ALBERT

Description: Abundance-based model evaluations with observations provide critical tests for the simulated mean state in models of intercontinental pollution transport, and under certain conditions may also offer constraints on model responses to emission changes. We compile multiyear measurements of peroxy acetyl nitrate (PAN) available from five mountaintop sites and apply them in a proof-of-concept approach that exploits an ensemble of global chemical transport models (HTAP1) to identify an observational “emergent constraint”. In April, when the signal from anthropogenic emissions on PAN is strongest, simulated PAN at northern midlatitude mountaintops correlates strongly with PAN source–receptor relationships (the response to 20 % reductions in precursor emissions within northern midlatitude continents; hereafter, SRRs). This finding implies that PAN measurements can provide constraints on PAN SRRs by limiting the SRR range to that spanned by the subset of models simulating PAN within the observed range. In some cases, regional anthropogenic volatile organic compound (AVOC) emissions, tracers of transport from different source regions, and SRRs for ozone also correlate with PAN SRRs. Given the large observed interannual variability in the limited available datasets, establishing strong constraints will require matching meteorology in the models to the PAN measurements. Application of this evaluation approach to the chemistry–climate models used to project changes in atmospheric composition will require routine, long-term mountaintop PAN measurements to discern both the climatological SRR signal and its interannual variability.

Description: Understanding the properties and life cycle processes of aerosol particles in regional air masses is crucial for constraining the climate impacts of aerosols on a global scale. In this study, characteristics of aerosols in the boundary layer (BL) and free troposphere (FT) of a remote continental region in the western US were studied using a high-resolution time-of-flight aerosol mass spectrometer (HR-AMS) deployed at the Mount Bachelor Observatory (MBO; 2763 m a.s.l.) in central Oregon in summer 2013. In the absence of wildfire influence, the average (±1σ) concentration of non-refractory submicrometer particulate matter (NR-PM1) at MBO was 2.8 (±2.8) µg m−3 and 84 % of the mass was organic. The other NR-PM1 components were sulfate (11 %), ammonium (2.8 %), and nitrate (0.9 %). The organic aerosol (OA) at MBO from these clean periods showed clear diurnal variations driven by the boundary layer dynamics with significantly higher concentrations occurring during daytime, upslope conditions. NR-PM1 contained a higher mass fraction of sulfate and was frequently acidic when MBO resided in the FT. In addition, OA in the FT was found to be highly oxidized (average O∕C of 1.17) with low volatility while OA in BL-influenced air masses was moderately oxidized (average O∕C of 0.67) and semivolatile. There are indications that the BL-influenced OA observed at MBO was more enriched in organonitrates and organosulfur compounds (e.g., MSA) and appeared to be representative of biogenic secondary organic aerosol (SOA) originated in the BL. A summary of the chemical compositions of NR-PM1 measured at a number of other high-altitude locations in the world is presented and similar contrasts between FT and BL aerosols were observed. The significant compositional and physical differences observed between FT and BL aerosols may have important implications for understanding the climate effects of regional background aerosols.

Description: Atmospheric chemistry and transport of mercury play a key role in the global mercury cycle. However, there are still considerable knowledge gaps concerning the fate of mercury in the atmosphere. This is the second part of a model intercomparison study investigating the impact of atmospheric chemistry and emissions on mercury in the atmosphere. While the first study focused on ground-based observations of mercury concentration and deposition, here we investigate the vertical and interhemispheric distribution and speciation of mercury from the planetary boundary layer to the lower stratosphere. So far, there have been few model studies investigating the vertical distribution of mercury, mostly focusing on single aircraft campaigns. Here, we present a first comprehensive analysis based on various aircraft observations in Europe, North America, and on intercontinental flights. The investigated models proved to be able to reproduce the distribution of total and elemental mercury concentrations in the troposphere including interhemispheric trends. One key aspect of the study is the investigation of mercury oxidation in the troposphere. We found that different chemistry schemes were better at reproducing observed oxidized mercury patterns depending on altitude. High concentrations of oxidized mercury in the upper troposphere could be reproduced with oxidation by bromine while elevated concentrations in the lower troposphere were better reproduced by OH and ozone chemistry. However, the results were not always conclusive as the physical and chemical parameterizations in the chemistry transport models also proved to have a substantial impact on model results.

Description: US background ozone (O3) includes O3 produced from anthropogenic O3 precursors emitted outside of the USA, from global methane, and from any natural sources. Using a suite of sensitivity simulations in the GEOS-Chem global chemistry transport model, we estimate the influence from individual background sources versus US anthropogenic sources on total surface O3 over 10 continental US regions from 2004 to 2012. Evaluation with observations reveals model biases of +0–19 ppb in seasonal mean maximum daily 8 h average (MDA8) O3, highest in summer over the eastern USA. Simulated high-O3 events cluster too late in the season. We link these model biases to excessive regional O3 production (e.g., US anthropogenic, biogenic volatile organic compounds (BVOCs), and soil NOx, emissions), or coincident missing sinks. On the 10 highest observed O3 days during summer (O3_top10obs_JJA), US anthropogenic emissions enhance O3 by 5–11 ppb and by less than 2 ppb in the eastern versus western USA. The O3 enhancement from BVOC emissions during summer is 1–7 ppb higher on O3_top10obs_JJA days than on average days, while intercontinental pollution is up to 2 ppb higher on average versus on O3_top10obs_JJA days. During the summers of 2004–2012, monthly regional mean US background O3 MDA8 levels vary by up to 15 ppb from year to year. Observed and simulated summertime total surface O3 levels on O3_top10obs_JJA days decline by 3 ppb (averaged over all regions) from 2004–2006 to 2010–2012, reflecting rising US background (+2 ppb) and declining US anthropogenic O3 emissions (−6 ppb) in the model. The model attributes interannual variability in US background O3 on O3_top10obs days to natural sources, not international pollution transport. We find that a 3-year averaging period is not long enough to eliminate interannual variability in background O3 on the highest observed O3 days.

Description: Biomass burning (BB) is one of the most important contributors to atmospheric aerosols on a global scale, and wildfires are a large source of emissions that impact regional air quality and global climate. As part of the Biomass Burning Observation Project (BBOP) field campaign in summer 2013, we deployed a high-resolution time-of-flight aerosol mass spectrometer (HR-AMS) coupled with a thermodenuder at the Mt. Bachelor Observatory (MBO, ∼  2.8 km above sea level) to characterize the impact of wildfire emissions on aerosol loading and properties in the Pacific Northwest region of the United States. MBO represents a remote background site in the western US, and it is frequently influenced by transported wildfire plumes during summer. Very clean conditions were observed at this site during periods without BB influence where the 5 min average (±1σ) concentration of non-refractory submicron aerosols (NR-PM1) was 3.7 ± 4.2 µg m−3. Aerosol concentration increased substantially (reaching up to 210 µg m−3 of NR-PM1) for periods impacted by transported BB plumes, and aerosol composition was overwhelmingly organic. Based on positive matrix factorization (PMF) of the HR-AMS data, three types of BB organic aerosol (BBOA) were identified, including a fresh, semivolatile BBOA-1 (O ∕ C  =  0.35; 20 % of OA mass) that correlated well with ammonium nitrate; an intermediately oxidized BBOA-2 (O ∕ C  =  0.60; 17 % of OA mass); and a highly oxidized BBOA-3 (O ∕ C  =  1.06; 31 % of OA mass) that showed very low volatility with only  ∼  40 % mass loss at 200 °C. The remaining 32 % of the OA mass was attributed to a boundary layer (BL) oxygenated OA (BL-OOA; O ∕ C  =  0.69) representing OA influenced by BL dynamics and a low-volatility oxygenated OA (LV-OOA; O ∕ C  =  1.09) representing regional aerosols in the free troposphere. The mass spectrum of BBOA-3 resembled that of LV-OOA and had negligible contributions from the HR-AMS BB tracer ions – C2H4O2+ (m∕z = 60.021) and C3H5O2+ (m∕z = 73.029); nevertheless, it was unambiguously related to wildfire emissions. This finding highlights the possibility that the influence of BB emission could be underestimated in regional air masses where highly oxidized BBOA (e.g., BBOA-3) might be a significant aerosol component but where primary BBOA tracers, such as levoglucosan, are depleted. We also examined OA chemical evolution for persistent BB plume events originating from a single fire source and found that longer solar radiation led to higher mass fraction of the chemically aged BBOA-2 and BBOA-3 and more oxidized aerosol. However, an analysis of the enhancement ratios of OA relative to CO (ΔOA ∕ΔCO) showed little difference between BB plumes transported primarily at night versus during the day, despite evidence of substantial chemical transformation in OA induced by photooxidation. These results indicate negligible net OA production in photochemically aged wildfire plumes observed in this study, for which a possible reason is that SOA formation was almost entirely balanced by BBOA volatilization. Nevertheless, the formation and chemical transformation of BBOA during atmospheric transport can significantly influence downwind sites with important implications for health and climate.

Description: Biomass burning emissions emit a significant amount of trace gases and aerosols and can affect atmospheric chemistry and radiative forcing for hundreds or thousands of kilometres downwind. They can also contribute to exceedances of air quality standards and have negative impacts on human health. We present a case study of an intense wildfire plume from Siberia that affected the air quality across the Pacific Northwest on 6–10 July 2012. Using satellite measurements (MODIS True Colour RGB imagery and MODIS AOD), we track the wildfire smoke plume from its origin in Siberia to the Pacific Northwest where subsidence ahead of a subtropical Pacific High made the plume settle over the region. The normalized enhancement ratios of O3 and PM1 relative to CO of 0.26 and 0.08 are consistent with a plume aged 6–10 days. The aerosol mass in the plume was mainly submicron in diameter (PM1 ∕ PM2.5 = 0.96) and the part of the plume sampled at the Whistler High Elevation Monitoring Site (2182 m a.s.l.) was 88 % organic material. Stable atmospheric conditions along the coast limited the initial entrainment of the plume and caused local anthropogenic emissions to build up. A synthesis of air quality from the regional surface monitoring networks describes changes in ambient O3 and PM2.5 during the event and contrasts them to baseline air quality estimates from the AURAMS chemical transport model without wildfire emissions. Overall, the smoke plume contributed significantly to the exceedances in O3 and PM2.5 air quality standards and objectives that occurred at several communities in the region during the event. Peak enhancements in 8 h O3 of 34–44 ppbv and 24 h PM2.5 of 10–32 µg m−3 were attributed to the effects of the smoke plume across the Interior of British Columbia and at the Whistler Peak High Elevation Site. Lesser enhancements of 10–12 ppbv for 8 h O3 and of 4–9 µg m−3 for 24 h PM2.5 occurred across coastal British Columbia and Washington State. The findings suggest that the large air quality impacts seen during this event were a combination of the efficient transport of the plume across the Pacific, favourable entrainment conditions across the BC interior, and the large scale of the Siberian wildfire emissions. A warming climate increases the risk of increased wildfire activity and events of this scale reoccurring under appropriate meteorological conditions.

Description: We present month-long observations of speciated acyl peroxy nitrates (APNs), including PAN, PPN, MPAN, APAN, and the sum of PiBN and PnBN, measured at the Mount Bachelor Observatory (MBO) as part of the INTEX-B collaborative field campaign during spring 2006. APN abundances, measured by thermal dissociation-chemical ionization mass spectrometry (TD-CIMS), are discussed in terms of differing contributions from the boundary layer and the free troposphere and in the context of previous APN measurements in the NE Pacific region. PAN mixing ratios range from 11 to 3955 pptv, with a mean value of 334 pptv for the full measurement period. PPN is linearly correlated with PAN (r2=0.96), with an average abundance of 6.5% relative to PAN; other APNs are generally

Description: Interannual variations in background tropospheric trace gases (such as carbon monoxide, CO) are largely driven by variations in emissions (especially wildfires), transport pathways and tropospheric oxidizing capacity. Understanding this variability is essential to quantify the intercontinental contribution to US air quality. We investigate the interannual variability of long-range transport of Asian pollutants to the Northeast Pacific via measurements from the Mt. Bachelor Observatory (MBO: 43.98° N, 121.69° W; 2.7 km above sea level) and GEOS-Chem chemical transport model simulations in spring 2005 vs. the INTEX-B campaign during spring 2006. Measurements of CO at MBO were significantly enhanced during spring 2005 relative to the same time in 2006 (the INTEX-B study period); a monthly mean decline in CO of 41 ppbv was observed between April 2005 and April 2006. Meteorological indices show that long-range transport of CO from the heavily industrialized region of East Asia was significantly greater in 2005 than in 2006. In addition, spring 2005 was an anomalously strong biomass burning season in Southeast Asia. Data presented by Yurganov et al. (2008) using MOPITT satellite retrievals from this area reveal an average CO burden anomaly (referenced to March 2000–February 2002 mean values) between October 2004 through April 2005 of 2.6 Tg CO vs. 0.6 Tg CO for the same period a year later. The Naval Research Laboratory's global aerosol transport model shows that emissions from these fires were efficiently transported to MBO throughout April 2005. Asian dust transport, however, was substantially greater in 2006 than 2005, particularly in May. Monthly mean aerosol light scattering coefficient at 532 nm (σsp) at MBO more than doubled from 2.7 Mm−1 in May 2005 to 6.2 Mm−1 in May 2006. We also evaluate CO interannual variability throughout the western US via Earth System Research Laboratory ground site data and throughout the Northern Hemisphere via MOPITT and TES satellite observations. Both in the Northeast Pacific and on larger scales, we reveal a significant decrease (from 2–21%) in springtime maximum CO between 2005 and 2006, evident in all platforms and the GEOS-Chem model. We attribute this to (a) anomalously strong biomass burning in Southeast Asia during winter 2004 through spring 2005, and (b) the transport pattern in 2006 which limited the inflow of Asian pollution to the lower free troposphere over western North America.

Description: We use an ensemble of aircraft, satellite, sonde, and surface observations for April–May 2006 (NASA/INTEX-B aircraft campaign) to better understand the mechanisms for transpacific ozone pollution and its implications for North American air quality. The observations are interpreted with a global 3-D chemical transport model (GEOS-Chem). OMI NO2 satellite observations constrain Asian anthropogenic NOx emissions and indicate a factor of 2 increase from 2000 to 2006 in China. Satellite observations of CO from AIRS and TES indicate two major events of Asian transpacific pollution during INTEX-B. Correlation between TES CO and ozone observations shows evidence for transpacific ozone pollution. The semi-permanent Pacific High and Aleutian Low cause splitting of transpacific pollution plumes over the Northeast Pacific. The northern branch circulates around the Aleutian Low and has little impact on North America. The southern branch circulates around the Pacific High and impacts western North America. Both aircraft measurements and model results show sustained ozone production driven by peroxyacetylnitrate (PAN) decomposition in the southern branch, roughly doubling the transpacific influence from ozone produced in the Asian boundary layer. Model simulation of ozone observations at Mt. Bachelor Observatory in Oregon (2.7 km altitude) indicates a mean Asian ozone pollution contribution of 9±3 ppbv to the mean observed concentration of 54 ppbv, reflecting mostly an enhancement in background ozone rather than episodic Asian plumes. Asian pollution enhanced surface ozone concentrations by 5–7 ppbv over western North America in spring 2006. The 2000–2006 rise in Asian anthropogenic emissions increased the influence by 1–2 ppbv.

Description: New observational evidence of the trans-Pacific transport of Asian dust and its contribution to the ambient particulate matter (PM) levels in North America was revealed, based on the interannual variations between Asian dust storms and the ambient PM levels in western North America from year 2000 to 2006. A high correlation was found between them with an R2 value of 0.83. From analysis of the differences in the correlation between 2005 and 2006, three factors explain the variation of trans-Pacific transport and influences of Asian dust storms on PM levels in western North America. These were identified by modeling results and the re-analysis data. They were 1) Strength of frontal cyclones from Mongolia to north eastern China: The frontal cyclones in East Asia not only bring strong cold air outbreaks, generating dust storms in East Asia, but also lift Asian dust into westerly winds of the free troposphere for trans-Pacific transport; 2) Pattern of transport pathway over the North Pacific: The circulation patterns of westerlies over the North Pacific govern the trans-Pacific transport pattern. Strong zonal airflow of the westerly jet in the free troposphere over the North Pacific favor significant trans-Pacific transport of Asian dust; 3) Variation of precipitation in the North Pacific: The scavenging of Asian dust particles by precipitation is a major process of dust removal on the trans-Pacific transport pathway; therefore, variation of precipitation in the North Pacific could affect trans-Pacific transport of Asian dust.