime HO2(*) levels, reconstructed from the base model results taking into account the sensitivity toward speciated RO2 (organic peroxy) radicals, as recently reported from one of the participating instruments in the HO2 measurement mode, were 93% higher than the observations made by the single instrument. This also indicates an overprediction of the HO2 to OH recycling. Together with the good model-measurement agreement for OH, it implies a missing OH source in the model. Modeled OH and HO2(*) could only be matched to the observations by addition of a strong unknown loss process for HO2(*) that recycles OH at a high yield. Adding to the base model, instead, the recently proposed isomerization mechanism of isoprene peroxy radicals (Peeters and Müller, 2010) increased OH and HO2(*) by 28% and 13% on average. Although these were still only 4% higher than the OH observations made by one of the instruments, larger overestimations (42–70%) occurred with respect to the OH observations made by the other three instruments. The overestimation in OH could be diminished only when reactive alkanes (HC8) were solely introduced to the model to explain the missing fraction of observed OH reactivity. Moreover, the overprediction of HO2(*) became even larger than in the base case. These analyses imply that the rates of the isomerization are not readily supported by the ensemble of radical observations. One of the measurement days was characterized by low isoprene concentrations (∼0.5 ppb) and OH reactivity that was well explained by the observed species, especially before noon. For this selected period, as opposed to the general behavior, the model tended to underestimate HO2(*). We found that this tendency is associated with high NOx concentrations, suggesting that some HO2 production or regeneration processes under high NOx conditions were being overlooked; this might require revision of ozone production regimes.


2009 ◽  
Vol 9 (11) ◽  
pp. 3731-3743 ◽  
Author(s):  
M. Mena-Carrasco ◽  
G. R. Carmichael ◽  
J. E. Campbell ◽  
D. Zimmerman ◽  
Y. Tang ◽  
...  

Abstract. The impact of Mexico City (MCMA) emissions is examined by studying its effects on air quality, photochemistry, and on ozone production regimes by combining model products and aircraft observations from the MILAGRO experiment during March 2006. The modeled influence of MCMA emissions to enhancements in surface level NOx, CO, and O3 concentrations (10–30% increase) are confined to distances <200 km, near surface. However, the extent of the influence is significantly larger at higher altitudes. Broader MCMA impacts (some 900 km Northeast of the city) are shown for specific outflow conditions in which enhanced ozone, NOy, and MTBE mixing ratios over the Gulf of Mexico are linked to MCMA by source tagged tracers and sensitivity runs. This study shows that the "footprint" of MCMA on average is fairly local, with exception to reactive nitrogen, which can be transported long range in the form of PAN, acting as a reservoir and source of NOx with important regional ozone formation implications. The simulated effect of MCMA emissions of anthropogenic aerosol on photochemistry showed a maximum regional decrease of 40% in J[NO2→NO+O], and resulting in the reduction of ozone production by 5–10%. Observed ozone production efficiencies are evaluated as a function of distance from MCMA, and by modeled influence from MCMA. These tend to be much lower closer to MCMA, or in those points where modeled contribution from MCMA is large. This research shows that MCMA emissions do effect on regional air quality and photochemistry, both contributing large amounts of ozone and its precursors, but with caveat that aerosol concentrations hinder formation of ozone to its potential due to its reduction in photolysis rates.


2010 ◽  
Vol 3 (4) ◽  
pp. 2291-2314
Author(s):  
G. Sarwar ◽  
K. W. Appel ◽  
A. G. Carlton ◽  
R. Mathur ◽  
K. Schere ◽  
...  

Abstract. A new condensed toluene mechanism is incorporated into the Community Multiscale Air Quality Modeling system. Model simulations are performed using the CB05 chemical mechanism containing the existing (base) and the new toluene mechanism for the western and eastern US for a summer month. With current estimates of tropospheric emission burden, the new toluene mechanism increases monthly mean daily maximum 8-h ozone by 1.0–3.0 ppbv in Los Angeles, Portland, Seattle, Chicago, Cleveland, northeastern US, and Detroit compared to that with the base toluene chemistry. It reduces model mean bias for ozone at elevated observed ozone mixing ratios. While the new mechanism increases predicted ozone, it does not enhance ozone production efficiency. Sensitivity study suggests that it can further enhance ozone if elevated toluene emissions are present. While changes in total fine particulate mass are small, predictions of in-cloud SOA increase substantially.


2016 ◽  
Author(s):  
Imran A. Girach ◽  
Narendra Ojha ◽  
Prabha R. Nair ◽  
Andrea Pozzer ◽  
Yogesh K. Tiwari ◽  
...  

Abstract. We present ship-borne measurements of surface ozone, carbon monoxide and methane over the Bay of Bengal (BoB), the first time such measurements have been taken during the summer monsoon season, as a part of the Continental Tropical Convergence Zone (CTCZ) experiment during 2009. O3, CO, and CH4 mixing ratios exhibited significant spatial and temporal variability in the ranges of 8–54 nmol mol−1, 50–200 nmol mol−1, and 1.57–2.15 µmol mol−1, with means of 29.7 ± 6.8 nmol mol−1, 96 ± 25 nmol mol−1, and 1.83 ± 0.14 µmol mol−1, respectively. The average mixing ratios of trace gases over northern BoB (O3: 30 ± 7 nmol mol−1, CO: 95 ± 25 nmol mol−1, CH4: 1.86 ± 0.12 µmol mol−1), in airmasses from northern or central India, did not differ much from those over central BoB (O3: 27 ± 5 nmol mol−1, CO: 101 ± 27 nmol mol−1, CH4: 1.72 ± 0.14 µmol mol−1), in airmasses from southern India. Spatial variability is observed to be most significant for CH4. The ship-based observations, in conjunction with backward air trajectories and ground-based measurements over the Indian region, are analyzed to estimate a net ozone production of 1.5–4 nmol mol−1 day−1 in the outflow. Ozone mixing ratios over the BoB showed large reductions (by ~ 20 nmol mol−1) during four rainfall events. Temporal changes in the meteorological parameters, in conjunction with ozone vertical profiles, indicate that these low ozone events are associated with downdrafts of free-tropospheric ozone-poor airmasses. While the observed variations in O3 and CO are successfully reproduced using the Weather Research and Forecasting model with Chemistry (WRF-Chem), this model overestimates mean concentrations by about 20 %, generally overestimating O3 mixing ratios during the rainfall events. Analysis of the chemical tendencies from model simulations for a low-O3 event on August 10, 2009, captured successfully by the model, shows the key role of horizontal advection in rapidly transporting ozone-rich airmasses across the BoB. Our study fills a gap in the availability of trace gas measurements over the BoB, and when combined with data from previous campaigns, reveals large seasonal amplitude (~ 39 and ~ 207 nmol mol−1 for O3 and CO, respectively) over the northern BoB.


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