Chemical ageing and transformation of diffusivity in semi-solid multi-component organic aerosol particles

Recent experimental evidence underlines the importance of reduced diffusivity in amorphous semi-solid or glassy atmospheric aerosols. This paper investigates the impact of diffusivity on the ageing of multi-component reactive organic particles representative of atmospheric cooking aerosols. We apply and extend the recently developed KM-SUB model in a study of a 12-component mixture containing oleic and palmitoleic acids. We demonstrate that changes in the diffusivity may explain the evolution of chemical loss rates in ageing semi-solid particles, and we resolve surface and bulk processes under transient reaction conditions considering diffusivities altered by oligomerisation. This new model treatment allows prediction of the ageing of mixed organic multi-component aerosols over atmospherically relevant time scales and conditions. We illustrate the impact of changing diffusivity on the chemical half-life of reactive components in semisolid particles, and we demonstrate how solidification and crust formation at the particle surface can affect the chemical transformation of organic aerosols.

The effect of extratropical cyclones on satellite-retrieved aerosol properties over ocean

Extratropical cyclones may have a signicant effect on column aerosol properties over ocean. European Centre for Medium Range Weather Forecasts (ECMWF) derived storm-centric composites of MODerate resolution Imaging Spectroradiometer (MODIS) and Advanced Along-Track Scanning Radiometer (AATSR) aerosol optical depth and aerosol size parameters are produced for the North Atlantic and the South Atlantic oceans. It is found that retrieved aerosol optical depth and aerosol size both increase near the center of the composite extratropical cyclones. Using composites of ECMWF ERA-Interim reanalysis data, it is demonstrated that wind speed is a considerably more likely explanatory variable than relative humidity for the aerosol observations. A comparison of composites for both MODIS and AATSR, which uses a wind speed dependent sea-surface brightness model in the aerosol retrieval, suggests that although surface brightness eects may contribute towards some of the observations, wind speed dependent emission of sea salt also appears to make a signicant contribution to the observed aerosol properties.

Chemical ageing and transformation of diffusivity in semi-solid multi-component organic aerosol particles

Recent experimental evidence underlines the importance of reduced diffusivity in amorphous semi-solid or glassy atmospheric aerosols. This paper investigates the impact of diffusivity on the ageing of multi-component reactive organic particles approximating atmospheric cooking aerosols. We apply and extend the recently developed KMSUB model in a study of a 12-component mixture containing oleic and palmitoleic acids. We demonstrate that changes in the diffusivity may explain the evolution of chemical loss rates in ageing semi-solid particles, and we resolve surface and bulk processes under transient reaction conditions considering diffusivities altered by oligomerisation. This new model treatment allows prediction of the ageing of mixed organic multi-component aerosols over atmospherically relevant timescales and conditions. We illustrate the impact of changing diffusivity on the chemical half-life of reactive components in semi-solid particles, and we demonstrate how solidification and crust formation at the particle surface can affect the chemical transformation of organic aerosols.

The GRAPE aerosol retrieval algorithm

The aerosol component of the Oxford-Rutherford Aerosol and Cloud (ORAC) combined cloud and aerosol retrieval scheme is described and the theoretical performance of the algorithm is analysed. ORAC is an optimal estimation retrieval scheme for deriving cloud and aerosol properties from measurements made by imaging satellite radiometers and, when applied to cloud free radiances, provides estimates of aerosol optical depth at a wavelength of 550 nm, aerosol effective radius and surface reflectance at 550 nm. The aerosol retrieval component of ORAC has several incarnations ��� this paper addresses the version which operates in conjunction with the cloud retrieval component of ORAC (described by Watts et al., 1998), as applied in producing the Global Retrieval of ATSR Cloud Parameters and Evaluation (GRAPE) data-set.

Validation of the GRAPE single view aerosol retrieval for ATSR-2 and insights into the long term global AOD trend over the ocean

The Global Retrieval of ATSR Cloud Parameters and Evaluation (GRAPE) project has produced a global data-set of cloud and aerosol properties from the Along Track Scanning Radiometer-2 (ATSR-2) instrument, covering the time period 1995��������2001. This paper presents the validation of aerosol optical depths (AODs) over the ocean from this product against AERONET sun-photometer measurements, as well as a comparison to the Advanced Very High Resolution Radiometer (AVHRR) optical depth product produced by the Global Aerosol Climatology Project (GACP). The GRAPE AOD over ocean is found to be in good agreement with AERONET measurements, with a Pearson's correlation coefficient of 0.79 and a best-fit slope of 1.0����0.1, but with a positive bias of 0.08����0.04. Although the GRAPE and GACP datasets show reasonable agreement, there are significant differences. These discrepancies are explored, and suggest that the downward trend in AOD reported by GACP may arise from changes in sampling due to the orbital drift of the AVHRR instruments.

Determining the contribution of volcanic ash and boundary layer aerosol in backscatter lidar returns: a three���component atmosphere approach

A solution of the lidar equation is discussed, that permits combining backscatter and depolarization measurements to quantitatively distinguish two different aerosol types with different depolarization properties. The method has been successfully applied to simultaneous observations of volcanic ash and boundary layer aerosol obtained in Exeter, United Kingdom, on 16 and 18 April 2010, permitting the contribution of the two aerosols to be quantified separately. First a subset of the atmospheric profiles is used where the two aerosol types belong to clearly distinguished layers, for the purpose of characterizing the ash in terms of lidar ratio and depolarization. These quantities are then used in a three���component atmosphere solution scheme of the lidar equation applied to the full data set, in order to compute the optical properties of both aerosol types separately. On 16 April a thin ash layer, 100���400 m deep, is observed (average and maximum estimated ash optical depth: 0.11 and 0.2); it descends from ���2800 to ���1400 m altitude over a 6���hour period. On 18 April a double ash layer, ���400 m deep, is observed just above the morning boundary layer (average and maximum estimated ash optical depth: 0.19 and 0.27). In the afternoon the ash is entrained into the boundary layer, and the latter reaches a depth of ���1800 m (average and maximum estimated ash optical depth: 0.1 and 0.15). An additional ash layer, with a very small optical depth, was observed on 18 April at an altitude of 3500���4000 m. By converting the lidar optical measurements using estimates of volcanic ash specific extinction, derived from other works, the observations seem to suggest approximate peak ash concentrations of ���1500 and ���1000 mg/m3,respectively, on the two observations dates.

A novel satellite mission concept for upper air water vapour, aerosol and cloud observations using integrated path differential absorption LiDAR limb sounding

We propose a new satellite mission to deliver high quality measurements of upper air water vapour. The concept centres around a LiDAR in limb sounding by occultation geometry, designed to operate as a very long path system for differential absorption measurements. We present a preliminary performance analysis with a system sized to send 75 mJ pulses at 25 Hz at four wavelengths close to 935 nm, to up to 5 microsatellites in a counter-rotating orbit, carrying retroreflectors characterized by a reflected beam divergence of roughly twice the emitted laser beam divergence of 15 ��rad. This provides water vapour profiles with a vertical sampling of 110 m; preliminary calculations suggest that the system could detect concentrations of less than 5 ppm. A secondary payload of a fairly conventional medium resolution multispectral radiometer allows wide-swath cloud and aerosol imaging. The total weight and power of the system are estimated at 3 tons and 2,700 W respectively. This novel concept presents significant challenges, including the performance of the lasers in space, the tracking between the main spacecraft and the retroreflectors, the refractive effects of turbulence, and the design of the telescopes to achieve a high signal-to-noise ratio for the high precision measurements. The mission concept was conceived at the Alpbach Summer School 2010.

Aerosol-induced correlation between visibility and atmospheric electricity.

Atmospheric aerosol acts to both reduce the background concentration of natural cluster ions, and to attenuate optical propagation. Hence, the presence of aerosol has two consequences, the reduction of the air���s electrical conductivity and the visual range. Ion-aerosol theory and Koschmieder���s visibility theory are combined here to derive the related non-linear variation of the atmospheric electric potential gradient with visual range. A substantial sensitivity is found under poor visual range conditions, but, for good visual range conditions the sensitivity diminishes and little influence of local aerosol on the fair weather potential gradient occurs. This allows visual range measurements, made simply and routinely at many meteorological sites, to provide inference about the local air���s electrical properties.

The roles of aerosol, water vapor and cloud in future global dimming/brightening

Observational evidence indicates significant regional trends in solar radiation at the surface in both all-sky and cloud-free conditions. Negative trends in the downwelling solar surface irradiance (SSI) have become known as ���dimming��� while positive trends have become known as ���brightening���. We use the Met Office Hadley Centre HadGEM2 climate model to model trends in cloud-free and total SSI from the pre-industrial to the present-day and compare these against observations. Simulations driven by CMIP5 emissions are used to model the future trends in dimming/brightening up to the year 2100. The modeled trends are reasonably consistent with observed regional trends in dimming and brightening which are due to changes in concentrations in anthropogenic aerosols and, potentially, changes in cloud cover owing to the aerosol indirect effects and/or cloud feedback mechanisms. The future dimming/brightening in cloud-free SSI is not only caused by changes in anthropogenic aerosols: aerosol impacts are overwhelmed by a large dimming caused by increases in water vapor. There is little trend in the total SSI as cloud cover decreases in the climate model used here, and compensates the effect of the change in water vapor. In terms of the surface energy balance, these trends in SSI are obviously more than compensated by the increase in the downwelling terrestrial irradiance from increased water vapor concentrations. However, the study shows that while water vapor is widely appreciated as a greenhouse gas, water vapor impacts on the atmospheric transmission of solar radiation and the future of global dimming/brightening should not be overlooked.

Aerosol contribution to the rapid warming of near-term climate under RCP 2.6

The importance of aerosol emissions for near term climate projections is investigated by analysing simulations with the HadGEM2-ES model under two different emissions scenarios: RCP2.6 and RCP4.5. It is shown that the near term warming projected under RCP2.6 is greater than under RCP4.5, even though the greenhouse gas forcing is lower. Rapid and substantial reductions in sulphate aerosol emissions due to a reduction of coal burning in RCP2.6 lead to a reduction in the negative shortwave forcing due to aerosol direct and indirect effects. Indirect effects play an important role over the northern hemisphere oceans, especially the subtropical northeastern Pacific where an anomaly of 5-10\,Wm$^{-2}$ develops. The pattern of surface temperature change is consistent with the expected response to this surface radiation anomaly, whilst also exhibiting features that reflect redistribution of energy, and feedbacks, within the climate system. These results demonstrate the importance of aerosol emissions as a key source of uncertainty in near term projections of global and regional climate.

Possible role of aerosol transmission in a hospital outbreak of influenza.

BACKGROUND: We examined the role of aerosol transmission of influenza in an acute ward setting. METHODS: We investigated a seasonal influenza A outbreak that occurred in our general medical ward (with open bay ward layout) in 2008. Clinical and epidemiological information was collected in real time during the outbreak. Spatiotemporal analysis was performed to estimate the infection risk among patients. Airflow measurements were conducted, and concentrations of hypothetical virus-laden aerosols at different ward locations were estimated using computational fluid dynamics modeling. RESULTS: Nine inpatients were infected with an identical strain of influenza A/H3N2 virus. With reference to the index patient's location, the attack rate was 20.0% and 22.2% in the "same" and "adjacent" bays, respectively, but 0% in the "distant" bay (P =���.04). Temporally, the risk of being infected was highest on the day when noninvasive ventilation was used in the index patient; multivariate logistic regression revealed an odds ratio of 14.9 (95% confidence interval, 1.7-131.3; P =���.015). A simultaneous, directional indoor airflow blown from the "same" bay toward the "adjacent" bay was found; it was inadvertently created by an unopposed air jet from a separate air purifier placed next to the index patient's bed. Computational fluid dynamics modeling revealed that the dispersal pattern of aerosols originated from the index patient coincided with the bed locations of affected patients. CONCLUSIONS: Our findings suggest a possible role of aerosol transmission of influenza in an acute ward setting. Source and engineering controls, such as avoiding aerosol generation and improving ventilation design, may warrant consideration to prevent nosocomial outbreaks.

Ground-based aerosol optical depth trends at three high-altitude sites in Switzerland and Southern Germany from 1995���2010

Ground-based aerosol optical depth (AOD) climatologies at three high-altitude sites in Switzerland (Jungfraujoch and Davos) and Southern Germany (Hohenpeissenberg) are updated and re-calibrated for the period 1995 ��� 2010. In addition, AOD time-series are augmented with previously unreported data, and are homogenized for the first time. Trend analysis revealed weak AOD trends (�� = 500 nm) at Jungfraujoch (JFJ; +0.007 decade-1), Davos (DAV; +0.002 decade-1) and Hohenpeissenberg (HPB; -0.011 decade-1) where the JFJ and HPB trends were statistically significant at the 95% and 90% confidence levels. However, a linear trend for the JFJ 1995 ��� 2005 period was found to be more appropriate than for 1995 ��� 2010 due to the influence of stratospheric AOD which gave a trend -0.003 decade-1 (significant at 95% level). When correcting for a recently available stratospheric AOD time-series, accounting for Pinatubo (1991) and more recent volcanic eruptions, the 1995 ��� 2010 AOD trends decreased slightly at DAV and HPB but remained weak at +0.000 decade-1 and -0.013 decade-1 (significant at 95% level). The JFJ 1995 ��� 2005 AOD time-series similarly decreased to -0.003 decade-1 (significant at 95% level). We conclude that despite a more detailed re40 analysis of these three time-series, which have been extended by five years to the end of 2010, a significant decrease in AOD at these three high-altitude sites has still not been observed.

Cloud droplet size and liquid water path retrievals from zenith radiance measurements: examples from the Atmospheric Radiation Measurement Program and the Aerosol Robotic Network

The ground-based Atmospheric Radiation Measurement Program (ARM) and NASA Aerosol Robotic Net- work (AERONET) routinely monitor clouds using zenith ra- diances at visible and near-infrared wavelengths. Using the transmittance calculated from such measurements, we have developed a new retrieval method for cloud effective droplet size and conducted extensive tests for non-precipitating liquid water clouds. The underlying principle is to combine a liquid-water-absorbing wavelength (i.e., 1640 nm) with a non-water-absorbing wavelength for acquiring information on cloud droplet size and optical depth. For simulated stratocumulus clouds with liquid water path less than 300 g m���2 and horizontal resolution of 201 m, the retrieval method underestimates the mean effective radius by 0.8��m, with a root-mean-squared error of 1.7 ��m and a relative deviation of 13%. For actual observations with a liquid water path less than 450 g m���2 at the ARM Oklahoma site during 2007��� 2008, our 1.5-min-averaged retrievals are generally larger by around 1 ��m than those from combined ground-based cloud radar and microwave radiometer at a 5-min temporal resolution. We also compared our retrievals to those from combined shortwave flux and microwave observations for relatively homogeneous clouds, showing that the bias between these two retrieval sets is negligible, but the error of 2.6 ��m and the relative deviation of 22 % are larger than those found in our simulation case. Finally, the transmittance-based cloud effective droplet radii agree to better than 11 % with satellite observations and have a negative bias of 1 ��m. Overall, the retrieval method provides reasonable cloud effective radius estimates, which can enhance the cloud products of both ARM and AERONET.

Aerosol forcing in the Climate Model Intercomparison Project (CMIP5) simulations by HadGEM2-ES and the role of ammonium nitrate

The latest Hadley Centre climate model, HadGEM2-ES, includes Earth system components such as interactive chemistry and eight species of tropospheric aerosols. It has been run for the period 1860���2100 in support of the fifth phase of the Climate Model Intercomparison Project (CMIP5). Anthropogenic aerosol emissions peak between 1980 and 2020, resulting in a present-day all-sky top of the atmosphere aerosol forcing of ���1.6 and ���1.4 W m���2 with and without ammonium nitrate aerosols, respectively, for the sum of direct and first indirect aerosol forcings. Aerosol forcing becomes significantly weaker in the 21st century, being weaker than ���0.5 W m���2 in 2100 without nitrate. However, nitrate aerosols become the dominant species in Europe and Asia and decelerate the decrease in global mean aerosol forcing. Considering nitrate aerosols makes aerosol radiative forcing 2���4 times stronger by 2100 depending on the representative concentration pathway, although this impact is lessened when changes in the oxidation properties of the atmosphere are accounted for. Anthropogenic aerosol residence times increase in the future in spite of increased precipitation, as cloud cover and aerosol-cloud interactions decrease in tropical and midlatitude regions. Deposition of fossil fuel black carbon onto snow and ice surfaces peaks during the 20th century in the Arctic and Europe but keeps increasing in the Himalayas until the middle of the 21st century. Results presented here confirm the importance of aerosols in influencing the Earth's climate, albeit with a reduced impact in the future, and suggest that nitrate aerosols will partially replace sulphate aerosols to become an important anthropogenic species in the remainder of the 21st century.

Updated estimate of aerosol direct radiative forcing from satellite observations and comparison against the Hadley Centre climate model

The fourth assessment report of the Intergovernmental Panel on Climate Change (IPCC) includes a comparison of observation-based and modeling-based estimates of the aerosol direct radiative forcing. In this comparison, satellite-based studies suggest a more negative aerosol direct radiative forcing than modeling studies. A previous satellite-based study, part of the IPCC comparison, uses aerosol optical depths and accumulation-mode fractions retrieved by the Moderate Resolution Imaging Spectroradiometer (MODIS) at collection 4. The latest version of MODIS products, named collection 5, improves aerosol retrievals. Using these products, the direct forcing in the shortwave spectrum defined with respect to present-day natural aerosols is now estimated at ���1.30 and ���0.65 Wm���2 on a global clear-sky and all-sky average, respectively, for 2002. These values are still significantly more negative than the numbers reported by modeling studies. By accounting for differences between present-day natural and preindustrial aerosol concentrations, sampling biases, and investigating the impact of differences in the zonal distribution of anthropogenic aerosols, good agreement is reached between the direct forcing derived from MODIS and the Hadley Centre climate model HadGEM2-A over clear-sky oceans. Results also suggest that satellite estimates of anthropogenic aerosol optical depth over land should be coupled with a robust validation strategy in order to refine the observation-based estimate of aerosol direct radiative forcing. In addition, the complex problem of deriving the aerosol direct radiative forcing when aerosols are located above cloud still needs to be addressed.