Surface ozone in the Colorado northern Front Range and the influence of oil and gas development during FRAPPE/DISCOVER-AQ in summer 2014

High mixing ratios of ozone (O3) in the northern Front Range (NFR) of Colorado are not limited to the urban Denver area but were also observed in rural areas where oil and gas activity is the primary source of O3 precursors. On individual days, oil and gas O3 precursors can contribute in excess of 30 ppb to O3 growth and can lead to exceedances of the EPA O3 National Ambient Air Quality Standard. Data used in this study were gathered from continuous surface O3 monitors for June–August 2013–2015 as well as additional flask measurements and mobile laboratories that were part of the FRAPPE/DISCOVER-AQ field campaign of July–August 2014. Overall observed O3 levels during the summer of 2014 were lower than in 2013, likely due to cooler and damper weather than an average summer. This study determined the median hourly surface O3 mixing ratio in the NFR on summer days with limited photochemical production to be approximately 45–55 ppb. Mobile laboratory and flask data collected on three days provide representative case studies of different O3 formation environments in and around Greeley, Colorado. Observations of several gases (including methane, ethane, CO, nitrous oxide) along with O3 are used to identify sources of O3 precursor emissions. A July 23 survey demonstrated low O3 (45–60 ppb) while August 3 and August 13 surveys recorded O3 levels of 75–80 ppb or more. August 3 exemplifies influence of moderate urban and high oil and gas O3 precursor emissions. August 13 demonstrates high oil and gas emissions, low agricultural emissions, and CO measurements that were well correlated with ethane from oil and gas, suggesting an oil and gas related activity as a NOx and O3 precursor source. Low isoprene levels indicated that they were not a significant contributor to O3 precursors measured during the case studies

On the origin of elevated surface ozone concentrations at Izana Observatory, Tenerife during late March 1996

The origin of relatively high surface ozone concentrations measured at Izana Observatory (Canary Islands) during the end of March 1996 is studied using a coupled chemistry-GCM (ECHAM4) at T63 resolution (1.875° × 1.875°). Meteorological fields (geopotential height, potential vorticity, specific humidity), and a model-simulated stratospheric ozone tracer as well as 3-D back trajectories, show the stratospheric origin of these relatively high surface ozone values caused by cross-tropopause exchange at the western flank of an upper level trough/cut-off low (COL) over the extratropical North-Atlantic Ocean. The good agreement between observations and model results (within 10–15%) indicates that the high resolution chemistry-GCM is a useful tool towards the understanding of natural sources controlling background surface ozone variability. The results underscore the importance of stratosphere-troposphere exchange (STE) during late winter/early spring for lower free tropospheric ozone at subtropical latitudes

Validation of northern latitude Tropospheric Emission Spectrometer stare ozone profiles with ARC-IONS sondes during ARCTAS: sensitivity, bias and error analysis

We compare Tropospheric Emission Spectrometer (TES) versions 3 and 4, V003 and V004, respectively, nadir-stare ozone profiles with ozonesonde profiles from the Arctic Intensive Ozonesonde Network Study (ARCIONS, http://croc.gsfc.nasa.gov/arcions/ during the Arctic Research on the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) field mission. The ozonesonde data are from launches timed to match Aura's overpass, where 11 coincidences spanned 44° N to 71° N from April to July 2008. Using the TES "stare" observation mode, 32 observations are taken over each coincidental ozonesonde launch. By effectively sampling the same air mass 32 times, comparisons are made between the empirically-calculated random errors to the expected random errors from measurement noise, temperature and interfering species, such as water. This study represents the first validation of high latitude (>70°) TES ozone. We find that the calculated errors are consistent with the actual errors with a similar vertical distribution that varies between 5% and 20% for V003 and V004 TES data. In general, TES ozone profiles are positively biased (by less than 15%) from the surface to the upper-troposphere (~1000 to 100 hPa) and negatively biased (by less than 20%) from the upper-troposphere to the lower-stratosphere (100 to 30 hPa) when compared to the ozonesonde data. Lastly, for V003 and V004 TES data between 44° N and 71° N there is variability in the mean biases (from −14 to +15%), mean theoretical errors (from 6 to 13%), and mean random errors (from 9 to 19%)

Technical Note: Ozonesonde climatology between 1995 and 2011: description, evaluation and applications

An ozone climatology based on ozonesonde measurements taken over the last 17 yr has been constructed for model evaluation and comparisons to other observations. Vertical ozone profiles for 42 stations around the globe have been compiled for the period 1995–2011, in pressure and tropopause-referenced altitudes. For each profile, the mean, standard deviation, median, the half-width are provided, as well as information about interannual variability. Regional aggregates are formed in combining stations with similar ozone characteristics. The Hellinger distance is introduced as a new diagnostic to identify stations that describe similar shapes of ozone probability distribution functions (PDFs). In this way, 12 regions were selected covering at least 2 stations and the variability among those stations is discussed. Significant variability with longitude of ozone distributions in the troposphere and lower stratosphere in the northern mid- and high latitudes is found. The representativeness of regional aggregates is discussed for high northern latitudes, Western Europe, Eastern US, and Japan, using independent observations from surface stations and MOZAIC aircraft data. Good agreement exists between ozonesondes and aircraft observations in the mid-troposphere and between ozonesondes and surface observations for Western Europe. For Eastern US and high northern latitudes, surface ozone values from ozonesondes are biased 10 ppb high compared to independent measurements. An application of the climatology is presented using the NCAR CAM-Chem model. The climatology allows evaluation of the model performance regarding ozone averages, seasonality, interannual variability, and the shape of ozone distributions. The new assessment of the key features of ozone distributions gives deeper insights into the performance of models

A new interpretation of total column BrO during Arctic spring

Emission of bromine from sea-salt aerosol, frost flowers, ice leads, and snow results in the nearly complete removal of surface ozone during Arctic spring. Regions of enhanced total column BrO observed by satellites have traditionally been associated with these emissions. However, airborne measurements of BrO and O3 within the convective boundary layer (CBL) during the ARCTAS and ARCPAC field campaigns at times bear little relation to enhanced column BrO. We show that the locations of numerous satellite BrO "hotspots" during Arctic spring are consistent with observations of total column ozone and tropopause height, suggesting a stratospheric origin to these regions of elevated BrO. Tropospheric enhancements of BrO large enough to affect the column abundance are also observed, with important contributions originating from above the CBL. Closure of the budget for total column BrO, albeit with significant uncertainty, is achieved by summing observed tropospheric partial columns with calculated stratospheric partial columns provided that natural, short-lived biogenic bromocarbons supply between 5 and 10 ppt of bromine to the Arctic lowermost stratosphere. Proper understanding of bromine and its effects on atmospheric composition requires accurate treatment of geographic variations in column BrO originating from both the stratosphere and troposphere. Copyright 2010 by the American Geophysical Union

Characterizing summertime chemical boundary conditions for airmasses entering the US West Coast

The objective of this study is to analyze the pollution inflow into California during summertime and how it impacts surface air quality through combined analysis of a suite of observations and global and regional models. The focus is on the transpacific pollution transport investigated by the NASA Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) mission in June 2008. Additional observations include satellite retrievals of carbon monoxide and ozone by the EOS Aura Tropospheric Emissions Spectrometer (TES), aircraft measurements from the MOZAIC program and ozonesondes. We compare chemical boundary conditions (BC) from the MOZART-4 global model, which are commonly used in regional simulations, with measured concentrations to quantify both the accuracy of the model results and the variability in pollution inflow. Both observations and model reflect a large variability in pollution inflow on temporal and spatial scales, but the global model captures only about half of the observed free tropospheric variability. Model tracer contributions show a large contribution from Asian emissions in the inflow. Recirculation of local US pollution can impact chemical BC, emphasizing the importance of consistency between the global model simulations used for BC and the regional model in terms of emissions, chemistry and transport. Aircraft measurements in the free troposphere over California show similar concentration ranges, variability and source contributions as free tropospheric air masses over ocean, but caution has to be taken that local pollution aloft is not misinterpreted as inflow. A flight route specifically designed to sample boundary conditions during ARCTAS-CARB showed a prevalence of plumes transported from Asia and thus may not be fully representative for average inflow conditions. Sensitivity simulations with a regional model with altered BCs show that the temporal variability in the pollution inflow does impact modeled surface concentrations in California. We suggest that time and space varying chemical boundary conditions from global models provide useful input to regional models, but likely still lead to an underestimate of peak surface concentrations and the variability associated with long-range pollution transport

Characteristics of tropospheric ozone depletion events in the Arctic spring: analysis of the ARCTAS, ARCPAC, and ARCIONS measurements and satellite BrO observations

Arctic ozone depletion events (ODEs) are caused by halogen catalyzed ozone loss. In situ chemistry, advection of ozone-poor air mass, and vertical mixing in the lower troposphere are important factors affecting ODEs. To better characterize the ODEs, we analyze the combined set of surface, ozonesonde, and aircraft in situ measurements of ozone and bromine compounds during the Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS), the Aerosol, Radiation, and Cloud Processes affecting Arctic Climate (ARCPAC), and the Arctic Intensive Ozonesonde Network Study (ARCIONS) experiments (April 2008). Tropospheric BrO columns retrieved from satellite measurements and back trajectory calculations are also used to investigate the characteristics of observed ODEs. In situ observations from these field experiments are inadequate to validate tropospheric BrO columns derived from satellite measurements. In view of this difficulty, we construct an ensemble of tropospheric column BrO estimates from two satellite (OMI and GOME-2) measurements and with three independent methods of calculating stratospheric BrO columns. Furthermore, we select analysis methods that do not depend on the absolute magnitude of column BrO, such as time-lagged correlation analysis of ozone and tropospheric column BrO, to understand characteristics of ODEs. Time-lagged correlation analysis between in situ (surface and ozonesonde) measurements of ozone and satellite derived tropospheric BrO columns indicates that the ODEs are due to either local halogen-driven ozone loss or short-range (∼1 day) transport from nearby regions with ozone depletion. The effect of in situ ozone loss is also evident in the diurnal variation difference between low (10th and 25th percentiles) and higher percentiles of surface ozone concentrations at Alert, Canada. Aircraft observations indicate low-ozone air mass transported from adjacent high-BrO regions. Correlation analyses of ozone with potential temperature and time-lagged tropospheric BrO column show that the vertical extent of local ozone loss is surprisingly deep (1–2 km) at Resolute and Churchill, Canada. The unstable boundary layer during ODEs at Churchill could potentially provide a source of free-tropospheric BrO through convective transport and explain the significant negative correlation between free-tropospheric ozone and tropospheric BrO column at this site