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Ambient concentrations of trace elements with 2 h time resolution were measured in PM<sub>10–2.5</sub>, PM<sub>2.5–1.0</sub> and PM<sub>1.0–0.3</sub> size ranges at kerbside, urban background and rural sites in London during winter 2012. Samples were collected using rotating drum impactors (RDIs) and subsequently analysed with synchrotron radiation-induced X-ray fluorescence spectrometry (SR-XRF). Quantification of kerb and urban increments (defined as kerb-to-urban and urban-to-rural concentration ratios, respectively), and assessment of diurnal and weekly variability provided insight into sources governing urban air quality and the effects of urban micro-environments on human exposure. Traffic-related elements yielded the highest kerb increments, with values in the range of 10.4 to 16.6 for SW winds (3.3–6.9 for NE) observed for elements influenced by brake wear (e.g. Cu, Sb, Ba) and 5.7 to 8.2 for SW (2.6–3.0 for NE) for other traffic-related processes (e.g. Cr, Fe, Zn). Kerb increments for these elements were highest in the PM<sub>10–2.5</sub> mass fraction, roughly twice that of the PM<sub>1.0–0.3</sub> fraction. These elements also showed the highest urban increments (~ 3.0), although no difference was observed between brake wear and other traffic-related elements. All elements influenced by traffic exhibited higher concentrations during morning and evening rush hours, and on weekdays compared to weekends, with the strongest trends observed at the kerbside site, and additionally enhanced by winds coming directly from the road, consistent with street canyon effects. Elements related to mineral dust (e.g. Al, Si, Ca, Sr) showed significant influences from traffic-induced resuspension, as evidenced by moderate kerb (3.4–5.4 for SW, 1.7–2.3 for NE) and urban (~ 2) increments and increased concentrations during peak traffic flow. Elements related to regional transport showed no significant enhancement at kerb or urban sites, with the exception of PM<sub>10–2.5</sub> sea salt (factor of up to 2), which may be influenced by traffic-induced resuspension of sea and/or road salt. Heavy-duty vehicles appeared to have a larger effect than passenger vehicles on the concentrations of all elements influenced by resuspension (including sea salt) and wearing processes. Trace element concentrations in London were influenced by both local and regional sources, with coarse and intermediate fractions dominated by traffic-induced resuspension and wearing processes and fine particles influenced by regional transport.
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Despite the need to understand the impact of changes in emissions and climate on tropospheric ozone, the attribution of tropospheric interannual ozone variability to specific processes has proven difficult. Here, we analyze the stratospheric contribution to tropospheric ozone variability and trends from 1953 to 2005 in the Northern Hemisphere (NH) mid-latitudes using four ensemble simulations of the free running (FR) Whole Atmosphere Community Climate Model (WACCM). The simulations are externally forced with observed time-varying (1) sea-surface temperatures (SSTs), (2) greenhouse gases (GHGs), (3) ozone depleting substances (ODS), (4) quasi-biennial oscillation (QBO), (5) solar variability (SV) and (6) stratospheric sulfate surface area density (SAD). A detailed representation of stratospheric chemistry is simulated, including the ozone loss due to volcanic eruptions and polar stratospheric clouds. In the troposphere, ozone production is represented by CH<sub>4</sub>–NO<sub>x</sub> smog chemistry, where surface chemical emissions remain interannually constant. Despite the simplicity of its tropospheric chemistry, at many NH measurement locations, the interannual ozone variability in the FR WACCM simulations is significantly correlated with the measured interannual variability. This suggests the importance of the external forcing applied in these simulations in driving interannual ozone variability. The variability and trend in the simulated 1953–2005 tropospheric ozone from 30 to 90° N at background surface measurement sites, 500 hPa measurement sites and in the area average are largely explained on interannual timescales by changes in the 30–90° N area averaged flux of ozone across the 100 hPa surface and changes in tropospheric methane concentrations. The average sensitivity of tropospheric ozone to methane (percent change in ozone to a percent change in methane) from 30 to 90° N is 0.17 at 500 hPa and 0.21 at the surface; the average sensitivity of tropospheric ozone to the 100 hPa ozone flux (percent change in ozone to a percent change in the ozone flux) from 30 to 90° N is 0.19 at 500 hPa and 0.11 at the surface. The 30–90° N simulated downward residual velocity at 100 hPa increased by 15% between 1953 and 2005. However, the impact of this on the 30–90° N 100 hPa ozone flux is modulated by the long-term changes in stratospheric ozone. The ozone flux decreases from 1965 to 1990 due to stratospheric ozone depletion, but increases again by approximately 7% from 1990 to 2005. The first empirical orthogonal function of interannual ozone variability explains from 40% (at the surface) to over 80% (at 150 hPa) of the simulated ozone interannual variability from 30 to 90° N. This identified mode of ozone variability shows strong stratosphere–troposphere coupling, demonstrating the importance of the stratosphere in an attribution of tropospheric ozone variability. The simulations, with no change in emissions, capture almost 50% of the measured ozone change during the 1990s at a variety of locations. This suggests that a large portion of the measured change is not due to changes in emissions, but can be traced to changes in large-scale modes of ozone variability. This emphasizes the difficulty in the attribution of ozone changes, and the importance of natural variability in understanding the trends and variability of ozone. We find little relation between the El Niño–Southern Oscillation (ENSO) index and large-scale tropospheric ozone variability over the long-term record.
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Emission inventories of elemental carbon (EC) and organic carbon (OC) contain large uncertainties both in their spatial and temporal distributions for different source types. An inverse model was used to evaluate EC and OC emissions based on 1 year of hourly measurements from the St. Louis–Midwest supersite. The input to the model consisted of continuous measurements of EC and OC obtained for 2002 using two semicontinuous analyzers. High resolution meteorological simulations were performed for the entire time period using the Weather Research and Forecasting Model (WRF). These were used to simulate hourly back trajectories at the measurement site using a Lagrangian model (FLEXPART-WRF). In combination, an Eulerian model (CAMx: The Comprehensive Air Quality Model with Extensions ) was used to simulate the impacts at the measurement site using known emissions inventories for point and area sources from the Lake Michigan Directors Consortium (LADCO) as well as for open burning from the Fire Inventory from NCAR (FINN). By considering only passive transport of pollutants, the Bayesian inversion simplifies to a single least squares inversion. The inverse model combines forward Eulerian simulations with backward Lagrangian simulations to yield estimates of emissions from sources in current inventories as well as from emissions that might be missing in the inventories. The CAMx impacts were disaggregated into separate time chunks in order to determine improved diurnal, weekday and monthly temporal patterns of emissions. Because EC is a primary species, the inverse model estimates can be interpreted directly as emissions. In contrast, OC is both a primary and a secondary species. As the inverse model does not differentiate between direct emissions and formation in the plume of those direct emissions, the estimates need to be interpreted as contributions to measured concentrations. Emissions of EC and OC in the St. Louis region from on-road, non-road, marine/aircraft/railroad (MAR), "other" and point sources were revised slightly downwards on average. In particular, both MAR and point sources had a more pronounced diurnal variation than in the inventory. The winter peak in "other" emissions was not corroborated by the inverse model. On-road emissions have a larger difference between weekday and weekends in the inverse estimates than in the inventory, and appear to be poorly simulated or characterized in the winter months. The model suggests that open burning emissions are significantly underestimated in the inventory. Finally, contributions of unknown sources seems to be from areas to the south of St. Louis and from afternoon and nighttime emissions.
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The Arctic region is known to be very sensitive to climate change. Clouds and in particular mixed-phase clouds (MPCs) remain one of the greatest sources of uncertainties in the modelling of the Arctic response to climate change due to an inaccurate representation of their variability and their quantification. In this study, we present a characterisation of the vertical, spatial and seasonal variability of Arctic clouds and MPCs over the entire Arctic region based on satellite active remote sensing observations. MPC properties in the region of the Svalbard archipelago (78° N, 15° E) are also investigated. The occurrence frequency of clouds and MPCs are determined from CALIPSO/CLOUDSAT measurements processed with the DARDAR retrieval algorithm, which allow for a reliable cloud thermodynamic phase classification (warm liquid, supercooled liquid, ice, mixing of ice and supercooled liquid). Significant differences are observed between MPC properties over the entire Arctic region and over the Svalbard region. Results show that MPCs are encountered all year long, with a minimum occurrence of 30% in winter and 50% during the rest of the year on average over the entire Arctic. Over the Svalbard region, MPC occurrence is more constant with time with larger values (55%) compared to the average observed in the Arctic. MPCs are especially located at low altitudes, below 3000 m, where their frequency of occurrence reaches 90%, particularly during winter, spring and autumn. Moreover, results highlight that MPCs are statistically more frequent above open sea than land or sea ice. The temporal and spatial distribution of MPCs over the Svalbard region seems to be linked to the supply of moister air and warmer water from the North Atlantic Ocean, which contribute to the initiation of the liquid water phase. Over the whole Arctic, and particularly in western regions, the increase of MPC occurrence from spring to autumn could be connected to the sea ice melting. During this period, the open water transports some of the warm water from the North Atlantic Ocean to the rest of the Arctic region. This facilitates the vertical transfer of moisture and thus the persistence of the liquid phase. Particular attention is also paid to the measurement uncertainties and how they could affect our conclusions.
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This study focuses on the analysis of Aerosol Robotic Network (AERONET) aerosol data obtained over Alborán Island (35.90° N, 3.03° W, 15 m a.s.l.) in the western Mediterranean from July 2011 to January 2012. Additional aerosol data from the three nearest AERONET stations (Málaga, Oujda and Palma de Mallorca) and the Maritime Aerosol Network (MAN) were also analyzed in order to investigate the temporal and spatial variations of aerosol over this scarcely explored region. High aerosol loads over Alborán were mainly associated with desert dust transport from North Africa and occasional advection of anthropogenic fine particles from central European urban-industrial areas. The fine particle load observed over Alborán was surprisingly similar to that obtained over the other three nearest AERONET stations, suggesting homogeneous spatial distribution of fine particle loads over the four studied sites in spite of the large differences in local sources. The results from MAN acquired over the Mediterranean Sea, Black Sea and Atlantic Ocean from July to November 2011 revealed a pronounced predominance of fine particles during the cruise period.
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We present ozone measurements made using state-of-the-art ultraviolet photometers onboard three long-duration stratospheric balloons launched as part of the Concordiasi campaign in austral spring 2010. Ozone loss rates calculated by matching air parcels sampled at different times and places during the polar spring are in agreement with rates previously derived from ozonesonde measurements, for the vortex average, ranging between 2 and 7 ppbv per sunlit hour or between 25 and 110 ppbv per day. However, the geographical coverage of these long-duration stratospheric balloon platforms provides new insights into the temporal and spatial patterns of ozone loss over Antarctica. Very large ozone loss rates of up to 230 ppbv per day (16 ppbv per sunlit hour) are observed for air masses that are downwind of the Antarctic Peninsula and/or over the East Antarctic region. The ozone loss rate maximum downstream of the Antarctic Peninsula region is consistent with high PSC occurrence from CALIPSO and large ClO abundances from MLS satellite observations for 12–22 September 2010, and with a chemical box model simulation using JPL 2011 kinetics with full chlorine activation.
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Solid fuel emissions, including those from biomass burning, are increasing in urban areas across the European Union due to rising energy costs and government incentives to use renewable energy sources for heating. In order to help protect human health as well as to improve air quality and pollution abatement strategies, the sources of combustion aerosols, their contributions, and the processes they undergo need to be better understood. A high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) was therefore deployed at an urban background site between January and February 2012 to investigate solid fuel organic aerosols (SFOA) in London. The variability of SFOA was examined and the factors governing the split between the two SFOA factors derived from Positive Matrix Factorisation (PMF) were assessed. The concentrations of both factors were found to increase during the night and during cold periods, consistent with domestic space heating activities. The split between the two factors is likely governed predominantly by differences in burn conditions where SFOA1 best represents more efficient burns and SFOA2 best represents less efficient burns. The differences in efficiency may be due to burner types or burn phase, for example. Different fuel types and levels of atmospheric processing also likely contribute to the two factors. As the mass spectral profile of SFOA is highly variable, the findings from this study may have implications for improving future source apportionment and factorisation analyses. <br><br> During the winter, SFOA was found to contribute 38% to the total non-refractory submicron organic aerosol (OA) mass, with similar contributions from both SFOA factors (20% from SFOA1 and 18% from SFOA2). A similar contribution of SFOA was derived for the same period from a compact time-of-flight AMS (cToF-AMS), which measured for a full calendar year at the same site. The seasonality of SFOA was investigated using the year-long data set where concentrations were greatest in the autumn and winter. During the summer, SFOA contributed 11% to the organic fraction, where emissions resulted from different anthropogenic activities such as barbecues and domestic garden wood burning. The significant contribution of SFOA to total organic mass throughout the year suggests that the negative effects on health and air quality, as well as climate, are not just confined to winter as exposure to these aerosols and the associated black carbon can also occur during the summer, which may have significant implications for air-quality policies and mitigation strategies.
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We present a study on validation of the National Institute for Environmental Studies Transport Model (NIES TM) by comparing to observed vertical profiles of atmospheric CO<sub>2</sub>. The model uses a hybrid sigma-isentropic (σ–θ) vertical coordinate that employs both terrain-following and isentropic parts switched smoothly in the stratosphere. The model transport is driven by reanalyzed meteorological fields and designed to simulate seasonal and diurnal cycles, synoptic variations, and spatial distributions of atmospheric chemical constituents in the troposphere. The model simulations were run for biosphere, fossil fuel, air–ocean exchange, biomass burning and inverse correction fluxes of carbon dioxide (CO<sub>2</sub>) by GOSAT Level 4 product. We compared the NIES TM simulated fluxes with data from the HIAPER Pole-to-Pole Observations (HIPPO) Merged 10 s Meteorology, Atmospheric Chemistry, and Aerosol Data, including HIPPO-1, HIPPO-2 and HIPPO-3 from 128.0° E to −84.0° W, and 87.0° N to −67.2° S. <br><br> The simulation results were compared with CO<sub>2</sub> observations made in January and November 2009, and March and April 2010. The analysis attests that the model is good enough to simulate vertical profiles with errors generally within 1–2 ppmv, except for the lower stratosphere in the Northern Hemisphere high latitudes.
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