Items

Advanced search

Particle mass yield from β-caryophyllene ozonolysis

The influence of second-generation products on the particle mass yield of β-caryophyllene ozonolysis was systematically tested and quantified. The approach was to vary the relative concentrations of first- and second-generation products by adjusting the concentration of ozone while observing changes in particle mass yield. For all wall-loss corrected organic particle mass concentrations Morg of this study (0.5 < Morg < 230 μg m−3), the data show that the particle-phase organic material was composed for the most part of second-generation products. For 0.5< Morg < 10 μg m−3, a range which overlaps with atmospheric concentrations, the particle mass yield was 10 to 20% and was not sensitive to ozone exposure, implying that the constituent molecules were rapidly produced at all investigated ozone exposures. In contrast, for Morg > 10 μg m−3 the particle mass yield increased to as high as 70% for the ultimate yield corresponding to the greatest ozone exposures. These differing dependencies on ozone exposure under different regimes of Morg are explained by a combination of the ozonolysis lifetimes of the first-generation products and the volatility distribution of the resulting second-generation products. First-generation products that have short lifetimes produce low-volatility second-generation products whereas first-generation products that have long lifetimes produce high-volatility second-generation products. The ultimate particle mass yield was defined by mass-based stoichiometric yields αi of α0 = 0.17 ± 0.05, α1 = 0.11 ± 0.17, and α2 = 1.03 ± 0.30 for corresponding saturation concentrations of 1, 10, and 100 μg m−3. Terms α0 and α1 had low sensitivity to the investigated range of ozone exposure whereas term α2 increased from 0.32 ± 0.13 to 1.03 ± 0.30 as the ozone exposure was increased. These findings potentially allow for simplified yet accurate parameterizations in air quality and climate models that seek to represent the ozonolysis particle mass yields of certain classes of biogenic compounds.
One decade of parallel fine (PM2.5) and coarse (PM10–PM2.5) particulate matter measurements in Europe: trends and variability

The trends and variability of PM10, PM2.5 and PMcoarse concentrations at seven urban and rural background stations in five European countries for the period between 1998 and 2010 were investigated. Collocated or nearby PM measurements and meteorological observations were used in order to construct Generalized Additive Models, which model the effect of each meteorological variable on PM concentrations. In agreement with previous findings, the most important meteorological variables affecting PM concentrations were wind speed, wind direction, boundary layer depth, precipitation, temperature and number of consecutive days with synoptic weather patterns that favor high PM concentrations. Temperature has a negative relationship to PM2.5 concentrations for low temperatures and a positive relationship for high temperatures. The stationary point of this relationship varies between 5 and 15 °C depending on the station. PMcoarse concentrations increase for increasing temperatures almost throughout the temperature range. Wind speed has a monotonic relationship to PM2.5 except for one station, which exhibits a stationary point. Considering PMcoarse, concentrations tend to increase or stabilize for large wind speeds at most stations. It was also observed that at all stations except one, higher PM2.5 concentrations occurred for east wind direction, compared to west wind direction. Meteorologically adjusted PM time series were produced by removing most of the PM variability due to meteorology. It was found that PM10 and PM2.5 concentrations decrease at most stations. The average trends of the raw and meteorologically adjusted data are −0.4 μg m−3 yr−1 for PM10 and PM2.5 size fractions. PMcoarse have much smaller trends and after averaging over all stations, no significant trend was detected at the 95% level of confidence. It is suggested that decreasing PMcoarse in addition to PM2.5 can result in a faster decrease of PM10 in the future. The trends of the 90th quantile of PM10 and PM2.5 concentrations were examined by quantile regression in order to detect long term changes in the occurrence of very large PM concentrations. The meteorologically adjusted trends of the 90th quantile were significantly larger (as an absolute value) on average over all stations (−0.6 μg m−3 yr−1).
Atmospheric mercury observations from Antarctica: seasonal variation and source and sink region calculations

Long term atmospheric mercury measurements in the Southern Hemisphere are scarce and in Antarctica completely absent. Recent studies have shown that the Antarctic continent plays an important role in the global mercury cycle. Therefore, long term measurements of gaseous elemental mercury (GEM) were initiated at the Norwegian Antarctic Research Station, Troll (TRS) in order to improve our understanding of atmospheric transport, transformation and removal processes of GEM. GEM measurements started in February 2007 and are still ongoing, and this paper presents results from the first four years. The mean annual GEM concentration of 0.93 ± 0.19 ng m−3 is in good agreement with other recent southern-hemispheric measurements. Measurements of GEM were combined with the output of the Lagrangian particle dispersion model FLEXPART, for a statistical analysis of GEM source and sink regions. It was found that the ocean is a source of GEM to TRS year round, especially in summer and fall. On time scales of up to 20 days, there is little direct transport of GEM to TRS from Southern Hemisphere continents, but sources there are important for determining the overall GEM load in the Southern Hemisphere and for the mean GEM concentration at TRS. Further, the sea ice and marginal ice zones are GEM sinks in spring as also seen in the Arctic, but the Antarctic oceanic sink seems weaker. Contrary to the Arctic, a strong summer time GEM sink was found, when air originates from the Antarctic plateau, which shows that the summertime removal mechanism of GEM is completely different and is caused by other chemical processes than the springtime atmospheric mercury depletion events. The results were corroborated by an analysis of ozone source and sink regions.
Tight coupling of particle size, number and composition in atmospheric cloud droplet activation

The substantial uncertainty in the indirect effect of aerosol particles on radiative forcing in large part arises from the influences of atmospheric aerosol particles on (i) the brightness of clouds, exerting significant shortwave cooling with no appreciable compensation in the long wave, and on (ii) their ability to precipitate, with implications for cloud cover and lifetime. Predicting the ambient conditions at which aerosol particles may become cloud droplets is largely reliant on an equilibrium relationship derived by Köhler (1936). However, the theoretical basis of the relationship restricts its application to particles solely comprising involatile compounds and water, whereas a substantial fraction of particles in the real atmosphere will contain potentially thousands of semi-volatile organic compounds in addition to containing semi-volatile inorganic components such as ammonium nitrate. We show that equilibration of atmospherically reasonable concentrations of organic compounds with a growing particle as the ambient humidity increases has potentially larger implications on cloud droplet formation than any other equilibrium compositional dependence, owing to inextricable linkage between the aerosol composition, a particles size and concentration under ambient conditions. Whilst previous attempts to account for co-condensation of gases other than water vapour have been restricted to one inorganic condensate, our method demonstrates that accounting for the co-condensation of any number of organic compounds substantially decreases the saturation ratio of water vapour required for droplet activation. This effect is far greater than any other compositional dependence; more so even than the unphysical effect of surface tension reduction in aqueous organic mixtures, ignoring differences in bulk and surface surfactant concentrations.
Observed temporal evolution of global mean age of stratospheric air for the 2002 to 2010 period

An extensive observational data set, consisting of more than 106 SF6 vertical profiles from MIPAS measurements distributed over the whole globe has been condensed into monthly zonal means of mean age of air for the period September 2002 to January 2010, binned at 10° latitude and 1–2 km altitude. The data were analysed with respect to their temporal variation by fitting a regression model consisting of a constant and a linear increase term, 2 proxies for the QBO variation, sinusoidal terms for the seasonal and semi-annual variation and overtones for the correction of the shapes to the observed data set. The impact of subsidence of mesospheric SF6-depleted air and in-mixing into non-polar latitudes on mid-latitudinal absolute age of air and its linear increase was assessed and found to be small. The linear increase of mean age of stratospheric air was found to be positive and partly larger than the trend derived by Engel et al. (2009) for most of the Northern mid-latitudes, the middle stratosphere in the tropics, and parts of the Southern mid-latitudes, as well as for the Southern polar upper stratosphere. Multi-year decrease of age of air was found for the lowermost and the upper stratospheric tropics, for parts of Southern mid-latitudes, and for the Northern polar regions. Analysis of the amplitudes and phases of the seasonal variation shed light on the coupling of stratospheric regions to each other. In particular, the Northern mid-latitude stratosphere is well coupled to the tropics, while the Northern lowermost mid-latitudinal stratosphere is decoupled, confirming the separation of the shallow branch of the Brewer-Dobson circulation from the deep branch. We suggest an overall increased tropical upwelling, together with weakening of mixing barriers, especially in the Northern Hemisphere, as a hypothetical model to explain the observed pattern of linear multi-year increase/decrease, and amplitudes and phase shifts of the seasonal variation.
Primary and secondary sources of formaldehyde in urban atmospheres: Houston Texas region

We evaluate the rates of secondary production and primary emission of formaldehyde (CH2O) from petrochemical industrial facilities and on-road vehicles in the Houston Texas region. This evaluation is based upon ambient measurements collected during field studies in 2000, 2006 and 2009. The predominant CH2O source (92 ± 4% of total) is secondary production formed during the atmospheric oxidation of highly reactive volatile organic compounds (HRVOCs) emitted from the petrochemical facilities. Smaller contributions are primary emissions from these facilities (4 ± 2%), and secondary production (~3%) and primary emissions (~1%) from vehicles. The primary emissions from both sectors are well quantified by current emission inventories. Since secondary production dominates, control efforts directed at primary CH2O emissions cannot address the large majority of CH2O sources in the Houston area, although there may still be a role for such efforts. Ongoing efforts to control alkene emissions from the petrochemical facilities, as well as volatile organic compound emissions from the motor vehicle fleet, will effectively reduce the CH2O concentrations in the Houston region. We do not address other emission sectors, such as off-road mobile sources or secondary formation from biogenic hydrocarbons. Previous analyses based on correlations between ambient concentrations of CH2O and various marker species have suggested much larger primary emissions of CH2O, but those results neglect confounding effects of dilution and loss processes, and do not demonstrate the causes of the observed correlations. Similar problems must be suspected in any source apportionment analysis of secondary species based upon correlations of ambient concentrations of pollutants.
Climatic effects of 1950–2050 changes in US anthropogenic aerosols – Part 1: Aerosol trends and radiative forcing

We calculate decadal aerosol direct and indirect (warm cloud) radiative forcings from US anthropogenic sources over the 1950–2050 period. Past and future aerosol distributions are constructed using GEOS-Chem and historical emission inventories and future projections from the IPCC A1B scenario. Aerosol simulations are evaluated with observed spatial distributions and 1980–2010 trends of aerosol concentrations and wet deposition in the contiguous US. Direct and indirect radiative forcing is calculated using the GISS general circulation model and monthly mean aerosol distributions from GEOS-Chem. The radiative forcing from US anthropogenic aerosols is strongly localized over the eastern US. We find that its magnitude peaked in 1970–1990, with values over the eastern US (east of 100° W) of −2.0 W m−2 for direct forcing including contributions from sulfate (−2.0 W m−2), nitrate (−0.2 W m−2), organic carbon (−0.2 W m−2), and black carbon (+0.4 W m−2). The uncertainties in radiative forcing due to aerosol radiative properties are estimated to be about 50%. The aerosol indirect effect is estimated to be of comparable magnitude to the direct forcing. We find that the magnitude of the forcing declined sharply from 1990 to 2010 (by 0.8 W m−2 direct and 1.0 W m−2 indirect), mainly reflecting decreases in SO2 emissions, and project that it will continue declining post-2010 but at a much slower rate since US SO2 emissions have already declined by almost 60% from their peak. This suggests that much of the warming effect of reducing US anthropogenic aerosol sources has already been realized. The small positive radiative forcing from US BC emissions (+0.3 W m−2 over the eastern US in 2010; 5% of the global forcing from anthropogenic BC emissions worldwide) suggests that a US emission control strategy focused on BC would have only limited climate benefit.
Aerosols in the CALIOPE air quality modelling system: evaluation and analysis of PM levels, optical depths and chemical composition over Europe

The CALIOPE air quality modelling system is developed and applied to Europe with high spatial resolution (12 km × 12 km). The modelled daily-to-seasonal aerosol variability over Europe in 2004 is evaluated and analysed. Aerosols are estimated from two models, CMAQv4.5 (AERO4) and BSC-DREAM8b. CMAQv4.5 calculates biogenic, anthropogenic and sea salt aerosol and BSC-DREAM8b provides the natural mineral dust contribution from North African deserts. For the evaluation, we use daily PM10, PM2.5 and aerosol components data from 55 stations of the EMEP/CREATE network and total, coarse and fine aerosol optical depth (AOD) data from 35 stations of the AERONET sun photometer network. Annual correlations between modelled and observed values for PM10 and PM2.5 are 0.55 and 0.47, respectively. Correlations for total, coarse and fine AOD are 0.51, 0.63, and 0.53, respectively. The higher correlations of the PM10 and the coarse mode AOD are largely due to the accurate representation of the African dust influence in the forecasting system. Overall PM and AOD levels are underestimated. The evaluation of the aerosol components highlights underestimations in the fine fraction of carbonaceous matter (EC and OC) and secondary inorganic aerosols (SIA; i.e. nitrate, sulphate and ammonium). The scores of the bulk parameters are significantly improved after applying a simple model bias correction based on the observed aerosol composition. The simulated PM10 and AOD present maximum values over the industrialized and populated Po Valley and Benelux regions. SIA are dominant in the fine fraction representing up to 80% of the aerosol budget in latitudes north of 40° N. In southern Europe, high PM10 and AOD are linked to the desert dust transport from the Sahara which contributes up to 40% of the aerosol budget. Maximum seasonal ground-level concentrations (PM10 > 30 μg m−3) are found between spring and early autumn. We estimate that desert dust causes daily exceedances of the PM10 European air quality limit value (50 μg m−3) in large areas south of 45° N with more than 75 exceedances per year in the southernmost regions.
Climatic effects of 1950–2050 changes in US anthropogenic aerosols – Part 2: Climate response

We investigate the climate response to changing US anthropogenic aerosol sources over the 1950–2050 period by using the NASA GISS general circulation model (GCM) and comparing to observed US temperature trends. Time-dependent aerosol distributions are generated from the GEOS-Chem chemical transport model applied to historical emission inventories and future projections. Radiative forcing from US anthropogenic aerosols peaked in 1970–1990 and has strongly declined since due to air quality regulations. We find that the regional radiative forcing from US anthropogenic aerosols elicits a strong regional climate response, cooling the central and eastern US by 0.5–1.0 °C on average during 1970–1990, with the strongest effects on maximum daytime temperatures in summer and autumn. Aerosol cooling reflects comparable contributions from direct and indirect (cloud-mediated) radiative effects. Absorbing aerosol (mainly black carbon) has negligible warming effect. Aerosol cooling reduces surface evaporation and thus decreases precipitation along the US east coast, but also increases the southerly flow of moisture from the Gulf of Mexico resulting in increased cloud cover and precipitation in the central US. Observations over the eastern US show a lack of warming in 1960–1980 followed by very rapid warming since, which we reproduce in the GCM and attribute to trends in US anthropogenic aerosol sources. Present US aerosol concentrations are sufficiently low that future air quality improvements are projected to cause little further warming in the US (0.1 °C over 2010–2050). We find that most of the warming from aerosol source controls in the US has already been realized over the 1980–2010 period.
Influence of aerosols and thin cirrus clouds on the GOSAT-observed CO2: a case study over Tsukuba

Lidar observations of vertical profiles of aerosols and thin cirrus clouds were made at Tsukuba (36.05° N, 140.12° E), Japan, to investigate the influence of aerosols and thin cirrus clouds on the column-averaged dry-air mole fraction of carbon dioxide (XCO2) retrieved from observation data of the Thermal And Near-infrared Sensor for carbon Observation Fourier Transform Spectrometer, measured in the Short-Wavelength InfraRed band (TANSO-FTS SWIR), onboard the Greenhouse gases Observing SATellite (GOSAT). The lidar system measured the backscattering ratio, depolarization ratio, and/or the wavelength exponent of atmospheric particles. The lidar observations and ground-based high-resolution FTS measurements at the Tsukuba Total Carbon Column Observing Network (Tsukuba TCCON) site were recorded simultaneously during passages of GOSAT over Tsukuba. GOSAT SWIR XCO2 data (Version 01.xx) released in August 2010 were compared with the lidar and Tsukuba TCCON data. High-altitude aerosols and thin cirrus clouds had a large impact on the GOSAT SWIR XCO2 results. By taking into account the observed aerosol/cirrus vertical profiles and using a more adequate solar irradiance database in the GOSAT SWIR retrieval, the difference between the GOSAT SWIR XCO2 data and the Tsukuba TCCON data was reduced. The 3-band retrieval approach where the aerosol and cirrus profiles were retrieved gave us the best results and the retrieved XCO2 data followed the seasonal cycle of ~8 ppm observed at Tsukuba TCCON site.