Carbon Monoxide Mixing Ratios Research Articles

Air quality simulation over South Asia using Hemispheric Transport of Air Pollution version-2 (HTAP-v2) emission inventory and Model for Ozone and Related chemical Tracers (MOZART-4)

This study presents the distribution of tropospheric ozone and related species for South Asia using the Model for Ozone and Related chemical Tracers (MOZART-4) and Hemispheric Transport of Air Pollution version-2 (HTAP-v2) emission inventory. The model present-day simulated ozone (O3), carbon monoxide (CO) and nitrogen dioxide (NO2) are evaluated against surface-based, balloon-borne and satellite-based (MOPITT and OMI) observations. The model systematically overestimates surface O3 mixing ratios (range of mean bias about: 1–30 ppbv) at different ground-based measurement sites in India. Comparison between simulated and observed vertical profiles of ozone shows a positive bias from the surface up to 600 hPa and a negative bias above 600 hPa. The simulated seasonal variation in surface CO mixing ratio is consistent with the surface observations, but has a negative bias of about 50–200 ppb which can be attributed to a large part to the coarse model resolution. In contrast to the surface evaluation, the model shows a positive bias of about 15–20 × 1017 molecules/cm2 over South Asia when compared to satellite derived CO columns from the MOPITT instrument. The model also overestimates OMI retrieved tropospheric column NO2 abundance by about 100–250 × 1013 molecules/cm2. A response to 20% reduction in all anthropogenic emissions over South Asia shows a decrease in the anuual mean O3 mixing ratios by about 3–12 ppb, CO by about 10–80 ppb and NOX by about 3–6 ppb at the surface level. During summer monsoon, O3 mixing ratios at 200 hPa show a decrease of about 6–12 ppb over South Asia and about 1–4 ppb over the remote northern hemispheric western Pacific region.

In situ vertical profiles of aerosol extinction, mass, and composition over the southeast United States during SENEX and SEAC<sup>4</sup>RS: observations of a modest aerosol enhancement aloft

Abstract. Vertical profiles of submicron aerosol from in situ aircraft-based measurements were used to construct aggregate profiles of chemical, microphysical, and optical properties. These vertical profiles were collected over the southeastern United States (SEUS) during the summer of 2013 as part of two separate field studies: the Southeast Nexus (SENEX) study and the Study of Emissions and Atmospheric Composition, Clouds, and Climate Coupling by Regional Surveys (SEAC4RS). Shallow cumulus convection was observed during many profiles. These conditions enhance vertical transport of trace gases and aerosol and create a cloudy transition layer on top of the sub-cloud mixed layer. The trace gas and aerosol concentrations in the transition layer were modeled as a mixture with contributions from the mixed layer below and the free troposphere above. The amount of vertical mixing, or entrainment of air from the free troposphere, was quantified using the observed mixing ratio of carbon monoxide (CO). Although the median aerosol mass, extinction, and volume decreased with altitude in the transition layer, they were ~10 % larger than expected from vertical mixing alone. This enhancement was likely due to secondary aerosol formation in the transition layer. Although the transition layer enhancements of the particulate sulfate and organic aerosol (OA) were both similar in magnitude, only the enhancement of sulfate was statistically significant. The column integrated extinction, or aerosol optical depth (AOD), was calculated for each individual profile, and the transition layer enhancement of extinction typically contributed less than 10 % to the total AOD. Our measurements and analysis were motivated by two recent studies that have hypothesized an enhanced layer of secondary aerosol aloft to explain the summertime enhancement of AOD (2–3 times greater than winter) over the southeastern United States. The first study attributes the layer aloft to secondary organic aerosol (SOA) while the second study speculates that the layer aloft could be SOA or secondary particulate sulfate. In contrast to these hypotheses, the modest enhancement we observed in the transition layer was not dominated by OA and was not a large fraction of the summertime AOD.

Carbon monoxide distribution and microbial consumption in the Southern Yellow Sea

Two cruises were conducted in the Southern Yellow Sea (SYS) in late July and early August 2008 to study marine carbon monoxide (CO) distribution, sea-to-air flux, and microbial consumption. Surface water dissolved CO showed an apparently higher average concentration (31.9% higher) during the second cruise than during the first cruise. Surface water CO concentrations were found to follow an apparent diurnal variation, during which CO concentrations varied by a factor of 8–14. Atmospheric CO mixing ratios ranged from 194 to 596 ppbv with an average of 390 ppbv for the first cruise, and from 53 to 238 ppbv with an average of 124 ppbv for the second one. Average sea-to-air CO fluxes (W92) were estimated to be 4.58 μmol m−2 d−1 and 0.08 μmol m−2 d−1 for the first and second cruise, respectively. Incubation experiments were conducted at 12 stations during the second cruise; results showed that surface-water microbial CO consumption rate constants (Kco) ranged from 0.07 to 0.83 h−1, with an average of 0.33 h−1. Microbial CO uptake typically followed first-order reaction kinetics at most of the studied stations.

Search for horizontal and vertical variations of CO in the day and night side lower mesosphere of Venus from CSHELL/IRTF [formula omitted] observations

High-resolution (R~43,000) spectroscopic observations of both day and night sides of Venus were acquired using CSHELL at IRTF between 2202 and 2207cm−1 (4.53–4.54μm) during the latest maximal eastern and western elongations of Venus in two four-nights observing runs in August 2012 and November 2013. Their purpose was to investigate the effect of the recent (from 2007 onwards) decrease of sulfur dioxide (SO2) at the cloud top level on the spatial distribution of carbon monoxide (CO), since both species are involved in the mesospheric photochemical cycles. Observations of neighboring CO2 lines are fully consistent with the previously determined aerosol scale height in the 68–74km range. We could therefore determine CO mixing ratio on both day and night sides of Venus, taking into account both scattered solar and thermal components, as well as the overlying CO dayglow on the day side. CO spatial distribution is mostly unchanged compared to previous measurements, ranging from 25ppmv to 45ppmv at 70km. The scattered solar component reveals an increase in CO with increasing altitude with a scale height of (5±0.5)km between 70 and 76km. Horizontal variability is found to be weak, with a possible increase towards higher latitudes on the day side of about 10ppmv. Yet the accuracy of our absolute values of CO mixing ratio is limited by several assumptions, and we cannot rule out that some of the variability we measure for CO could alternatively be explained by other changes occurring in the Venusian atmosphere, e.g. changes in both dT/dz and aerosol scale height.

On the use of MOZAIC-IAGOS data to assess the ability of the MACC reanalysis to reproduce the distribution of ozone and CO in the UTLS over Europe

MOZAIC-IAGOS data are used to assess the ability of the MACC reanalysis (REAN) to reproduce distributions of ozone (O3) and carbon monoxide (CO), along with vertical and inter-annual variability in the upper troposphere/lower stratosphere region (UTLS) over Europe for the period 2003–2010. A control run (CNTRL, without assimilation) is compared with the MACC reanalysis (REAN, with assimilation) to assess the impact of assimilation. On average over the period, REAN underestimates ozone by 60 ppbv in the lower stratosphere (LS), whilst CO is overestimated by 20 ppbv. In the upper troposphere (UT), ozone is overestimated by 50 ppbv, while CO is partly over or underestimated by up to 20 ppbv. As expected, assimilation generally improves model results but there are some exceptions. Assimilation leads to increased CO mixing ratios in the UT which reduce the biases of the model in this region but the difference in CO mixing ratios between LS and UT has not changed and remains underestimated after assimilation. Therefore, this leads to a significant positive bias of CO in the LS after assimilation. Assimilation improves estimates of the amplitude of the seasonal cycle for both species. Additionally, the observations clearly show a general negative trend of CO in the UT which is rather well reproduced by REAN. However, REAN misses the observed inter-annual variability in summer. The O3–CO correlation in the Ex-UTLS is rather well reproduced by the CNTRL and REAN, although REAN tends to miss the lowest CO mixing ratios for the four seasons and tends to oversample the extra-tropical transition layer (ExTL region) in spring. This evaluation stresses the importance of the model gradients for a good description of the mixing in the Ex-UTLS region, which is inherently difficult to observe from satellite instruments.

Meteorological controls on the diurnal variability of carbon monoxide mixing ratio at a mountaintop monitoring site in the Appalachian Mountains

The variability of trace gases such as carbon monoxide (CO) at surface monitoring stations is affected by meteorological forcings that are particularly complicated over mountainous terrain. A detailed understanding of the impact of meteorological forcings on trace gas variability is challenging, but is vital to distinguish trace gas measurements affected by local pollutant sources from measurements representative of background mixing ratios. In the present study, we investigate the meteorological and CO characteristics at Pinnacles (38.61 N, 78.35 W, 1017 m above mean sea level), a mountaintop monitoring site in northwestern Virginia, USA, in the Appalachian Mountains, from 2009 to 2012, and focus on understanding the dominant meteorological forcings affecting the CO variability on diurnal timescales. The annual mean diurnal CO cycle shows a minimum in the morning between 0700 and 0900 LST and a maximum in the late afternoon between 1600 and 2000 LST, with a mean (median) daily CO amplitude of 39.2±23.7 ppb (33.2 ppb). CO amplitudes show large day-to-day variability. The largest CO amplitudes, in which CO mixing ratios can change >100 ppb in <3 h, occur in the presence of synoptic disturbances. Under fair weather conditions, local- to regional-scale transport processes are found to be more important drivers of the diurnal CO variability. On fair weather days with northwesterly winds, boundary layer dilution causes a daytime CO decrease, resembling the variability observed atop tall towers in flat terrain. Fair weather days with a wind shift from the northwest to the south are characterised by an afternoon CO increase and resemble the variability observed at mountaintops influenced by the vertical transport of polluted air from adjacent valleys.

Variability of aerosol particle number concentrations observed over the western Pacific in the spring of 2009

AbstractAirborne measurements of aerosols were conducted over the western Pacific in the spring of 2009 during the Aerosol Radiative Forcing in East Asia (A‐FORCE) aircraft campaign. The A‐FORCE flights intensively covered an important vertical‐latitudinal range in the outflow region of East Asia (0–9 km altitude; 27°N–38°N). This paper presents the variability of aerosol particle number concentrations obtained by condensation particle counters and a Single‐Particle Soot Photometer (SP2), with the focus on those in the free troposphere. The number concentration data include total condensation nuclei with particle diameters (dp) larger than 10 nm (total CN10), PM0.17‐CN10 (dp ~10–130 nm), and SP2 black carbon (NBC; dp ~75–850 nm). Large increases in total CN10 that were not associated with NBC were observed in the free troposphere, suggesting influences from new particle formation (NPF). Statistical characteristics of total CN10, PM0.17‐CN10, and NBC in the lower troposphere (LT; 0–3 km), middle troposphere (MT; 3–6 km), and upper troposphere (UT; 6–9 km) are investigated. The correlation between total CN10 and NBC, along with the ratio of PM0.17 to total CN10 and carbon monoxide mixing ratio (CO), is used to interpret the observed variability. The median concentrations of total CN10 and PM0.17‐CN10 in the UT were higher than those in the MT by a factor of ~1.4 and ~1.6, respectively. We attribute the enhancements of CN10 in the UT to NPF. Possible mechanisms affecting NPF in the free troposphere are discussed.

Effect of different emission inventories on modeled ozone and carbon monoxide in Southeast Asia

Abstract. In order to improve our understanding of air quality in Southeast Asia, the anthropogenic emissions inventory must be well represented. In this work, we apply different anthropogenic emission inventories in the Weather Research and Forecasting Model with Chemistry (WRF-Chem) version 3.3 using Model for Ozone and Related Chemical Tracers (MOZART) gas-phase chemistry and Global Ozone Chemistry Aerosol Radiation and Transport (GOCART) aerosols to examine the differences in predicted carbon monoxide (CO) and ozone (O3) surface mixing ratios for Southeast Asia in March and December 2008. The anthropogenic emission inventories include the Reanalysis of the TROpospheric chemical composition (RETRO), the Intercontinental Chemical Transport Experiment-Phase B (INTEX-B), the MACCity emissions (adapted from the Monitoring Atmospheric Composition and Climate and megacity Zoom for the Environment projects), the Southeast Asia Composition, Cloud, Climate Coupling Regional Study (SEAC4RS) emissions, and a combination of MACCity and SEAC4RS emissions. Biomass-burning emissions are from the Fire Inventory from the National Center for Atmospheric Research (NCAR) (FINNv1) model. WRF-Chem reasonably predicts the 2 m temperature, 10 m wind, and precipitation. In general, surface CO is underpredicted by WRF-Chem while surface O3 is overpredicted. The NO2 tropospheric column predicted by WRF-Chem has the same magnitude as observations, but tends to underpredict the NO2 column over the equatorial ocean and near Indonesia. Simulations using different anthropogenic emissions produce only a slight variability of O3 and CO mixing ratios, while biomass-burning emissions add more variability. The different anthropogenic emissions differ by up to 30% in CO emissions, but O3 and CO mixing ratios averaged over the land areas of the model domain differ by ~4.5% and ~8%, respectively, among the simulations. Biomass-burning emissions create a substantial increase for both O3 and CO by ~29% and ~16%, respectively, when comparing the March biomass-burning period to the December period with low biomass-burning emissions. The simulations show that none of the anthropogenic emission inventories are better than the others for predicting O3 surface mixing ratios. However, the simulations with different anthropogenic emission inventories do differ in their predictions of CO surface mixing ratios producing variations of ~30% for March and 10–20% for December at Thai surface monitoring sites.

Seasonal and interannual variability of carbon monoxide based on MOZAIC observations, MACC reanalysis, and model simulations over an urban site in India

AbstractThe spatial and temporal variations of carbon monoxide (CO) are analyzed over a tropical urban site, Hyderabad (17°27′N, 78°28′E) in central India. We have used vertical profiles from the Measurement of ozone and water vapor by Airbus in‐service aircraft (MOZAIC) aircraft observations, Monitoring Atmospheric Composition and Climate (MACC) reanalysis, and two chemical transport model simulations (Model for Ozone And Related Tracers (MOZART) and MRI global Chemistry Climate Model (MRI‐CCM2)) for the years 2006–2008. In the lower troposphere, the CO mixing ratio showed strong seasonality, with higher levels (&gt;300 ppbv) during the winter and premonsoon seasons associated with a stable anticyclonic circulation, while lower CO values (up to 100 ppbv) were observed in the monsoon season. In the planetary boundary layer (PBL), the seasonal distribution of CO shows the impact of both local meteorology and emissions. While the PBL CO is predominantly influenced by strong winds, bringing regional background air from marine and biomass burning regions, under calm conditions CO levels are elevated by local emissions. On the other hand, in the free troposphere, seasonal variation reflects the impact of long‐range transport associated with the Intertropical Convergence Zone and biomass burning. The interannual variations were mainly due to transition from El Niño to La Niña conditions. The overall modified normalized mean biases (normalization based on the observed and model mean values) with respect to the observed CO profiles were lower for the MACC reanalysis than the MOZART and MRI‐CCM2 models. The CO in the PBL region was consistently underestimated by MACC reanalysis during all the seasons, while MOZART and MRI‐CCM2 show both positive and negative biases depending on the season.

Measurements of carbon monoxide mixing ratios in Houston using a compact high-power CW DFB-QCL-based QEPAS sensor

Measurements of carbon monoxide (CO) mixing ratios in Houston, Texas, during the period from May 16, 2013 to May 28, 2013 were performed using a sensitive, selective, compact, and portable quartz-enhanced photoacoustic spectroscopy (QEPAS)-based CO sensor employing a high-power continuous wave (CW) distributed feedback quantum cascade laser (DFB-QCL). The minimum detectable CO concentration was 3 ppbv for the strong, interference-free R(6) absorption line at 2,169.2 cm−1 and a 5 s data acquisition time. The average CO concentration during the measurement period was 299.1 ± 81.4 ppb with observed minimum and maximum values of 210.5 and 4,307.9 ppb, respectively. A commercially available electrochemical sensor was employed in-line for simultaneous measurements to confirm the response of the CW DFB-QCL-based QEPAS sensor to variations of the CO mixing ratios. Moderate agreement (R 2 = 0.7) was found between both sets of CO measurements.

Distributions of ozone and related trace gases at an urban site in western India

Continuous in-situ measurements of surface ozone (O3), carbon monoxide (CO) and oxides of nitrogen (NOx) were conducted at Udaipur city in India during April 2010 to March 2011. We have analyzed the data to investigate both diurnal and seasonal variations in the mixing ratios of trace gases. The diurnal distribution of O3 showed highest values in the afternoon hours and lower values from evening till early morning. The mixing ratios of CO and NOx showed a sharp peak in the morning hours but lowest in the afternoon hours. The daily mean data of O3, CO and NOx varied in the ranges of 5–51 ppbv, 145–795 ppbv and 3–25 ppbv, respectively. The mixing ratios of O3 were highest of 28 ppbv and lowest 19 ppbv during the pre-monsoon and monsoon seasons, respectively. While the mixing ratios of both CO and NOx showed highest and lowest values during the winter and monsoon seasons, respectively. The diurnal pattern of O3 is mainly controlled by the variations in photochemistry and planetary boundary layer (PBL) depth. On the other hand, the seasonality of O3, CO and NOx were governed by the long-range transport associated mainly with the summer and winter monsoon circulations over the Indian subcontinent. The back trajectory data indicate that the seasonal variations in trace gases were caused mainly by the shift in long-range transport pattern. In monsoon season, flow of marine air and negligible presence of biomass burning in India resulted in lowest O3, CO and NOx values. The mixing ratios of CO and NOx show tight correlations during winter and pre-monsoon seasons, while poor correlation in the monsoon season. The emission ratio of ∆CO/∆NOx showed large seasonal variability but values were lower than those measured over the Indo Gangetic Plains (IGP). The mixing ratios of CO and NOx decreased with the increase in wind speed, while O3 tended to increase with the wind speed. Effects of other meteorological parameters in the distributions of trace gases were also noticed.

Black carbon and carbon monoxide over Bay of Bengal during W_ICARB: Source characteristics

The ship borne measurements of near-surface black carbon (BC) and carbon monoxide (CO) were carried out over Bay of Bengal (BoB) during the winter period of 2009 under W_ICARB, the second phase of ‘Integrated Campaign for Aerosols, gases and Radiation Budget (ICARB)’. The CO mixing ratio and BC mass concentration varied in the ranges of 80–480 ppbv and 75–10,000 ng m−3, respectively over this marine region. The BC and CO showed similar variations over northern BoB where airmass from Indo-Gangetic Plain (IGP) region prevailed during the observations period leading to a very strong positive correlation. The association of BC and CO was poor over the eastern and southern part of BoB could be due to the removal of BC aerosols by rain and/or processes of dilution and mixing while transported over to BoB. The highest value of CO observed over eastern BoB was partially due to biomass burning over East Asia. The BC/CO ratio for IGP airmass found to be 20.3 ng m−3 ppb−1 and ∼16 ng m−3 ppb−1 during winter and pre-monsoon, respectively which indicate the role of biomass burning as the source of BC over the region. Based on the emission flux of CO from various inventories and observed BC/CO ratios during pre-monsoon and winter, the BC emission for India is estimated to be in the range of 0.78–1.23 Tg year−1. The analysis of scavenging of BC revealed the loss rate of BC due to relative humidity 0.39 ± 0.08 ng m−3 ppb−1 RH (%)−1 over northern BoB and 0.53 ± 0.04 ng m−3 ppb−1 RH (%)−1 over the southern-BoB during winter.

Assessment of carbon monoxide (CO) adjusted non-methane hydrocarbon (NMHC) emissions of a motor fleet – A long tunnel study

Speciated hydrocarbons (NMHCs) and CO were simultaneously measured by evenly distributed samples along the entire length (12.9 km) of the tunnel in different traffic conditions. Four passes (two round-trips) were made at four different fleet speeds (i.e., 45, 65, 75 and 85 km h−1). Individual NMHC and CO mixing ratios were observed to be sensitive to the fleet speed, which is compounded by driving conditions and traffic volumes. We propose using ratios of NMHCs to CO to cancel out the factor of traffic volumes to determine CO-normalized NMHC emissions, such that a less biased comparison can be made between different fleet speeds in this study and even between different studies. Moreover, to obtain robust CO-normalized NMHC emissions which are sufficiently representative of the fleet speeds, only samples collected deep inside the long-tunnels between 8 and 12 km were used.Of the 61 target NMHCs, isomers of butane, pentane, ethylene, acetylene and toluene were the most abundant species regardless of the driving conditions. We observed that different driving conditions not only affected the emission strengths but also altered the compositions of the NMHCs. To simplify the data analysis, the target NMHCs were classified into four chemical groups, i.e., alkanes, alkenes, aromatics and alkynes. For the slower and more congested driving condition (fleet speed = 45 km h−1), the CO-normalized NMHC emissions were the highest, with alkanes contributing to approximately 60% of the total NMHC levels, suggesting poorer fuel utilization at slower driving conditions. In terms of the CO-normalized ozone forming potentials (OFPs), the contribution of the alkanes diminished dramatically to approximately 9–22% despite their high weight percentage, whereas the contribution of the alkenes was enhanced significantly to 50–60% from their weight percent of only approximately 26%.Our total NMHC to CO ratios of 0.06–0.20 for the four fleet speeds generally fall within the range constrained by many other tunnel or chassis dynamometer studies; however, the sensitivity to the driving conditions and the robustness with the long-tunnel data are better demonstrated in this study.

Temporal Variation of Particulate Matter (PM) and Potential Sources at an Urban Site of Udaipur in Western India

Measurements of mass concentrations of particulate matters (PM_(2.5) and PM_(10)) and mixing ratio of carbon monoxide (CO) were made at an urban site of Udaipur (24.58°N, 73.68°E) in India from April 2010 to March 2011. Concentrations of PM_(2.5), PM_(10) and CO show strong diurnal and seasonal variations. The highest concentrations coincide with the rush traffic and lower nocturnal boundary layer depth. The lowest concentrations in the afternoon hours are attributed to the dilution caused by higher boundary layer height and reduced traffic. The levels of trace constituents during the weekend were significantly reduced compared to the weekdays of observations. The daily PM_(2.5), PM_(10) and CO varied in the large ranges of 8-111 μg/m^3, 28-350 μg/m^3 and 145-795 ppbv, respectively. PM_(2.5) and CO show strong seasonality with higher and lower values during winter and monsoon seasons, respectively, while PM_(10) shows highest value during the premonsoon season. Flow of cleaner marine air and negligible biomass burning resulted in lower values in the monsoon season. Long-rang transport and extensive biomass burning caused higher values in winter and pre-monsoon seasons. Back trajectories show seasonal shift in the long- range transport which is consistent with the seasonality of aerosols and CO. Except for the monsoon season, mass concentrations of PM_(2.5) and PM_(10) show good correlation (typically r^2 ＞ 0.5). Relations of PM_(2.5) and PM_(10) with CO varied with the season but show good correlations (r^2 ＞ 0.5) during the winter season, while poor correlation during monsoon. The correlations suggest dominance of combustion related emissions particularly during winter season. Monthly emission ratios of ΔPM_(2.5)/ΔPM_(10), ΔPM_(2.5)/ΔCO and ΔPM_(10)/ΔCO varied in the ranges of 0.19-0.31 μg/m^3/ppbv, 0.05-0.10 μg/m^3/ppbv and 0.15-0.25 μg/m^3/ppbv, respectively. The mass concentration of PM_(2.5) tends to decrease with the increasing wind speed, while PM_(10) increases with wind speed.

Distribution and Variation of Carbon Monoxide in the Tropical Troposphere and Lower Stratosphere

AbstractThe authors examine the distribution and variation of carbon monoxide (CO) in the tropics from the surface to the lower stratosphere. By analyzing space-borne microwave limb sounder (MLS) measurements, measurements of pollution in the troposphere (MOPITT) and modern-era retrospective analysis for research and applications (MERRA) meteorological products, and atmospheric chemistry and climate model intercomparison project (ACCMIP) surface emission inventories, the influences of atmospheric dynamics and surface emissions are investigated. The results show that there are four centers of highly concentrated CO mixing ratio over tropical areas in different seasons: two in the Northern Hemisphere and another two in the Southern Hemisphere. All of these centers correspond to local deep convective systems and monsoons/anticyclones. The authors suggest that both deep convections and anticyclones affect CO in the tropical troposphere and lower stratosphere — the former helping to transport CO from the lower...

Free-troposphere ozone and carbon monoxide over the North Atlantic for 2001–2011

Abstract. In situ measurements of carbon monoxide (CO) and ozone (O3) at the Pico Mountain Observatory (PMO) located in the Azores, Portugal, are analyzed together with results from an atmospheric chemical transport model (GEOS-Chem) and satellite remote sensing data (AIRS (Atmospheric Infrared Sounder) for CO, and TES (Tropospheric Emission Spectrometer) for O3) to examine the evolution of free-troposphere CO and O3 over the North Atlantic for 2001–2011. GEOS-Chem captured the seasonal cycles for CO and O3 well but significantly underestimated the mixing ratios of CO, particularly in spring. Statistically significant (using a significance level of 0.05) decreasing trends were found for both CO and O3 based on harmonic regression analysis of the measurement data. The best estimates of the possible trends for CO and O3 measurements are −0.31 ± 0.30 (2-σ) ppbv yr−1 and −0.21 ± 0.11 (2-σ) ppbv yr−1, respectively. Similar decreasing trends for both species were obtained with GEOS-Chem simulation results. The most important factor contributing to the decreases in CO and O3 at PMO over the past decade is the decline in anthropogenic emissions from North America, which more than compensate for the impacts from increasing Asian emissions. It is likely that climate change in the past decade has also affected the intercontinental transport of O3.

Long-term measurements of aerosol and carbon monoxide at the ZOTTO tall tower to characterize polluted and pristine air in the Siberian taiga

Abstract. Siberia is one of few continental regions in the Northern Hemisphere where the atmosphere may sometimes approach pristine background conditions. We present the time series of aerosol and carbon monoxide (CO) measurements between September 2006 and December 2011 at the Zotino Tall Tower Observatory (ZOTTO) in Central Siberia (61° N; 89° E). We investigate the seasonal, weekly and diurnal variations of aerosol properties (including absorption and scattering coefficients and derived parameters, such as equivalent black carbon (BCe), Ångström exponent, single scattering albedo, and backscattering ratio) and the CO mixing ratios. Criteria were established to distinguish polluted from near-pristine air masses, providing quantitative characteristics for each type. Depending on the season, 23–36% of the sampling time at ZOTTO was found to be representative of a clean atmosphere. The summer pristine data indicate that primary biogenic and secondary organic aerosol formation are quite strong particle sources in the Siberian taiga. The summer seasons 2007–2008 were dominated by an Aitken mode around 80 nm size, whereas the summer 2009 with prevailing easterly winds produced particles in the accumulation mode around 200 nm size. We found these differences to be mainly related to air temperature, through its effect on the production rates of biogenic volatile organic compounds (VOC) precursor gases. In winter, the particle size distribution peaked at 160 nm, and the footprint of clean background air was characteristic for aged particles from anthropogenic sources at great distances from ZOTTO and diluted biofuel burning emissions from domestic heating. The wintertime polluted air originates mainly from large cities south and southwest of the site; these particles have a dominant mode around 100 nm, and the ΔBCe / ΔCO ratio of 7–11 ng m−3 ppb−1 suggests dominant contributions from coal and biofuel burning for heating. During summer, anthropogenic emissions are the dominant contributor to the pollution particles at ZOTTO, while only 12% of the polluted events are classified as biomass-burning-dominated, but then often associated with extremely high CO concentrations and aerosol absorption coefficients. Two biomass-burning case studies revealed different ΔBCe / ΔCO ratios from different fire types, with the agricultural fires in April~2008 yielding a very high ratio of 21 ng m−3 ppb−1. Overall, we find that anthropogenic sources dominate the aerosol population at ZOTTO most of the time, even during nominally clean episodes in winter, and that near-pristine conditions are encountered only in the growing season and then only episodically.

Using Bayesian optimization method and FLEXPART tracer model to evaluate CO emission in East China in springtime

Carbon monoxide (CO) is of great interest as a restriction factor for pollutants related to incomplete combustions. This study attempted to evaluate CO emission in East China using the analytical Bayesian inverse method and observations at Mount Hua in springtime. The mixing ratio of CO at the receptor was calculated using 5-day source-receptor relationship (SRR) simulated by a Lagrangian Particle Dispersion Model (FLEXPART) and CO emission flux. The stability of the inversion solution was evaluated on the basis of repeated random sampling simulations. The inversion results demonstrated that there were two city cluster regions (the Beijing-Tianjin-Hebei region and the low reaches of the Yangtze River Delta) where the difference between a priori (Intercontinental Chemical Transport Experiment-Phase B, INTEX-B) and a posteriori was statistically significant and the a priori might underestimate the CO emission flux by 37 %. A correction factor (a posteriori/a priori) of 1.26 was suggested for CO emission in China in spring. The spatial distribution and magnitude of the CO emission flux were comparable to the latest regional emission inventory in Asia (REAS2.0). Nevertheless, further evaluation is still necessary in view of the larger uncertainties for both the analytical inversion and the bottom-up statistical approaches.

Impact of Wildfires on Ozone Exceptional Events in the Western U.S.

Wildfires generate substantial emissions of nitrogen oxides (NOx) and volatile organic compounds (VOCs). As such, wildfires contribute to elevated ozone (O3) in the atmosphere. However, there is a large amount of variability in the emissions of O3 precursors and the amount of O3 produced between fires. There is also significant interannual variability as seen in median O3, organic carbon and satellite derived carbon monoxide mixing ratios in the western U.S. To better understand O3 produced from wildfires, we developed a statistical model that estimates the maximum daily 8 h average (MDA8) O3 as a function of several meteorological and temporal variables for three urban areas in the western U.S.: Salt Lake City, UT; Boise, ID; and Reno, NV. The model is developed using data from June-September 2000-2012. For these three locations, the statistical model can explain 60, 52, and 27% of the variability in daily MDA8. The Statistical Model Residual (SMR) can give information on additional sources of O3 that are not explained by the usual meteorological pattern. Several possible O3 sources can explain high SMR values on any given day. We examine several cases with high SMR that are due to wildfire influence. The first case considered is for Reno in June 2008 when the MDA8 reached 82 ppbv. The wildfire influence for this episode is supported by PM concentrations, the known location of wildfires at the time and simulations with the Weather and Research Forecasting Model with Chemistry (WRF-Chem) which indicates transport to Reno from large fires burning in California. The contribution to the MDA8 in Reno from the California wildfires is estimated to be 26 ppbv, based on the SMR, and 60 ppbv, based on WRF-Chem. The WRF-Chem model also indicates an important role for peroxyacetyl nitrate (PAN) in producing O3 during transport from the California wildfires. We hypothesize that enhancements in PAN due to wildfire emissions may lead to regional enhancements in O3 during high fire years. The second case is for the Salt Lake City (SLC) region for August 2012. During this period the MDA8 reached 83 ppbv and the SMR suggests a wildfire contribution of 19 ppbv to the MDA8. The wildfire influence is supported by PM2.5 data, the known location of wildfires at the time, HYSPLIT dispersion modeling that indicates transport from fires in Idaho, and results from the CMAQ model that confirm the fire impacts. Concentrations of PM2.5 and O3 are enhanced during this period, but overall there is a poor relationship between them, which is consistent with the complexities in the secondary production of O3. A third case looks at high MDA8 in Boise, ID, during July 2012 and reaches similar conclusions. These results support the use of statistical modeling as a tool to quantify the influence from wildfires on urban O3 concentrations.

Free troposphere as a major source of CCN for the equatorial pacific boundary layer: long-range transport and teleconnections

Abstract. Airborne aerosol measurements in the central equatorial Pacific during PASE (Pacific Atmospheric Sulfur Experiment) revealed that cloud condensation nuclei (CCN) activated in marine boundary layer (MBL) clouds were strongly influenced by entrainment from the free troposphere (FT). About 65% entered at sizes effective as CCN in MBL clouds, while ~25% entered the MBL too small to activate but subsequently grew via gas to particle conversion. The remaining ~10% were inferred to be sea salt aerosol. FT aerosols at low carbon monoxide (CO) mixing ratios (&lt; 63 ppbv) were mostly volatile at 360 °C with a number mode peak of around 30–40 nm dry diameter and tended to be associated with cloud outflow from distant (3000 km or more) deep convection. Higher CO concentrations were commonly associated with trajectories from South America and the Amazon region (ca. ~10 000 km away) and occurred in layers indicative of combustion sources (biomass burning season) partially scavenged by precipitation. These had number modes near 60–80 nm dry diameter with a large fraction of CCN.2 (those activated at 0.2% supersaturation and representative of MBL clouds) prior to entrainment into the MBL. Flight averaged concentrations of CCN.2 were similar for measurements near the surface, below the inversion and in the FT just above the inversion, confirming that subsidence and entrainment of FT aerosol strongly influenced MBL CCN.2. Concurrent flight-to-flight variations of CCN.2 at all altitudes below 3 km also imply MBL CCN.2 concentrations were in quasi-equilibrium with the FT over a 2–3 day timescale. The observed FT transport over thousands of kilometers indicates teleconnections between MBL CCN and cloud-scavenged sources of both natural and/or residual combustion origin. Nonetheless, in spite of its importance, this source of CCN number is not well represented in most current models and is generally not detectable by satellite because of the low aerosol scattering in such layers as a result of cloud scavenging. In addition, our measurements confirm nucleation in the MBL was not evident during PASE and argue against a localized linear relation in the MBL between dimethyl sulfide (DMS) and CCN suggested by the CLAW hypothesis. However, when the FT is not impacted by long-range transport, sulfate aerosol derived from DMS pumped aloft in the ITCZ (Inter-Tropical Convergence Zone) can provide a source of CCN to the boundary layer via FT teleconnections involving more complex non-linear processes.