High Ozone Mixing Ratios Research Articles

New particle formation at a peri-urban agricultural site

New Particle Formation (NPF) is a major source of ultrafine particles that affect both air quality and climate. Despite emissions from agricultural activities having a strong potential to lead to NPF, little is known about NPF within agricultural environments. The aim of the present study was to investigate the occurrence of NPF events at an agricultural site, and any potential relationship between agricultural emissions and NPF events. A field campaign was conducted for 3 months at the FR-Gri-ICOS site (France), at an experimental farm 25 km west of Paris city centre.16 NPF events have been identified from the analysis of particle number size distributions; 8 during the daytime, and 8 during the night-time. High solar radiation and ozone mixing ratios were observed during the days NPF occurred, suggesting photochemistry plays a key role in daytime NPF. These events were also associated with higher levels of VOCs such as isoprene, methanol, or toluene compared to non-event days. However, ammonia levels were lower during daytime NPF events, contributing to the hypothesis that daytime NPF events were not related to agricultural activities.On the other hand, temperature and ozone were lower during the nights when NPF events were observed, whereas relative humidity was higher. During these nights, higher concentrations of NO2 and ammonia were observed. As a result, agricultural activities, in particular the spreading of fertiliser on surrounding crops, are suspected to contribute to night-time NPF events.Finally, all the identified NPF events were also observed at SIRTA monitoring station 20 km from the FR-Gri ICOS site, showing that both night-time and daytime NPF events were regional processes. We hypothesise that night-time NPF may be related to fertiliser spreading over a regional scale, as opposed to the local activities at the farm. To our knowledge, this is the first time night-time NPF has been observed in the agricultural context.

Wintertime haze and ozone at Dinosaur National Monument

ABSTRACT Dinosaur National Monument (DINO) is located near the northeastern edge of the Uinta Basin and often experiences elevated levels of wintertime ground-level ozone. Previous studies have shown that high ozone mixing ratios in the Uinta Basin are driven by elevated levels of volatile organic compounds (VOCs) and nitrogen oxides (NOx) from regional oil and gas development coupled with temperature inversions and enhanced photochemistry from persistent snow cover. Here, we show that persistent snow cover and temperature inversions, along with abundant ammonia, also lead to wintertime haze in this region. A study was conducted at DINO from November 2018 through May 2020 where ozone, speciated fine and coarse aerosols, inorganic gases, and VOCs were measured. Three National Ambient Air Quality Standards (NAAQS) ozone exceedances were observed in the first winter, and no exceedances were observed in the second winter. In contrast, elevated levels of particulate matter were observed both winters, with 24-h averaged particle light extinction exceeding 100 Mm−1. These haze events were dominated by ammonium nitrate, and particulate organics were highly correlated with ammonium nitrate. Ammonium nitrate formation was limited by nitric acid in winter. As such, reductions in regional NOx emissions should reduce haze levels and improve visibility at DINO in winter. Long-term measurements of particulate matter from nearby Vernal, Utah, suggest that visibility impairment is a persistent issue in the Uinta Basin in winter. From April through October 2019, relatively clean conditions occurred, with average particle extinction of ~10 Mm−1. During this period, ammonium nitrate concentrations were lower by more than an order of magnitude, and contributions from coarse mass and soil to haze levels increased. VOC markers indicated that the high levels of observed pollutants in winter were likely from local sources related to oil and gas extraction activities. Implications: Elevated ground-level ozone and haze levels were observed at Dinosaur National Monument in winter. Haze episodes were dominated by ammonium nitrate, with 24-h averaged particle light extinction exceeding 100 Mm−1, reducing visual range near the surface to ~35 km. Despite elevated ammonium nitrate concentrations, additional gas-phase ammonia was available, such that any increase in NOx emissions in the region is likely to lead to even greater haze levels.

Iodide CIMS and <i>m</i>∕<i>z</i> 62: the detection of HNO<sub>3</sub> as NO<sub>3</sub><sup>−</sup> in the presence of PAN, peroxyacetic acid and ozone

Abstract. Chemical ionisation mass spectrometry (CIMS) using I− (the iodide anion), hereafter I-CIMS, as a primary reactant ion has previously been used to measure NO3 and N2O5 both in laboratory and field experiments. We show that reports of large daytime mixing ratios of NO3 and N2O5 (both usually present in detectable amounts only at night) are likely to be heavily biased by the ubiquitous presence of HNO3 in the troposphere and lower stratosphere. We demonstrate in a series of laboratory experiments that the CIMS detection of HNO3 at m/z 62 using I− ions is efficient in the presence of peroxy acetyl nitric anhydride (PAN) or peroxyacetic acid (PAA) and especially O3. We have characterised the dependence of the sensitivity to HNO3 detection on the presence of acetate anions (CH3CO2-, m/z 59, from either PAN or PAA). The loss of CH3CO2- via conversion to NO3- in the presence of HNO3 may represent a significant bias in I-CIMS measurements of PAN and PAA in which continuous calibration (e.g. via addition of isotopically labelled PAN) is not carried out. The greatest sensitivity to HNO3 at m/z 62 is achieved in the presence of ambient levels of O3 whereby the thermodynamically disfavoured, direct reaction of I− with HNO3 to form NO3- is bypassed by the formation of IOx-, which reacts with HNO3 to form, for example, iodic acid and NO3-. The ozone and humidity dependence of the detection of HNO3 at m/z 62 was characterised in laboratory experiments and applied to daytime, airborne measurements in which good agreement with measurements of the I−(HNO3) cluster ion (specific for HNO3 detection) was obtained. At high ozone mixing ratios, we show that the concentration of I− ions in our ion–molecule reactor (IMR) is significantly depleted. This is not reflected by changes in the measured I− signal at m/z 127 as the IOx- formed does not survive passage through the instrument but is likely detected after fragmentation to I−. This may result in a bias in measurements of trace gases using I-CIMS in stratospheric air masses unless a calibration gas is continuously added or the impact of O3 on sensitivity is characterised.

Does Organization in Turbulence Influence Ozone Removal by Deciduous Forests?

AbstractDry deposition is an important sink of tropospheric ozone and influences background and episodic ozone air pollution. Plant canopies remove ozone through uptake by plant stomata, leaf cuticles, and soil. Stomatal uptake of ozone injures vegetation, thereby altering local‐to‐global water and carbon cycling. Observed ozone fluxes are used to inform dry deposition parameterizations in chemical transport models but represent the net influence of several poorly constrained processes. Advancing understanding of the processes controlling dry deposition is key for building predictive ability of the terrestrial ozone sink and plant damage. Here, we constrain the influence of spatial structure in turbulence on ozone dry deposition with large eddy simulation coupled to a multilayer canopy model. We investigate whether organized turbulence separates areas of efficient leaf uptake from areas of high or low ozone mixing ratios. We simulate summertime midday conditions at three homogenous deciduous forests with varying leaf area, soil moisture, and ambient humidity. Sensitivity simulations perturb atmospheric stability, parameters related to ozone dry deposition, how quickly stomata respond to local atmospheric variations, and entrainment of ozone from atmospheric boundary layer growth. Overall, we find a low covariance between ozone and leaf uptake, in part due to counteracting influences from micrometeorological variations on ozone and leaf uptake individually versus the influence of leaf uptake on ozone. The low covariance between ozone and leaf uptake suggests that dry deposition parameterizations and interpretations of ozone flux observations can ignore the influence of organized turbulence on dry deposition.

The influence of typhoons on atmospheric composition deduced from IAGOS measurements over Taipei

Abstract. The research infrastructure IAGOS (In-Service Aircraft for a Global Observing System) equips commercial aircraft with instruments to monitor the composition of the atmosphere during flights around the world. In this article, we use data from two China Airlines aircraft based in Taipei (Taiwan) which provided daily measurements of ozone, carbon monoxide and water vapour throughout the summer of 2016. We present time series, from the surface to the upper troposphere, of ozone, carbon monoxide and relative humidity near Taipei, focusing on periods influenced by the passage of typhoons. We examine landing and take-off profiles in the vicinity of tropical cyclones using ERA-5 reanalyses to elucidate the origin of the anomalies in the vertical distribution of these chemical species. Results indicate a high ozone content in the upper- to middle-troposphere track of the storms. The high ozone mixing ratios are generally correlated with potential vorticity and anti-correlated with relative humidity, suggesting stratospheric origin. These results suggest that tropical cyclones participate in transporting air from the stratosphere to troposphere and that such transport could be a regular feature of typhoons. After the typhoons passed Taiwan, the tropospheric column was filled with substantially lower ozone mixing ratios due to the rapid uplift of marine boundary layer air. At the same time, the relative humidity increased, and carbon monoxide mixing ratios fell. Locally, therefore, the passage of typhoons has a positive effect on air quality at the surface, cleansing the atmosphere and reducing the mixing ratios of pollutants such as CO and O3.

High tropospheric ozone in Lhasa within the Asian summer monsoon anticyclone in 2013: influence of convective transport and stratospheric intrusions

Abstract. Balloon-borne measurements of ozone in Lhasa (29.66∘ N, 91.14∘ E; 3650 m above sea level) in August 2013 are investigated using backward trajectory calculations performed with the Chemical Lagrangian Model of the Stratosphere (CLaMS). Measurements show three time periods characterized by high ozone mixing ratios (OMRs) in the troposphere on 8, 11, and 18–20 August 2013 during the Asian summer monsoon (ASM) season. Here, we verified two different sources for the enhanced ozone values in the troposphere. First, transport of polluted air from the boundary layer, and second downward transport from the stratosphere by stratospheric intrusions. Air pollution from South Asia through convective and long-range transport plays a key role in enhancing middle tropospheric OMRs up to 90 % on 8 August and up to 125 % on 11 August 2013 compared to monthly mean ozone of August 2013. Stratospheric air intruded from the northern high-latitudes to the southeastern flank of the ASM anticyclone to the troposphere and is identified as the source of enhanced ozone according to backward trajectory calculation and satellite measurements by the Ozone Monitoring Instrument (OMI) and the Atmospheric Infrared Sounder (AIRS). Air parcels with high ozone moved from the high-latitude lower stratosphere to the middle and upper troposphere. These air parcels are then transported to Lhasa over long distances and enhanced upper and middle tropospheric ozone over Lhasa during 18–20 August 2013. Our findings demonstrate that the strong variability of ozone within the ASM anticyclone in the free troposphere is caused by transport from very different regions of the atmosphere.

Characteristics of volatile organic compounds, NO2, and effects on ozone formation at a site with high ozone level in Chengdu

Chengdu is a megacity in the southwest of China with high ozone (O3) mixing ratio. Observation of volatile organic compounds (VOCs), NO2 and O3 with high temporal resolution was conducted in Chengdu to investigate the chemical processes and causes of high O3 levels. The hourly mixing ratios of VOCs, NO2, and O3 were monitored by an online system from 28 August to 7 October, 2016. According to meteorological conditions, Chengdu, with relative warm weather and low wind speed, is favorable to O3 formation. Part of the O3 in Chengdu may be transported from the downtown area. In O3 episodes, the average mixing ratios of NO2 and O3 were 20.20 ppbv and 47.95 ppbv, respectively. In non-O3 episodes, the average mixing ratios of NO2 and O3 were 16.38 ppbv and 35.15 ppbv, respectively. The average mixing ratio of total VOCs (TVOCs) was 40.29 ppbv in non-O3 episodes, which was lower than that in O3 episodes (53.19 ppbv). Alkenes comprised 51.7% of the total O3 formation potential (OFP) in Chengdu, followed by aromatics which accounted for 24.2%. Ethylene, trans-pentene, propene, and BTEX (benzene, ethylbenzene, toluene, m/p-xylene, o-xylene) were also major contributors to the OFP in Chengdu. In O3 episodes, intensive secondary formations were observed during the campaign. Oxygenated VOCs (OVOCs), such as acetone, Methylethylketone (MEK), and Methylvinylketone (MVK) were abundant. Isoprene rapidly converted to MVK and Methacrolein (MACR) during O3 episodes. Acetone was mainly the oxidant of C3-C5 hydrocarbons.

Low modeled ozone production suggests underestimation of precursor emissions (especially NO<sub><i>x</i></sub>) in Europe

Abstract. High surface ozone concentrations, which usually occur when photochemical ozone production takes place, pose a great risk to human health and vegetation. Air quality models are often used by policy makers as tools for the development of ozone mitigation strategies. However, the modeled ozone production is often not or not enough evaluated in many ozone modeling studies. The focus of this work is to evaluate the modeled ozone production in Europe indirectly, with the use of the ozone–temperature correlation for the summer of 2010 and to analyze its sensitivity to precursor emissions and meteorology by using the regional air quality model, the Comprehensive Air Quality Model with Extensions (CAMx). The results show that the model significantly underestimates the observed high afternoon surface ozone mixing ratios (≥ 60 ppb) by 10–20 ppb and overestimates the lower ones (< 40 ppb) by 5–15 ppb, resulting in a misleading good agreement with the observations for average ozone. The model also underestimates the ozone–temperature regression slope by about a factor of 2 for most of the measurement stations. To investigate the impact of emissions, four scenarios were tested: (i) increased volatile organic compound (VOC) emissions by a factor of 1.5 and 2 for the anthropogenic and biogenic VOC emissions, respectively, (ii) increased nitrogen oxide (NOx) emissions by a factor of 2, (iii) a combination of the first two scenarios and (iv) increased traffic-only NOx emissions by a factor of 4. For southern, eastern, and central (except the Benelux area) Europe, doubling NOx emissions seems to be the most efficient scenario to reduce the underestimation of the observed high ozone mixing ratios without significant degradation of the model performance for the lower ozone mixing ratios. The model performance for ozone–temperature correlation is also better when NOx emissions are doubled. In the Benelux area, however, the third scenario (where both NOx and VOC emissions are increased) leads to a better model performance. Although increasing only the traffic NOx emissions by a factor of 4 gave very similar results to the doubling of all NOx emissions, the first scenario is more consistent with the uncertainties reported by other studies than the latter, suggesting that high uncertainties in NOx emissions might originate mainly from the road-transport sector rather than from other sectors. The impact of meteorology was examined with three sensitivity tests: (i) increased surface temperature by 4 ∘C, (ii) reduced wind speed by 50 % and (iii) doubled wind speed. The first two scenarios led to a consistent increase in all surface ozone mixing ratios, thus improving the model performance for the high ozone values but significantly degrading it for the low ozone values, while the third scenario had exactly the opposite effects. Overall, the modeled ozone is predicted to be more sensitive to its precursor emissions (especially traffic NOx) and therefore their uncertainties, which seem to be responsible for the model underestimation of the observed high ozone mixing ratios and ozone production.

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

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 2km 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 3km height. Furthermore, the capability of indicators to distinguish O3-precursor sensitivity along the vertical O3 profiles was investigated. Two sensitive scenarios, which had cut 30% anthropogenic NOX or VOC emissions, showed that O3-precursor indicators, specifically the ratios of O3/NOy, H2O2/HNO3 or H2O2/NOZ, could partly distinguish the O3-precursor sensitivity between VOCs-sensitive and NOx-sensitive along the vertical profiles. In urban area, the O3-precursor relationship transferred from VOCs-sensitive within the boundary layer to NOx-sensitive at approximately 1-3km above ground height, further confirming the dominant roles of transportation and photochemical production in high O3 peaks at the near-ground layer and 2km above ground height, respectively.

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

Abstract. 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 × 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 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.

Study of surface ozone at Port Blair, India, a remote marine station in the Bay of Bengal

This paper presents seasonal variation of surface ozone monitored continuously at site of the meteorological observatory at Port Blair, a maritime site of the Bay of Bengal for the period of August, 2005–March, 2007. Present observation depicts the characteristics of surface ozone at the remote marine site and the long range transport of pollutants from three different sides i.e., Indian Subcontinent, South East Asia and Indian Ocean. Very high ozone mixing ratio (~70–80ppbv) is occasionally observed during March and November at this site. A campaign mode of observation of trace gases (surface ozone, CO, NOx, CO2), aerosol concentration and its size, UV radiation at Port Blair was made to understand the role of transport on pollutants during March 16–26, 2002. During this period of observation, a near zero surface ozone of different time scales (~few hours) has been observed several times during the period of midnight to early morning. Simultaneously NOx (NO+NO2) (~40ppbv) and carbon monoxide was observed very high (300–600ppbv) during this period. Source of this high pollutant are not expected at this remote marine sites although wind patterns, 7-days isentropic back Trajectory analysis and MATCH Model output suggest that polluted air mass has come from eastern side of Indian subcontinent.

Nighttime ozone variability in the high latitude winter mesosphere

AbstractWe use satellite observations and a numerical model to investigate polar nighttime ozone at the secondary maximum, around 90–95 km. Observations from the MIPAS and SABER satellite instruments indicate that the highest ozone mixing ratios are seen during the late fall to early winter period in both hemispheres and for all years examined. Simulations using the Whole Atmosphere Community Climate Model (WACCM) find qualitatively the same seasonal evolution. Analysis of WACCM results shows that the high ozone concentration is due in part to the relatively quiet dynamical conditions in early winter. The mean circulation, which brings warmer temperatures and higher concentrations of H, is weaker in early winter than during middle and late winter. H in the late fall to early winter period drops to the lowest levels seen during the year due to lack of a source from photochemistry, weak transport into the region by the mean circulation, and continual loss due to diffusive separation. The low concentration of H leads to higher ozone.

DIAL measurement of lower tropospheric ozone over Saga (33.24° N, 130.29° E), Japan, and comparison with a chemistry–climate model

Abstract. We have improved an ozone DIfferential Absorption Lidar (DIAL) system, originally developed in March 2010. The improved DIAL system consists of a Nd:YAG laser and a 2 m Raman cell filled with 8.1 × 105 Pa of CO2 gas which generate four Stokes lines (276, 287, 299, and 312 nm) of stimulated Raman scattering, and two receiving telescopes with diameters of 49 and 10 cm. Using this system, 44 ozone profiles were observed in the 1–6 km altitude range over Saga (33.24° N, 130.29° E) in 2012. High-ozone layers were observed at around 2 km altitude during April and May. Ozone column amounts within the 1–6 km altitude range were almost constant (19.1 DU on average) from January to March, and increased to 26.7 DU from late April to July. From mid-July through August, ozone column amounts decreased greatly to 14.3 DU because of exchanges of continental and maritime air masses. Then in mid-September they increased again to 22.1 DU within 1−6 km, and subsequently decreased slowly to 17.3 DU, becoming almost constant by December. The Meteorological Research Institute's chemistry–climate model version 2 (MRI-CCM2) successfully predicted most of these ozone variations with the following exceptions. MRI-CCM2 could not predict the high-ozone volume mixing ratios measured at around 2 km altitude on 5 May and 11 May, possibly in part because emissions were assumed in the model to be constant (climatological data were used). Ozone volume mixing ratios predicted by MRI-CCM2 were low in the 2–6 km range on 7 July and high in the 1–4 km range on 19 July compared with those measured by DIAL.

Air quality over Europe: modelling gaseous and particulate pollutants

Abstract. Air quality over Europe using Models-3 (i.e., CMAQ, MM5, SMOKE) modelling system is performed for winter (i.e., January 2006) and summer (i.e., July 2006) months with the 2006 TNO gridded anthropogenic emissions database. Higher ozone mixing ratios are predicted in southern Europe while higher NO2 levels are simulated over western Europe. Elevated SO2 values are simulated over eastern Europe and higher PM2.5 concentrations over eastern and western Europe. Regional average results suggest that NO2 and PM2.5 are underpredicted, SO2 is overpredicted, while Max8hrO3 is overpredicted for low mixing ratios and is underpredicted for the higher mixing ratios. However, in a number of countries observed and predicted values are in good agreement for the pollutants examined here. Speciated PM2.5 components suggest that NO3 is dominant during winter over western Europe and in a few eastern countries due to the high NO2 mixing ratios. During summer NO3 is dominant only in regions with elevated NH3 emissions. For the rest of the domain SO4 is dominant. Low OC concentrations are simulated mainly due to the uncertain representation of SOA formation.

Ozone variations over the northern subtropical region revealed by ozonesonde observations in Hanoi

Seasonal and subseasonal variations in the ozone mixing ratio (OMR) are investigated by using continuous 7 year ozonesonde data from Hanoi (21°N, 106°E), Vietnam. The mean seasonal variations for the 7 years show large amplitude at the upper troposphere and lower stratosphere (UTLS) region (10–18 km) and at the lower troposphere (around 3 km) with standard deviations normalized by the annual mean value of about 30% for both regions. In the UTLS region, the seasonal variation in the OMR shows a minimum in winter and a maximum in spring to summer. The variation seems to be caused by the seasonal change in horizontal transport. Low OMR air masses are transported from the equatorial troposphere in winter by the anticyclonic flow associated with the equatorial convections, and high OMR air masses are transported from the midlatitude stratosphere in summer possibly due to Rossby wave breakings in the UT region and anticyclonic circulation associated with the Tibetan High in the LS region. In the lower troposphere, a spring maximum is found at 3 km height. Biomass burning and tropopause foldings are suggested as possible causes of this maximum. Subseasonal variations in the OMR show large amplitude in the UTLS region (at around 15 km) and in the boundary layer (below 1 km) with the standard deviations normalized by the annual mean larger than 40%. The OMR variations in the winter UTLS region have a negative correlation with the meridional wind. This relation indicates that the low OMRs observed at Hanoi has been transported from the equatorial region.

Ozone distribution in the lower troposphere over complex terrain in Central Chile

Observations were performed in 12 communities of Central Chile in order to determine the horizontal gradients of ozone in the Santiago Basin and surrounding valleys. Higher ozone mixing ratios were found northeast of the Santiago Basin and included east of the Aconcagua Valley (~70 km from Santiago) suggesting that photochemical pollution produced in Santiago is capable of passing through the Chacabuco mountain chain (~1.3 km) and have impact downwind from the regions with the largest NOx and VOC emissions. To complement existing surface observations, ozonesonde and tethersonde campaigns were performed in the Santiago Basin and the Aconcagua Valley. The results suggest ozone can accumulate in layers aloft (e.g., >102 ppb at 2 km) similarly to layers observed in complex topography coastal regions like Southern California. Layers of significant ozone concentrations having a near surface origin were observed above the mixed layer and below the subsidence inversion base. We propose that the ozone in this residual layer can be transported large distances (at least to 70 km) to further penetrate into the local environment under conditions of a well‐mixed boundary layer.

Statistical analysis of aerosol species, trace gasses, and meteorology in Chicago

Both canonical correlation analysis (CCA) and principal component analysis (PCA) were applied to atmospheric aerosol and trace gas concentrations and meteorological data collected in Chicago during the summer months of 2002, 2003, and 2004. Concentrations of ammonium, calcium, nitrate, sulfate, and oxalate particulate matter, as well as, meteorological parameters temperature, wind speed, wind direction, and humidity were subjected to CCA and PCA. Ozone and nitrogen oxide mixing ratios were also included in the data set. The purpose of statistical analysis was to determine the extent of existing linear relationship(s), or lack thereof, between meteorological parameters and pollutant concentrations in addition to reducing dimensionality of the original data to determine sources of pollutants. In CCA, the first three canonical variate pairs derived were statistically significant at the 0.05 level. Canonical correlation between the first canonical variate pair was 0.821, while correlations of the second and third canonical variate pairs were 0.562 and 0.461, respectively. The first canonical variate pair indicated that increasing temperatures resulted in high ozone mixing ratios, while the second canonical variate pair showed wind speed and humidity's influence on local ammonium concentrations. No new information was uncovered in the third variate pair. Canonical loadings were also interpreted for information regarding relationships between data sets. Four principal components (PCs), expressing 77.0 % of original data variance, were derived in PCA. Interpretation of PCs suggested significant production and/or transport of secondary aerosols in the region (PC1). Furthermore, photochemical production of ozone and wind speed's influence on pollutants were expressed (PC2) along with overall measure of local meteorology (PC3). In summary, CCA and PCA results combined were successful in uncovering linear relationships between meteorology and air pollutants in Chicago and aided in determining possible pollutant sources.

Influence of transport and mixing in autumn on stratospheric ozone variability over the Arctic in early winter

Abstract. Early winter ozone mixing ratios in the Arctic middle stratosphere show an interannual variability of about 10%. We show that ozone variability in early January is caused by dynamical processes during Arctic polar vortex formation in autumn (September to December). Observational data from satellites and ozone sondes are used in conjunction with simulations of the chemistry and transport model ATLAS to examine the relationship between the meridional and vertical origin of air enclosed in the polar vortex and its ozone amount. For this, we use a set of artificial model tracers to deduce the origin of the air masses in the vortex in January in latitude and altitude in September. High vortex mean ozone mixing ratios are correlated with a high fraction of air from low latitudes enclosed in the vortex and a high fraction of air that experienced small net subsidence (in a Lagrangian sense). As a measure for the strength of the Brewer-Dobson circulation and meridional mixing in autumn, we use the Eliassen-Palm flux through the mid-latitude tropopause averaged from September to November. In the lower stratosphere, this quantity correlates well with the origin of air enclosed in the vortex and reasonably well with the ozone amount in early winter.

Trends of AOT40 at three sites in the Catalan Pyrenees over the last 16 years

Ozone mixing ratios were monitored at three stations at different altitudes along the Catalan Pyrenees from 1994 to 2009. The AOT40 greatly exceeded the critical level for the protection of forest and semi-natural vegetation set by the UNECE’s CLRTAP and the target value and long-term objective for the protection of vegetation set by the European Directive 2008/50/EC. The AOT40 showed an overall increasing trend over time with a slight decrease during the last 3 years, although longer-term records of ozone levels are required before affirming with certainty a declining or stabilising trend. These results indicate that plant life in the Pyrenean region can be at risk of ozone damage due to the high ozone mixing ratios detected. Nevertheless, more effort is warranted to determine the uptake of ozone by vegetation in this mountainous range. An ozone flux-based index that takes into account the local environmental conditions, plant phenology, and nocturnal uptake of ozone would provide a more accurate assessment of the risk from ozone for the particular vegetation in each area.

Measurements of aerosol optical properties in central Tokyo during summertime using cavity ring-down spectroscopy: Comparison with conventional techniques

A highly sensitive cavity ring-down spectrometer (CRDS) was used to monitor the aerosol extinction coefficient at 532 nm. The performance of the spectrometer was evaluated using measurements of nearly monodisperse polystyrene particles with diameters between 150 and 500 nm. By comparing the observed results with those determined using Mie theory, the accuracy of the CRDS instrument was determined to be >97%, while the upper limit for the precision of the instrument was estimated to be 0.6–3.5% (typically 2%), depending on the particle number concentration, which was in the range of 30–2300 particles cm −3. Simultaneous measurements of the extinction ( b ext), scattering ( b sca) and absorption ( b abs) coefficients of ambient aerosols were performed in central Tokyo from 14 August to 2 September 2007 using the CRDS instrument, two nephelometers and a particle/soot absorption photometer (PSAP), respectively. The value of b ext measured using the CRDS instrument was compared with the sum of the b sca and b abs values measured with a nephelometer and a PSAP, respectively. Good agreement between the b ext and b sca + b abs values was obtained except for data on days when high ozone mixing ratios (>130 ppbv) were observed. During the high-O 3 days, the values for b sca + b abs were ∼7% larger than the value for b ext, possibly because the value for b abs measured by the PSAP was overestimated due to interference from coexisting non-absorbing aerosols such as secondary organic aerosols.