Items

Advanced search

Deposition nucleation viewed as homogeneous or immersion freezing in pores and cavities

Heterogeneous ice nucleation is an important mechanism for the glaciation of mixed phase clouds and may also be relevant for cloud formation and dehydration at the cirrus cloud level. It is thought to proceed through different mechanisms, namely contact, condensation, immersion and deposition nucleation. Conceptually, deposition nucleation is the only pathway that does not involve liquid water, but occurs by direct water vapor deposition onto a surface. This study challenges this classical view by putting forward the hypothesis that what is called deposition nucleation is in fact pore condensation and freezing (PCF) occurring in voids and cavities that may form between aggregated primary particles and host water at relative humidity RHw < 100% because of the inverse Kelvin effect. Homogeneous ice nucleation is expected to occur below 235 K when at least one pore is filled with water. Ice nucleation in pores may also happen in immersion mode but with a lower probability because it requires at least one active site in a water filled pore. Therefore a significant enhancement in ice nucleation efficiency is expected when temperature falls below 235 K. For a deposition nucleation process from water vapor no discontinuous change in ice nucleation efficiency should occur at T = 235 K because no liquid water is involved in this process. Studies on freezing in confinement carried out on mesoporous silica materials such as SBA-15, SBA-16, MCM-41, zeolites and KIT have shown that homogeneous ice nucleation occurs abruptly at T = 230–235 K in pores with diameters (D) of 3.5–4 nm or larger but only gradually at T = 210–230 K in pores with D = 2.5–3.5 nm. Pore analysis of clay minerals shows that kaolinites exhibit pore structures with pore diameters (Dp) of 20–50 nm. The mesoporosity of illites and montmorillonites is characterized by pores with Dp = 2–5 nm. The number and size of pores is distinctly increased in acid treated montmorillonites like K10. Water adsorption isotherms of MCM-41 show that pores with Dp = 3.5–4 nm fill with water at RHw = 56–60% in accordance with an inverse Kelvin effect. Water in such pores should freeze homogeneously for T < 235 K even before relative humidity with respect to ice (RHi) reaches ice saturation. Ice crystal growth by water vapor deposition from the gas phase is therefore expected to set in as soon as RHi > 100%. Pores with D > 7.5 nm fill with water at RHi > 100% for T < 235 K and are likely to freeze homogeneously as soon as they are filled with water. Given the pore structure of clay minerals, PCF should be highly efficient for T < 235 K and may occur at T > 235 K in particles that exhibit active sites for immersion freezing within pores. Most ice nucleation studies on clay minerals and mineral dusts indeed show a strong increase in ice nucleation efficiency when temperature is decreased below 235 K in accordance with PCF and are not explicable by the classical view of deposition nucleation. PCF is probably also the prevailing ice nucleation mechanism below water saturation for glassy, soot, and volcanic ash aerosols. No case could be identified that gives clear evidence of ice nucleation by water vapor deposition onto a solid surface.
Saharan dust aerosol over the central Mediterranean Sea: PM10 chemical composition and concentration versus optical columnar measurements

This study aims to determine the mineral contribution to PM10 in the central Mediterranean Sea, based on 7 yr of daily PM10 samplings made on the island of Lampedusa (35.5° N, 12.6° E). The chemical composition of the PM10 samples was determined by ion chromatography for the main ions, and, on selected samples, by particle-induced X-ray emission (PIXE) for the total content of crustal markers. Aerosol optical depth measurements were carried out in parallel to the PM10 sampling. The average PM10 concentration at Lampedusa over the period June 2004–December 2010 is 31.5 μg m−3, with low interannual variability. The annual means are below the EU annual standard for PM10, but 9.9% of the total number of daily data exceeds the daily threshold value established by the European Commission for PM (50 μg m−3, European Community, EC/30/1999). The Saharan dust contribution to PM10 was derived by calculating the contribution of Al, Si, Fe, Ti, non-sea-salt (nss) Ca, nssNa, and nssK oxides in samples in which PIXE data were available. Cases in which crustal content exceeded the 75th percentile of the crustal oxide content distribution were identified as elevated dust events. Using this threshold, we obtained 175 events. Fifty-five elevated dust events (31.6%) displayed PM10 higher than 50 μg m−3, with dust contributing by 33% on average. The crustal contribution to PM10 has an annual average value of 5.42 μg m−3, and reaches a value as high as 67.9 μg m−3 (corresponding to 49% of PM10) during an intense Saharan dust event. The crustal content estimated from a single tracer, such as Al or Ca, is in good agreement with the one calculated as the sum of the metal oxides. Conversely, larger crustal contents are derived by applying the EU guidelines for demonstration and subtraction of exceedances in PM10 levels due to high background of natural aerosol. The crustal aerosol amount and contribution to PM10 showed a very small seasonal dependence; conversely, the dust columnar burden displays an evident annual cycle, with a strong summer maximum (monthly average aerosol optical depth at 500 nm up to 0.28 in June–August). We found that 71.3% of the dust events identified from optical properties over the atmospheric column display a high dust content at the ground level. Conversely, the remaining 28.7% of cases present a negligible or small impact on the surface aerosol composition due to the transport processes over the Mediterranean Sea, where dust frequently travels above the marine boundary layer, especially in summer. Based on backward trajectories, two regions, one in Algeria–Tunisia, and one in Libya, are identified as main source areas for intense dust episodes occurring mainly in autumn and winter. Data on the bulk composition of mineral aerosol arising from these two source areas are scarce; results on characteristic ratios between elements show somewhat higher values of Ca / Al and (Ca + Mg) / Fe (2.5 ± 1.0, and 4.7 ± 2.0, respectively) for Algeria–Tunisia than for Libyan origin (Ca / Al = 1.9 ± 0.7 and (Ca + Mg) / Fe = 3.3 ± 1.1).
Comparison of MODIS 3 km and 10 km resolution aerosol optical depth retrievals over land with airborne sunphotometer measurements during ARCTAS summer 2008

Airborne sunphotometer measurements acquired by the NASA Ames Airborne Tracking Sunphotometer (AATS-14) aboard the NASA P-3 research aircraft are used to evaluate dark-target over-land retrievals of extinction aerosol optical depth (AOD) from spatially and temporally near-coincident measurements by the Moderate Resolution Imaging Spectroradiometer (MODIS) during the summer 2008 Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) field campaign. The new MODIS Collection 6 aerosol data set includes retrievals of AOD at both 10 km × 10 km and 3 km × 3 km (at nadir) resolution. In this paper we compare MODIS and AATS AOD at 553 nm in 58 10 km and 134 3 km retrieval grid cells. These AOD values were derived from data collected over Canada on four days during short time segments of five (four Aqua and one Terra) satellite overpasses of the P-3 during low-altitude P-3 flight tracks. Three of the five MODIS–AATS coincidence events were dominated by smoke: one included a P-3 transect of a well-defined smoke plume in clear sky, but two were confounded by the presence of scattered clouds above smoke. The clouds limited the number of MODIS retrievals available for comparison, and led to MODIS AOD retrievals that underestimated the corresponding AATS values. This happened because the MODIS aerosol cloud mask selectively removed 0.5 km pixels containing smoke and clouds before the aerosol retrieval. The other two coincidences (one Terra and one Aqua) occurred during one P-3 flight on the same day and in the same general area, in an atmosphere characterized by a relatively low AOD (< 0.3), spatially homogeneous regional haze from smoke outflow with no distinguishable plume. For the ensemble data set for MODIS AOD retrievals with the highest-quality flag, MODIS AOD agrees with AATS AOD within the expected MODIS over-land AOD uncertainty in 60% of the retrieval grid cells at 10 km resolution and 69% at 3 km resolution. These values improve to 65 % and 74%, respectively, when the cloud-affected case with the strongest plume is excluded. We find that the standard MODIS dark-target over-land retrieval algorithm fails to retrieve AOD for thick smoke, not only in cloud-contaminated regions but also in clear sky. We attribute this to deselection, by the cloud and/or bright surface masks, of 0.5 km resolution pixels that contain smoke.
Vehicle emissions of greenhouse gases and related tracers from a tunnel study: CO : CO2, N2O : CO2, CH4 : CO2, O2 : CO2 ratios, and the stable isotopes 13C and 18O in CO2 and CO

Measurements of CO2, CO, N2O and CH4 mole fractions, O2 / N2 ratios and the stable isotopes 13C and 18O in CO2 and CO have been performed in air samples from the Islisberg highway tunnel (Switzerland). The molar CO : CO2 ratios, with an average of (4.15 ± 0.34) ppb:ppm, are lower than reported in previous studies, pointing to a reduction in CO emissions from traffic. The 13C in CO2 reflects the isotopic composition of the fuel. 18O in CO2 is slightly depleted compared to the 18O in atmospheric O2, and shows significant variability. In contrast, the δ13C values of CO show that significant fractionation takes place during CO destruction in the catalytic converter. 13C in CO is enriched by 3&permil; compared to the 13C in the fuel burnt, while the 18O content is similar to that of atmospheric O2. We compute a fractionation constant of (−2.7 ± 0.7)&permil; for 13C during CO destruction. The N2O : CO2 average ratio of (1.8 ± 0.2) × 10−2 ppb:ppm is significantly lower than in past studies, showing a reduction in N2O emissions likely related to improvements in the catalytic converter technology. We also observed small CH4 emissions, with an average CH4 : CO2 ratio of (4.6 ± 0.2) × 10−2 ppb:ppm. The O2 : CO2 ratios of (−1.47 ± 0.01) ppm:ppm are very close to the expected, theoretically calculated values of O2 depletion per CO2 enhancement.
Column aerosol optical properties and aerosol radiative forcing during a serious haze-fog month over North China Plain in 2013 based on ground-based sunphotometer measurements

In January 2013, North China Plain experienced several serious haze events. Cimel sunphotometer measurements at seven sites over rural, suburban and urban regions of North China Plain from 1 to 30 January 2013 were used to further our understanding of spatial-temporal variation of aerosol optical parameters and aerosol radiative forcing (ARF). It was found that Aerosol Optical Depth at 500 nm (AOD500 nm) during non-pollution periods at all stations was lower than 0.30 and increased significantly to greater than 1.00 as pollution events developed. The Angstrom exponent (Alpha) was larger than 0.80 for all stations most of the time. AOD500 nm averages increased from north to south during both polluted and non-polluted periods on the three urban sites in Beijing. The fine mode AOD during pollution periods is about a factor of 2.5 times larger than that during the non-pollution period at urban sites but a factor of 5.0 at suburban and rural sites. The fine mode fraction of AOD675 nm was higher than 80% for all sites during January 2013. The absorption AOD675 nm at rural sites was only about 0.01 during pollution periods, while ~0.03–0.07 and 0.01–0.03 during pollution and non-pollution periods at other sites, respectively. Single scattering albedo varied between 0.87 and 0.95 during January 2013 over North China Plain. The size distribution showed an obvious tri-peak pattern during the most serious period. The fine mode effective radius in the pollution period was about 0.01–0.08 μm larger than during non-pollution periods, while the coarse mode radius in pollution periods was about 0.06–0.38 μm less than that during non-pollution periods. The total, fine and coarse mode particle volumes varied by about 0.06–0.34 μm3, 0.03–0.23 μm3, and 0.03–0.10 μm3, respectively, throughout January 2013. During the most intense period (1–16 January), ARF at the surface exceeded −50 W m−2, −180 W m−2, and −200 W m−2 at rural, suburban, and urban sites, respectively. The ARF readings at the top of the atmosphere were approximately −30 W m−2 in rural and −40–60 W m−2 in urban areas. Positive ARF at the top of the atmosphere at the Huimin suburban site was found to be different from others as a result of the high surface albedo due to snow cover.
Factors that influence surface PM2.5 values inferred from satellite observations: perspective gained for the US Baltimore–Washington metropolitan area during DISCOVER-AQ

During the NASA DISCOVER-AQ campaign over the US Baltimore, MD–Washington, D.C., metropolitan area in July 2011, the NASA P-3B aircraft performed extensive profiling of aerosol optical, chemical, and microphysical properties. These in situ profiles were coincident with ground-based remote sensing (AERONET) and in situ (PM2.5) measurements. Here, we use this data set to study the correlation between the PM2.5 observations at the surface and the column integrated measurements. Aerosol optical depth (AOD550 nm) calculated with the extinction (550 nm) measured during the in situ profiles was found to be strongly correlated with the volume of aerosols present in the boundary layer (BL). Despite the strong correlation, some variability remains, and we find that the presence of aerosol layers above the BL (in the buffer layer – BuL) introduces significant uncertainties in PM2.5 estimates based on column-integrated measurements (overestimation of PM2.5 by a factor of 5). This suggests that the use of active remote sensing techniques would dramatically improve air quality retrievals. Indeed, the relationship between the AOD550 nm and the PM2.5 is strongly improved by accounting for the aerosol present in and above the BL (i.e., integrating the aerosol loading from the surface to the top of the BuL). Since more than 15% of the AOD values observed during DISCOVER-AQ are dominated by aerosol water uptake, the f(RH)amb (ratio of scattering coefficient at ambient relative humidity (RH) to scattering coefficient at low RH; see Sect. 3.2) is used to study the impact of the aerosol hygroscopicity on the PM2.5 retrievals. The results indicate that PM2.5 can be predicted within a factor up to 2 even when the vertical variability of the f(RH)amb is assumed to be negligible. Moreover, f(RH = 80%) and RH measurements performed at the ground may be used to estimate the f(RH)amb during dry conditions (RHBL < 55%).
Aerosols and nucleation in eastern China: first insights from the new SORPES-NJU station

Aerosols and new particle formation were studied in the western part of the Yangtze River Delta (YRD) at the Station for Observing Regional Processes of the Earth System, Nanjing University (SORPES-NJU). Air ions in the diameter range 0.8–42 nm were measured using an air ion spectrometer, and a differential mobility particle sizer (DMPS) provided particle number size distributions between 6 and 800 nm. Additionally, meteorological data, trace gas concentrations, and PM2.5 values were recorded. During the measurement period from 18 November 2011 to 31 March 2012, the mean total particle concentration was found to be 23 000 cm−3 and the mean PM2.5 value was 90 μg m−3, well above national limits. We observed 26 new particle formation events occurred during the measurement period, producing 6 nm particles at a rate of about 1 cm−3 s−1. Typical particle growth rates were between 6 and 7 nm h−1. On average, new particle formation and growth were estimated to enhance cloud condensation nuclei concentration by about a factor of two during these event days. Ion measurements showed the typical cluster band below 2 nm, with total ion concentrations between about 600 and 1000 cm−3. A peculiar feature of the ion measurements were heightened ion cluster concentrations during the nights before the event days. At 2 nm, the formation rate of charged particles was only about 0.2% of the total rate, pointing towards an only marginal role of ion-induced nucleation. Based on observations, a simple empirical criterion was deducted to estimate particle formation probability. Dominated by radiation and relative humidity, the criterion can predict the occurrence of particle formation with a 90% accuracy. In a similar fashion, a reasonably accurate estimate of particle formation rates was derived. Combined, these parameters allow for a description of particle formation based on a few basic measured variables.
Contribution of ammonium nitrate to aerosol optical depth and direct radiative forcing by aerosols over East Asia

This study focused on the contribution of ammonium nitrate (NH4NO3) to aerosol optical depth (AOD) and direct radiative forcing (DRF) by aerosols over an East Asian domain. In order to evaluate the contribution, chemistry-transport model (CTM)-estimated AOD was combined with satellite-retrieved AOD, utilizing a data assimilation technique, over East Asia for the entire year of 2006. Using the assimilated AOD and CTM-estimated aerosol optical properties, the DRF by aerosols was estimated over East Asia via a radiative transfer model (RTM). Both assimilated AOD and estimated DRF values showed relatively good agreements with AOD and DRF by aerosols from AERONET. Based on these results, the contributions of NH4NO3 to AOD and DRF by aerosols (ΦAOD and ΦDRF) were estimated for the four seasons of 2006 over East Asia. Both ΦAOD and ΦDRF showed seasonal variations over East Asia within the ranges between 4.7% (summer) and 31.3% (winter) and between 4.7% (summer) and 30.7% (winter), respectively, under clear-sky conditions, showing annual average contributions of 15.6% and 15.3%. Under all-sky conditions, ΦDRF varied between 3.6% (summer) and 24.5% (winter), showing annual average contribution of 12.1% over East Asia. These annual average contributions of NH4NO3 to AOD and DRF are almost comparable to the annual average mass fractions of NH4NO3 in PM2.5 and PM10 (17.0% and 14.0%, respectively). ΦAOD and ΦDRF were even larger in the locations where NH3 and NOx emission rates are strong, such as the central East China (CEC) region and Sichuan Basin. For example, under clear-sky conditions, both ΦAOD and ΦDRF over the CEC region range between 6.9% (summer) and 47.9% (winter) and between 6.7% (summer) and 47.5% (winter), respectively. Based on this analysis, it was concluded that both ΦAOD and ΦDRF cannot be ignored in East Asian air quality and radiative forcing studies, particularly during winter.
A long-term satellite study of aerosol effects on convective clouds in Nordic background air

Aerosol-cloud interactions constitute a major uncertainty in future climate predictions. This study combines 10 years of ground-based aerosol particle measurements from two Nordic background stations (Vavihill and Hyytiälä) with MODIS (Moderate Resolution Imaging Spectroradiometer) satellite data of convective clouds. The merged data are used to examine how aerosols affect cloud droplet sizes and precipitation from convective clouds over the Nordic countries. From the satellite scenes, vertical profiles of cloud droplet effective radius (re) are created by plotting retrieved cloud top re against cloud top temperature for the clouds in a given satellite scene. The profiles have been divided according to aerosol number concentrations but also meteorological reanalysis parameters from the ECMWF (European Centre for Medium-Range Forecasts). Furthermore, weather radar data from the BALTEX (Baltic Sea Experiment) and precipitation data from several ground-based meteorological measurement stations have been investigated to determine whether aerosols affect precipitation intensity and amount. Small re throughout the entire cloud profiles is associated with high aerosol number concentrations at both stations. However, aerosol number concentrations seem to affect neither the cloud optical thickness nor the vertical extent of the clouds in this study. Cloud profiles with no or little precipitation have smaller droplets than those with more precipitation. Moreover, the amount of precipitation that reaches the ground is affected by meteorological conditions such as the vertical extent of the clouds, the atmospheric instability and the relative humidity in the lower atmosphere rather than the aerosol number concentration. However, lower precipitation rates are associated with higher aerosol number concentrations for clouds with similar vertical extent. The combination of these ground-based and remote-sensing datasets provides a unique long-term study of the effects of aerosols on convective clouds over the Nordic countries.
Atmospheric mercury speciation and mercury in snow over time at Alert, Canada

Ten years of atmospheric mercury speciation data and 14 years of mercury in snow data from Alert, Nunavut, Canada, are examined. The speciation data, collected from 2002 to 2011, includes gaseous elemental mercury (GEM), particulate mercury (PHg) and reactive gaseous mercury (RGM). During the winter-spring period of atmospheric mercury depletion events (AMDEs), when GEM is close to being completely depleted from the air, the concentration of both PHg and RGM rise significantly. During this period, the median concentrations for PHg is 28.2 pgm−3 and RGM is 23.9 pgm−3, from March to June, in comparison to the annual median concentrations of 11.3 and 3.2 pgm−3 for PHg and RGM, respectively. In each of the ten years of sampling, the concentration of PHg increases steadily from January through March and is higher than the concentration of RGM. This pattern begins to change in April when the levels of PHg peak and RGM begin to increase. In May, the high PHg and low RGM concentration regime observed in the early spring undergoes a transition to a regime with higher RGM and much lower PHg concentrations. The higher RGM concentration continues into June. The transition is driven by the atmospheric conditions of air temperature and particle availability. Firstly, a high ratio of the concentrations of PHg to RGM is reported at low temperatures which suggests that oxidized gaseous mercury partitions to available particles to form PHg. Prior to the transition, the median air temperature is −24.8 °C and after the transition the median air temperature is −5.8 °C. Secondly, the high PHg concentrations occur in the spring when high particle concentrations are present. The high particle concentrations are principally due to Arctic haze and sea salts. In the snow, the concentrations of mercury peak in May for all years. Springtime deposition of total mercury to the snow at Alert peaks in May when atmospheric conditions favour higher levels of RGM. Therefore, the conditions in the atmosphere directly impact when the highest amount of mercury will be deposited to the snow during the Arctic spring.