Items

Advanced search

Secondary organic aerosol formation exceeds primary particulate matter emissions for light-duty gasoline vehicles

The effects of photochemical aging on emissions from 15 light-duty gasoline vehicles were investigated using a smog chamber to probe the critical link between the tailpipe and ambient atmosphere. The vehicles were recruited from the California in-use fleet; they represent a wide range of model years (1987 to 2011), vehicle types and emission control technologies. Each vehicle was tested on a chassis dynamometer using the unified cycle. Dilute emissions were sampled into a portable smog chamber and then photochemically aged under urban-like conditions. For every vehicle, substantial secondary organic aerosol (SOA) formation occurred during cold-start tests, with the emissions from some vehicles generating as much as 6 times the amount of SOA as primary particulate matter (PM) after 3 h of oxidation inside the chamber at typical atmospheric oxidant levels (and 5 times the amount of SOA as primary PM after 5 × 106 molecules cm−3 h of OH exposure). Therefore, the contribution of light-duty gasoline vehicle exhaust to ambient PM levels is likely dominated by secondary PM production (SOA and nitrate). Emissions from hot-start tests formed about a factor of 3–7 less SOA than cold-start tests. Therefore, catalyst warm-up appears to be an important factor in controlling SOA precursor emissions. The mass of SOA generated by photooxidizing exhaust from newer (LEV2) vehicles was a factor of 3 lower than that formed from exhaust emitted by older (pre-LEV) vehicles, despite much larger reductions (a factor of 11–15) in nonmethane organic gas emissions. These data suggest that a complex and nonlinear relationship exists between organic gas emissions and SOA formation, which is not surprising since SOA precursors are only one component of the exhaust. Except for the oldest (pre-LEV) vehicles, the SOA production could not be fully explained by the measured oxidation of speciated (traditional) SOA precursors. Over the timescale of these experiments, the mixture of organic vapors emitted by newer vehicles appears to be more efficient (higher yielding) in producing SOA than the emissions from older vehicles. About 30% of the nonmethane organic gas emissions from the newer (LEV1 and LEV2) vehicles could not be speciated, and the majority of the SOA formed from these vehicles appears to be associated with these unspeciated organics. By comparing this study with a companion study of diesel trucks, we conclude that both primary PM emissions and SOA production for light-duty gasoline vehicles are much greater than for late-model (2007 and later) on-road heavy-duty diesel trucks.
Missing peroxy radical sources within a summertime ponderosa pine forest

Organic peroxy (RO2) and hydroperoxy (HO2) radicals are key intermediates in the photochemical processes that generate ozone, secondary organic aerosol and reactive nitrogen reservoirs throughout the troposphere. In regions with ample biogenic hydrocarbons, the richness and complexity of peroxy radical chemistry presents a significant challenge to current-generation models, especially given the scarcity of measurements in such environments. We present peroxy radical observations acquired within a ponderosa pine forest during the summer 2010 Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H2O, Organics and Nitrogen – Rocky Mountain Organic Carbon Study (BEACHON-ROCS). Total peroxy radical mixing ratios reach as high as 180 pptv (parts per trillion by volume) and are among the highest yet recorded. Using the comprehensive measurement suite to constrain a near-explicit 0-D box model, we investigate the sources, sinks and distribution of peroxy radicals below the forest canopy. The base chemical mechanism underestimates total peroxy radicals by as much as a factor of 3. Since primary reaction partners for peroxy radicals are either measured (NO) or underpredicted (HO2 and RO2, i.e., self-reaction), missing sources are the most likely explanation for this result. A close comparison of model output with observations reveals at least two distinct source signatures. The first missing source, characterized by a sharp midday maximum and a strong dependence on solar radiation, is consistent with photolytic production of HO2. The diel profile of the second missing source peaks in the afternoon and suggests a process that generates RO2 independently of sun-driven photochemistry, such as ozonolysis of reactive hydrocarbons. The maximum magnitudes of these missing sources (~120 and 50 pptv min−1, respectively) are consistent with previous observations alluding to unexpectedly intense oxidation within forests. We conclude that a similar mechanism may underlie many such observations.
Impacts of increasing the aerosol complexity in the Met Office global numerical weather prediction model

The inclusion of the direct and indirect radiative effects of aerosols in high-resolution global numerical weather prediction (NWP) models is being increasingly recognised as important for the improved accuracy of short-range weather forecasts. In this study the impacts of increasing the aerosol complexity in the global NWP configuration of the Met Office Unified Model (MetUM) are investigated. A hierarchy of aerosol representations are evaluated including three-dimensional monthly mean speciated aerosol climatologies, fully prognostic aerosols modelled using the CLASSIC aerosol scheme and finally, initialised aerosols using assimilated aerosol fields from the GEMS project. The prognostic aerosol schemes are better able to predict the temporal and spatial variation of atmospheric aerosol optical depth, which is particularly important in cases of large sporadic aerosol events such as large dust storms or forest fires. Including the direct effect of aerosols improves model biases in outgoing long-wave radiation over West Africa due to a better representation of dust. However, uncertainties in dust optical properties propagate to its direct effect and the subsequent model response. Inclusion of the indirect aerosol effects improves surface radiation biases at the North Slope of Alaska ARM site due to lower cloud amounts in high-latitude clean-air regions. This leads to improved temperature and height forecasts in this region. Impacts on the global mean model precipitation and large-scale circulation fields were found to be generally small in the short-range forecasts. However, the indirect aerosol effect leads to a strengthening of the low-level monsoon flow over the Arabian Sea and Bay of Bengal and an increase in precipitation over Southeast Asia. Regional impacts on the African Easterly Jet (AEJ) are also presented with the large dust loading in the aerosol climatology enhancing of the heat low over West Africa and weakening the AEJ. This study highlights the importance of including a more realistic treatment of aerosol–cloud interactions in global NWP models and the potential for improved global environmental prediction systems through the incorporation of more complex aerosol schemes.
Hygroscopicity, CCN and volatility properties of submicron atmospheric aerosol in a boreal forest environment during the summer of 2010

A Volatility-Hygroscopicity Tandem Differential Mobility Analyzer (VH-TDMA) was applied to study the hygroscopicity and volatility properties of submicron atmospheric aerosol particles in a boreal forest environment in Hyytiälä, Finland during the summer of 2010. Aitken and accumulation mode internally mixed particles (50 nm, 75 nm and 110 nm in diameter) were investigated. Hygroscopicity was found to increase with particle size. The relative mass fraction of organics and SO42- is probably the major contributor to the fluctuation of the hygroscopicity for all particle sizes. The Cloud Condensation Nuclei Counter (CCNC)-derived hygroscopicity parameter κ was observed to be slightly higher than κ calculated from VH-TDMA data under sub-saturated conditions, potential reasons for this behavior are discussed shortly. Also, the size-resolved volatility properties of particles were investigated. Upon heating, more small particles evaporated compared to large particles. There was a significant amount of aerosol volume (non-volatile material) left, even at heating temperatures of 280 °C. Using size resolved volatility-hygroscopicity analysis, we concluded that there was always hygroscopic material remaining in the particles at different heating temperatures, even at 280 °C. This indicates that the observed non-volatile aerosol material did not consist solely of black carbon.
Sulfur hexafluoride (SF6) emissions in East Asia determined by inverse modeling

Sulfur hexafluoride (SF6) has a global warming potential of around 22 800 over a 100-year time horizon and is one of the greenhouse gases regulated under the Kyoto Protocol. Around the year 2000 there was a reversal in the global SF6 emission trend, from a decreasing to an increasing trend, which was likely caused by increasing emissions in countries that are not obligated to report their annual emissions to the United Nations Framework Convention on Climate Change. In this study, SF6 emissions during the period 2006–2012 for all East Asian countries – including Mongolia, China, Taiwan, North Korea, South Korea and Japan – were determined by using inverse modeling and in situ atmospheric measurements. We found that the most important sources of uncertainty associated with these inversions are related to the choice of a priori emissions and their assumed uncertainty, the station network as well as the meteorological input data. Much lower uncertainties are due to seasonal variability in the emissions, inversion geometry and resolution, and the measurement calibration scale. Based on the results of these sensitivity tests, we estimate that the total SF6 emission in East Asia increased rapidly from 2404 ± 325 Mg yr−1 in 2006 to 3787 ± 512 Mg yr−1 in 2009 and stabilized thereafter. China contributed 60–72% to the total East Asian emission for the different years, followed by South Korea (8–16%), Japan (5–16%) and Taiwan (4–7%), while the contributions from North Korea and Mongolia together were less than 3% of the total. The per capita SF6 emissions are highest in South Korea and Taiwan, while the per capita emissions for China, North Korea and Japan are close to global average. During the period 2006–2012, emissions from China and from South Korea increased, while emissions from Taiwan and Japan decreased overall.
Processing of biomass-burning aerosol in the eastern Mediterranean during summertime

The aerosol chemical composition in air masses affected by wildfires from the Greek islands of Chios, Euboea and Andros, the Dalmatian Coast and Sicily, during late summer of 2012 was characterized at the remote background site of Finokalia, Crete. Air masses were transported several hundreds of kilometers, arriving at the measurement station after approximately half a day of transport, mostly during nighttime. The chemical composition of the particulate matter was studied by different high-temporal-resolution instruments, including an aerosol chemical speciation monitor (ACSM) and a seven-wavelength aethalometer. Despite the large distance from emission and long atmospheric processing, a clear biomass-burning organic aerosol (BBOA) profile containing characteristic markers is derived from BC (black carbon) measurements and positive matrix factorization (PMF) analysis of the ACSM organic mass spectra. The ratio of fresh to aged BBOA decreases with increasing atmospheric processing time and BBOA components appear to be converted to oxygenated organic aerosol (OOA). Given that the smoke was mainly transported overnight, it appears that the processing can take place in the dark. These results show that a significant fraction of the BBOA loses its characteristic AMS (aerosol mass spectrometry) signature and is transformed to OOA in less than a day. This implies that biomass burning can contribute almost half of the organic aerosol mass in the area during periods with significant fire influence.
Understanding the contributions of aerosol properties and parameterization discrepancies to droplet number variability in a global climate model

Aerosol indirect effects in climate models strongly depend on the representation of the aerosol activation process. In this study, we assess the process-level differences across activation parameterizations that contribute to droplet number uncertainty by using the adjoints of the Abdul-Razzak and Ghan (2000) and Fountoukis and Nenes (2005) droplet activation parameterizations in the framework of the Community Atmospheric Model version 5.1 (CAM5.1). The adjoint sensitivities of Nd to relevant input parameters are used to (i) unravel the spatially resolved contribution of aerosol number, mass, and chemical composition to changes in Nd between present-day and pre-industrial simulations and (ii) identify the key variables responsible for the differences in Nd fields and aerosol indirect effect estimates when different activation schemes are used within the same modeling framework. The sensitivities are computed online at minimal computational cost. Changes in aerosol number and aerosol mass concentrations were found to contribute to Nd differences much more strongly than chemical composition effects. The main sources of discrepancy between the activation parameterizations considered were the treatment of the water uptake by coarse mode particles, and the sensitivity of the parameterized Nd accumulation mode aerosol geometric mean diameter. These two factors explain the different predictions of Nd over land and over oceans when these parameterizations are employed. Discrepancies in the sensitivity to aerosol size are responsible for an exaggerated response to aerosol volume changes over heavily polluted regions. Because these regions are collocated with areas of deep clouds, their impact on shortwave cloud forcing is amplified through liquid water path changes. The same framework is also utilized to efficiently explore droplet number uncertainty attributable to hygroscopicity parameter of organic aerosol (primary and secondary). Comparisons between the parameterization-derived sensitivities of droplet number against predictions with detailed numerical simulations of the activation process were performed to validate the physical consistency of the adjoint sensitivities.
A tropical West Pacific OH minimum and implications for stratospheric composition

Most of the short-lived biogenic and anthropogenic chemical species that are emitted into the atmosphere break down efficiently by reaction with OH and do not reach the stratosphere. Here we show the existence of a pronounced minimum in the tropospheric column of ozone over the West Pacific, the main source region for stratospheric air, and suggest a corresponding minimum of the tropospheric column of OH. This has the potential to amplify the impact of surface emissions on the stratospheric composition compared to the impact when assuming globally uniform OH conditions. Specifically, the role of emissions of biogenic halogenated species for the stratospheric halogen budget and the role of increasing emissions of SO2 in Southeast Asia or from minor volcanic eruptions for the increasing stratospheric aerosol loading need to be reassessed in light of these findings. This is also important since climate change will further modify OH abundances and emissions of halogenated species. Our study is based on ozone sonde measurements carried out during the TransBrom cruise with the RV Sonne roughly along 140–150° E in October 2009 and corroborating ozone and OH measurements from satellites, aircraft campaigns and FTIR instruments. Model calculations with the GEOS-Chem Chemistry and Transport Model (CTM) and the ATLAS CTM are used to simulate the tropospheric OH distribution over the West Pacific and the transport pathways to the stratosphere. The potential effect of the OH minimum on species transported into the stratosphere is shown via modeling the transport and chemistry of CH2Br2 and SO2.
Seasonal variability and long-term evolution of tropospheric composition in the tropics and Southern Hemisphere

Impacts on tropospheric composition in the tropics and the Southern Hemisphere from biomass burning and other emission sources are studied using a global chemical transport model, surface measurements and satellite retrievals. Seasonal variations in observed CO at remote island sites are examined. Easter Island (eastern Pacific Ocean) is impacted indirectly by the hemispheric zonal transport of CO due to the burning in southern Africa/South America, via the westerlies. An increasing trend in CO by 0.33 ppb yr−1 in the past decade at Ascension Island is attributed to the combined effects of South American/southern Africa burnings and the increases in CH4 level. Compared to Easter Island and Ascension Island, much less contribution from biomass burning to atmospheric CO is found at the island of Mahé (western Indian Ocean), where the total CO peaks in January–February, reflecting the contributions of anthropogenic emissions from India. We also examine the 2000–2050 changes in atmospheric composition in the tropics and the Southern Hemisphere driven by future changes in emissions and climate. Changes in solar radiation (UV) over South Atlantic Ocean (SAO) in future January have dominant effects on the O3 distribution. More than 55% of O3 concentrations over the SAO in both present-day and future September are not directly affected by the emissions (including lightning) over the adjacent two continents but are attributable to the transport of O3 from surrounding areas due to CO and CH4 oxidation and stratospheric intrusion. High NOx emissions in both continents in 2050s increase PAN concentrations over remote oceans at the higher southern latitudes (> 35° S) as far as those near Australia, affecting the O3 budget over there. Future changes in biomass burning and anthropogenic NOx emissions in southern Africa lead to a new area of high O3 concentrations near South Africa. The resulted O3 outflow to the Indian Ocean is pronounced due to the effects of the persistent anticyclone. A general reduction in future OH radical concentrations is predicted over the remote marine boundary layer in the tropics and the Southern Hemisphere, as a result of the increases in CH4 and CO emissions.
Strong wintertime ozone events in the Upper Green River basin, Wyoming

During recent years, elevated ozone (O3) values have been observed repeatedly in the Upper Green River basin (UGRB), Wyoming, during wintertime. This paper presents an analysis of high ozone days in late winter 2011 (1 h average up to 166 ppbv – parts per billion by volume). Intensive operational periods (IOPs) of ambient monitoring were performed, which included comprehensive surface and boundary layer measurements. On IOP days, maximum O3 values are restricted to a very shallow surface layer. Low wind speeds in combination with low mixing layer heights (~ 50 m above ground level around noontime) are essential for accumulation of pollutants within the UGRB. Air masses contain substantial amounts of reactive nitrogen (NOx) and non-methane hydrocarbons (NMHC) emitted from fossil fuel exploration activities in the Pinedale Anticline. On IOP days particularly in the morning hours, reactive nitrogen (up to 69%), aromatics and alkanes (~ 10–15%; mostly ethane and propane) are major contributors to the hydroxyl (OH) reactivity. Measurements at the Boulder monitoring site during these time periods under SW wind flow conditions show the lowest NMHC / NOx ratios (~ 50), reflecting a relatively low reactive NMHC mixture, and a change from a NOx-limited regime towards a NMHC-limited regime as indicated by photochemical indicators, e.g., O3 /NOy, O3 /NOz, and O3 / HNO3 and the EOR (extent of reaction). OH production on IOP days is mainly due to nitrous acid (HONO). On a 24 h basis and as determined for a measurement height of 1.80 m above the surface HONO photolysis on IOP days can contribute ~ 83% to OH production on average, followed by alkene ozonolysis (~ 9%). Photolysis by ozone and HCHO photolysis contribute about 4% each to hydroxyl formation. High HONO levels (maximum hourly median on IOP days: 1096 pptv – parts per trillion by volume) are favored by a combination of shallow boundary layer conditions and enhanced photolysis rates due to the high albedo of the snow surface. HONO is most likely formed through (i) abundant nitric acid (HNO3) produced in atmospheric oxidation of NOx, deposited onto the snow surface and undergoing photo-enhanced heterogeneous conversion to HONO (estimated HONO production: 10.2 ± 40% ppbv h−1) and (ii) combustion-related emission of HONO (estimated HONO production: ~ 0.1 ± 30% ppbv h−1). HONO production is confined to the lowermost 10 m of the boundary layer. HONO, serves as the most important precursor for OH, strongly enhanced due to the high albedo of the snow cover (HONO photolysis rate 10.7 ± 30% ppbv h−1). OH radicals will oxidize NMHCs, mostly aromatics (toluene, xylenes) and alkanes (ethane, propane), eventually leading to an increase in ozone.