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Baseline levels and trends of ground level ozone in Canada and the United States

A statistical method was developed to extract baseline levels of ground level ozone in Canada and the US, and to quantify the temporal changes of baseline ozone levels on annual, seasonal, diurnal and decadal scales for the period 1997 to 2006 based on ground-level observations from 97 non-urban monitoring sites. Baseline ozone is defined here as ozone measured at a given site in the absence of strong local influences. The quantification of baseline levels involved using a Principal Component Analyses (PCA) to derive groups of commonly-varying sites in contiguous regions by season, followed by using backward air parcel trajectories to systematically select ozone mixing ratios associated with the baseline condition in each of the PCA-derived regions. Decadal trends were estimated by season for each of the regions using a generalized linear mixed model (GLMM). Baseline ozone mixing ratios determined by this method were found to vary geographically and seasonally. For the 1997–2006 period, baseline mixing ratios were calculated for annual and seasonal periods in seven regions of North America based on multi-site multi-year averages of the baseline data sets. The annual average (±1 standard deviation) baseline mixing ratios for the regions are as follows: Continental Eastern Canada=30±9 ppb, Continental Eastern US=30±10 ppb, Coastal Eastern Canada=27±9 ppb, Coastal Western Canada=19±10 ppb; Coastal Western US=39±10 ppb, Continental Western Canada=28±10 ppb and Continental Western US=46±7 ppb. Trends in the baseline mixing ratios were also found to vary by season and by geographical region. On a decadal scale, increasing baseline ozone trends (temperature-adjusted) were observed in all seasons along the Pacific coasts of Canada and the US, although the trends in California were not statistically significant. In the coastal zone of Pacific Canada, positive trends were found with a rate of increase of 0.28±0.26, 0.72±0.55, and 0.93±0.41 ppb/a in spring (MAM), summer (JJA) and winter (DJF), respectively. In the Atlantic coastal region, the trends were also positive in 3 of the 4 seasons (but only significantly so in MAM). In the high ozone precursor emission areas of the Eastern United States, decadal trends in baseline ozone are, in general, negative in the spring, summer and fall and appear to be controlled by the strong within-region changes induced by decreasing ozone precursor emissions.
Comparison of TOMS retrievals and UVMRP measurements of surface spectral UV radiation in the United States

Surface noontime spectral ultraviolet (UV) irradiances during May-September of 2000–2004 from the total ozone mapping spectrometer (TOMS) satellite retrievals are systematically compared with the ground measurements at 27 climatological sites maintained by the USDA UV-B Monitoring and Research Program. The TOMS retrievals are evaluated by two cloud screening methods and local air quality conditions to determine their bias dependencies on spectral bands, cloudiness, aerosol loadings, and air pollution. Under clear-sky conditions, TOMS retrieval biases vary from −3.4% (underestimation) to 23.6% (overestimation). Averaged over all sites, the relative mean biases for 305, 311, 325, and 368 nm are respectively 15.4, 7.9, 7.6, and 7.0% (overestimation). The bias enhancement for 305 nm by approximately twice that of other bands likely results from absorption by gaseous pollutants (SO2, O3), and aerosols that are not included in the TOMS algorithm. For all bands, strong positive correlations of the TOMS biases are identified with aerosol optical depth, which explains nearly 50% of the variances of TOMS biases. The more restrictive in-situ cloud screening method reduces the biases by 3.4–3.9% averaged over all sites. This suggests that the TOMS biases from the in-situ cloud contamination may account for approximately 25% for 305 nm and 50% for other bands of the total bias. The correlation coefficients between total-sky and clear-sky biases across 27 sites are 0.92, 0.89, 0.83, and 0.78 for 305, 311, 325, and 368 nm, respectively. The results show that the spatial characteristics of the TOMS retrieval biases are systematic, representative of both clear and total-sky conditions.
Observations of OH and HO2 radicals over West Africa

The hydroxyl radical (OH) plays a key role in the oxidation of trace gases in the troposphere. However, observations of OH and the closely related hydroperoxy radical (HO2) have been sparse, especially in the tropics. Based on a low-pressure laser-induced fluorescence technique (FAGE – Fluorescence Assay by Gas Expansion), an instrument has been developed to measure OH and HO2 aboard the Facility for Airborne Atmospheric Measurement (FAAM) BAe-146 research aircraft. During the African Monsoon Multidisciplinary Analyses (AMMA) campaign, observations of OH and HO2 (HOx) were made in the boundary layer and free troposphere over West Africa on 13 flights during July and August 2006. Mixing ratios of both OH and HO2 were found to be highly variable, but followed a diurnal cycle: OH varied from 1.3 pptv to below the instrumental limit of detection, with a median mixing ratio of 0.17 pptv. HO2 varied from 42.7 pptv to below the limit of detection, with a median mixing ratio of 8.0 pptv. A median HO2/OH ratio of 95 was observed. Daytime OH observations were compared with the primary production rate of OH from ozone photolysis in the presence of water vapour. Daytime HO2 observations were generally reproduced by a simple steady-state HOx calculation, where HOx was assumed to be formed from the primary production of OH and lost through HO2 self-reaction. Deviations between the observations and this simple model were found to be grouped into a number of specific cases: (a) within cloud, (b) in the presence of high levels of isoprene in the boundary layer and (c) within a biomass burning plume. HO2 was sampled in and around cloud, with significant short-lived reductions of HO2 observed. Up to 9 pptv of HO2 was observed at night, with HO2 above 6 pptv observed at altitudes above 6 km. In the forested boundary layer, HO2 was underestimated by a steady state calculation at altitudes below 500 m but overestimated between 500 m and 2 km. In a biomass burning plume, observed HO2 concentrations were significantly below those calculated.
Effects of ship wakes on ocean brightness and radiative forcing over ocean

Changes in surface albedo represent one of the main forcing agents that can counteract, to some extent, the positive forcing from increasing greenhouse gas concentrations. Here, we quantify the changes in ocean surface albedo from ship wakes and provide an estimate of radiative forcing over the global oceans. Our analysis is based on airborne radiation measurements over the Pacific Ocean near the California coast, where we determined that a ship wake increases reflected sunlight by more than 100% in some cases. Based on registered ships of 100 000 gross tonnage (GT), and assuming a global distribution of 30 000 ships, we estimated the global radiative forcing of ship wakes to be −0.003 Wm−2, which is comparable to the forcing of aircraft contrails, but not anticipated in the Intergovernmental Panel on Climate Change (IPCC) 2007 assessment report. From these results, we conclude that the climate impacts associated with ships will become more significant with growing ship traffic.
Observations of elevated formaldehyde over a forest canopy suggest missing sources from rapid oxidation of arboreal hydrocarbons

To better understand the processing of biogenic VOCs (BVOCs) in the pine forests of the US Sierra Nevada, we measured HCHO at Blodgett Research Station using Quantum Cascade Laser Spectroscopy (QCLS) during the Biosphere Effects on Aerosols and Photochemistry Experiment (BEARPEX) of late summer 2007. Four days of the experiment exhibited particularly copious HCHO, with midday peaks between 15–20 ppbv, while the other days developed delayed maxima between 8–14 ppbv in the early evening. From the expansive photochemical data set, we attempt to explain the observed HCHO concentrations by quantifying the various known photochemical production and loss terms in its chemical budget. Overall, known chemistry predicts a factor of 3–5 times less HCHO than observed. By examining diurnal patterns of the various budget terms we conclude that, during the high HCHO period, local, highly reactive oxidation chemistry produces an abundance of formaldehyde at the site. The results support the hypothesis of previous work at Blodgett Forest suggesting that large quantities of oxidation products, observed directly above the ponderosa pine canopy, are evidence of profuse emissions of very reactive volatile organic compounds (VR-VOCs) from the forest. However, on the majority of days, under generally cooler and more moist conditions, lower levels of HCHO develop primarily influenced by the influx of precursors transported into the region along with the Sacramento plume.
Quantifying the contributions to stratospheric ozone changes from ozone depleting substances and greenhouse gases

A state-of-the-art chemistry climate model coupled to a three-dimensional ocean model is used to produce three experiments, all seamlessly covering the period 1950–2100, forced by different combinations of long-lived Greenhouse Gases (GHGs) and Ozone Depleting Substances (ODSs). The experiments are designed to quantify the separate effects of GHGs and ODSs on the evolution of ozone, as well as the extent to which these effects are independent of each other, by alternately holding one set of these two forcings constant in combination with a third experiment where both ODSs and GHGs vary. We estimate that up to the year 2000 the net decrease in the column amount of ozone above 20 hPa is approximately 75% of the decrease that can be attributed to ODSs due to the offsetting effects of cooling by increased CO2. Over the 21st century, as ODSs decrease, continued cooling from CO2 is projected to account for more than 50% of the projected increase in ozone above 20 hPa. Changes in ozone below 20 hPa show a redistribution of ozone from tropical to extra-tropical latitudes with an increase in the Brewer-Dobson circulation. In addition to a latitudinal redistribution of ozone, we find that the globally averaged column amount of ozone below 20 hPa decreases over the 21st century, which significantly mitigates the effect of upper stratospheric cooling on total column ozone. Analysis by linear regression shows that the recovery of ozone from the effects of ODSs generally follows the decline in reactive chlorine and bromine levels, with the exception of the lower polar stratosphere where recovery of ozone in the second half of the 21st century is slower than would be indicated by the decline in reactive chlorine and bromine concentrations. These results also reveal the degree to which GHG-related effects mute the chemical effects of N2O on ozone in the standard future scenario used for the WMO Ozone Assessment. Increases in the residual circulation of the atmosphere and chemical effects from CO2 cooling more than halve the increase in reactive nitrogen in the mid to upper stratosphere that results from the specified increase in N2O between 1950 and 2100.
The spatial distribution of mineral dust and its shortwave radiative forcing over North Africa: modeling sensitivities to dust emissions and aerosol size treatments

A fully coupled meteorology-chemistry-aerosol model (WRF-Chem) is applied to simulate mineral dust and its shortwave (SW) radiative forcing over North Africa. Two dust emission schemes (GOCART and DUSTRAN) and two aerosol models (MADE/SORGAM and MOSAIC) are adopted in simulations to investigate the modeling sensitivities to dust emissions and aerosol size treatments. The modeled size distribution and spatial variability of mineral dust and its radiative properties are evaluated using measurements (ground-based, aircraft, and satellites) during the AMMA SOP0 campaign from 6 January to 3 February of 2006 (the SOP0 period) over North Africa. Two dust emission schemes generally simulate similar spatial distributions and temporal evolutions of dust emissions. Simulations using the GOCART scheme with different initial (emitted) dust size distributions require ~40% difference in total emitted dust mass to produce similar SW radiative forcing of dust over the Sahel region. The modal approach of MADE/SORGAM retains 25% more fine dust particles (radius<1.25 μm) but 8% less coarse dust particles (radius>1.25 μm) than the sectional approach of MOSAIC in simulations using the same size-resolved dust emissions. Consequently, MADE/SORGAM simulates 11% higher AOD, up to 13% lower SW dust heating rate, and 15% larger (more negative) SW dust radiative forcing at the surface than MOSAIC over the Sahel region. In the daytime of the SOP0 period, the model simulations show that the mineral dust heats the lower atmosphere with an average rate of 0.8 ± 0.5 K day−1 over the Niamey vicinity and 0.5 ± 0.2 K day−1 over North Africa and reduces the downwelling SW radiation at the surface by up to 58 W m−2 with an average of 22 W m−2 over North Africa. This highlights the importance of including dust radiative impact in understanding the regional climate of North Africa. When compared to the available measurements, the WRF-Chem simulations can generally capture the measured features of mineral dust and its radiative properties over North Africa, suggesting that the model is suitable for more extensive simulations of dust impact on regional climate over North Africa.
Evaluation of a regional air quality forecast model for tropospheric NO2 columns using the OMI/Aura satellite tropospheric NO2 product

Results from a regional air quality forecast model, AIRPACT-3, are compared to OMI tropospheric NO2 integrated column densities for an 18 month period over the Pacific Northwest. AIRPACT column densities are well correlated (r=0.75) to cloud-free (<35%) retrievals of tropospheric NO2 for monthly averages without wildfires, but are poorly correlated (r=0.21) with significant model over-predictions for months with wildfires when OMI and AIRPACT are compared over the entire domain. AIRPACT predicts higher NO2 in some northwestern US urban areas, and lower NO2 in the Vancouver, BC urban area, when compared to OMI. Model results are spatially averaged to the daily OMI swath. The Dutch KNMI (DOMINO) and NASA (Standard Product) retrievals of tropospheric NO2 from OMI (Collection-3) are compared. The NASA product is shown to be significantly different than the KNMI tropospheric NO2 product. The average difference in tropospheric columns, after applying the averaging kernels of the respective products to the model results, is shown to be larger in the summer (±50%) than winter (±20%).
The invigoration of deep convective clouds over the Atlantic: aerosol effect, meteorology or retrieval artifact?

Associations between cloud properties and aerosol loading are frequently observed in products derived from satellite measurements. These observed trends between clouds and aerosol optical depth suggest aerosol modification of cloud dynamics, yet there are uncertainties involved in satellite retrievals that have the potential to lead to incorrect conclusions. Two of the most challenging problems are addressed here: the potential for retrieved aerosol optical depth to be cloud-contaminated, and as a result, artificially correlated with cloud parameters; and the potential for correlations between aerosol and cloud parameters to be erroneously considered to be causal. Here these issues are tackled directly by studying the effects of the aerosol on convective clouds in the tropical Atlantic Ocean using satellite remote sensing, a chemical transport model, and a reanalysis of meteorological fields. Results show that there is a robust positive correlation between cloud fraction or cloud top height and the aerosol optical depth, regardless of whether a stringent filtering of aerosol measurements in the vicinity of clouds is applied, or not. These same positive correlations emerge when replacing the observed aerosol field with that derived from a chemical transport model. Model-reanalysis data is used to address the causality question by providing meteorological context for the satellite observations. A correlation exercise between the full suite of meteorological fields derived from model reanalysis and satellite-derived cloud fields shows that observed cloud top height and cloud fraction correlate best with model pressure updraft velocity and relative humidity. Observed aerosol optical depth does correlate with meteorological parameters but usually different parameters from those that correlate with observed cloud fields. The result is a near-orthogonal influence of aerosol and meteorological fields on cloud top height and cloud fraction. The results strengthen the case that the aerosol does play a role in invigorating convective clouds.
Development and application of a reactive plume-in-grid model: evaluation over Greater Paris

Emissions from major point sources are badly represented by classical Eulerian models. An overestimation of the horizontal plume dilution, a bad representation of the vertical diffusion as well as an incorrect estimate of the chemical reaction rates are the main limitations of such models in the vicinity of major point sources. The plume-in-grid method is a multiscale modeling technique that couples a local-scale Gaussian puff model with an Eulerian model in order to better represent these emissions. We present the plume-in-grid model developed in the air quality modeling system Polyphemus, with full gaseous chemistry. The model is evaluated on the metropolitan Île-de-France region, during six months (summer 2001). The subgrid-scale treatment is used for 89 major point sources, a selection based on the emission rates of NOx and SO2. Results with and without the subgrid treatment of point emissions are compared, and their performance by comparison to the observations on measurement stations is assessed. A sensitivity study is also carried out, on several local-scale parameters as well as on the vertical diffusion within the urban area. Primary pollutants are shown to be the most impacted by the plume-in-grid treatment. SO2 is the most impacted pollutant, since the point sources account for an important part of the total SO2 emissions, whereas NOx emissions are mostly due to traffic. The spatial impact of the subgrid treatment is localized in the vicinity of the sources, especially for reactive species (NOx and O3). Ozone is mostly sensitive to the time step between two puff emissions which influences the in-plume chemical reactions, whereas the almost-passive species SO2 is more sensitive to the injection time, which determines the duration of the subgrid-scale treatment. Future developments include an extension to handle aerosol chemistry, and an application to the modeling of line sources in order to use the subgrid treatment with road emissions. The latter is expected to lead to more striking results, due to the importance of traffic emissions for the pollutants of interest.