Items

Advanced search

Dependence of the single-scattering properties of small ice crystals on idealized shape models

The projections of small ice crystals (with maximum dimension <50 μm) appear quasi-circular when imaged by probes on aircraft flying through cloud. Therefore, idealized models constructed to calculate their single-scattering properties have included quasi-spherical models such as Chebyshev particles, Gaussian random spheres, and droxtals. Recently, an ice analogue grown from sodium fluorosilicate solution on a glass substrate, with several columns emanating from a common center of mass, was shown to be quasi-circular when imaged by state-of-the-art cloud probes. In this study, a new idealized model, called the budding Bucky ball (3B) that resembles the shape of the small ice analogue is developed. The corresponding single-scattering properties (scattering phase function P11 and asymmetry parameter g) are computed by a ray-tracing code. Compared with previously used models, 3B scatters less light in the forward and more light in the lateral and backward directions. The Chebyshev particles and Gaussian random spheres show smooth and featureless P11, whereas droxtals and 3Bs, which have a faceted structure, show several peaks in P11 associated with angles of minimum deviation. Overall, the difference in the forward (lateral; backward) scattering between models are up to 22% (994%; 132%), 20% (510%; 101%), and 16% (146%; 156%) for small ice crystals with respective area ratios of 0.85, 0.77, and 0.69. The g for different models varies by up to 25%, 23%, and 19% for particles with area ratios of 0.85, 0.77, and 0.69, respectively. Because the single-scattering properties of small ice crystals depend both on the choice of the idealized model and the area ratios used to characterize the small ice crystals, higher resolution observations of small ice crystals or direct observations of their single-scattering properties are required.
Pseudo steady states of HONO measured in the nocturnal marine boundary layer: a conceptual model for HONO formation on aqueous surfaces

A complete understanding of the formation mechanism of nitrous acid (HONO) in the ambient atmosphere is complicated by a lack of understanding of processes occurring when aqueous water is present. We report nocturnal measurements of HONO, SO2 and NO2 by differential optical absorption spectroscopy over the ocean surface in a polluted marine environment. In this aqueous environment, we observed reproducible pseudo steady states (PSS) of HONO every night, that are fully formed shortly after sunset, much faster than seen in urban environments. During the PSS period, HONO is constant with time, independent of air mass source and independent of the concentration of NO2. The independence of HONO on the concentration of NO2 implies a 0° order formation process, likely on a saturated surface, with reversible partitioning of HONO to the gas phase, through vaporization and deposition to the surface. We observed median HONO/NO2 ratios starting at 0.13 at the beginning of the PSS period (with an apparent lower bound of 0.03), rising to median levels of ~0.30 at the end of the PSS period (with an upper bound >1.0). The implication of these numbers is that they suggest a common surface mechanism of HONO formation on terrestrial and aqueous surfaces, with an increase in the HONO/NO2 ratio with the amount of water available at the surface. The levels of HONO during the nocturnal PSS period are positively correlated with temperature, consistent with a partitioning of HONO from the surface to the gas phase with an apparent enthalpy of vaporization of ΔHSNL (HONO)=55.5±5.4 kJ mol−1. The formation mechanism on aqueous surfaces is independent of relative humidity (RH), despite observation of a negative HONO-RH correlation. A conceptual model for HONO formation on ambient aqueous surfaces is presented, with the main elements being the presence of a surface nanolayer (SNL), highly acidic and saturated with N(IV) precursors, production of HNO3, that diffuses to underlying water layers, and HONO, which partitions reversibly between the SNL and the gas phase. Implications of the conceptual model are discussed.
African biomass burning plumes over the Atlantic: aircraft based measurements and implications for H2SO4 and HNO3 mediated smoke particle activation

Airborne measurements of trace gases and aerosol particles have been made in two aged biomass burning (BB) plumes over the East Atlantic (Gulf of Guinea). The plumes originated from BB in the Southern-Hemisphere African savanna belt. On the day of our measurements (13 August 2006), the plumes had ages of about 10 days and were respectively located in the middle troposphere (MT) at 3900–5500 m altitude and in the upper troposphere (UT) at 10 800–11 200 m. Probably, the MT plume was lifted by dry convection and the UT plume was lifted by wet convection. In the more polluted MT-plume, numerous measured trace species had markedly elevated abundances, particularly SO2 (up to 1400 pmol mol−1), HNO3 (5000–8000 pmol mol−1) and smoke particles with diameters larger than 270 nm (up to 2000 cm−3). Our MT-plume measurements indicate that SO2 released by BB had not experienced significant loss by deposition and cloud processes but rather had experienced OH-induced conversion to gas-phase sulfuric acid. By contrast, a significant fraction of the released NOy had experienced loss, most likely as HNO3 by deposition. In the UT-plume, loss of NOy and SO2 was more pronounced compared to the MT-plume, probably due to cloud processes. Building on our measurements and accompanying model simulations, we have investigated trace gas transformations in the ageing and diluting plumes and their role in smoke particle processing and activation. Emphasis was placed upon the formation of sulfuric acid and ammonium nitrate, and their influence on the activation potential of smoke particles. Our model simulations reveal that, after 13 August, the lower plume traveled across the Atlantic and descended to 1300 m and hereafter ascended again. During the travel across the Atlantic, the soluble mass fraction of smoke particles and their mean diameter increased sufficiently to allow the processed smoke particles to act as water vapor condensation nuclei already at very low water vapor supersaturations of only about 0.04%. Thereby, aged smoke particles had developed a potential to act as water vapor condensation nuclei in the formation of maritime clouds.
Saharan and Asian dust: similarities and differences determined by CALIPSO, AERONET, and a coupled climate-aerosol microphysical model

This study compares the properties of atmospheric dust from the Saharan deserts and the Asian deserts using data from CALIPSO and AERONET during 2006 and 2007 along with simulations using a coupled climate-microphysical sectional model. Saharan deserts are largely south of 30° N, while Asian ones are primarily north of 30° N, hence they experience different meteorological regimes. Saharan dust lifting occurs all year long, primarily due to subtropical weather systems. However, Asian dust is lifted mostly in spring when mid-latitude frontal systems lead to high winds. Rainfall is more abundant over Asia during the dust lifting events, leading to greater local dust removal than over the Sahara. However, most dust removal is due to sedimentation. Despite the different meteorological regimes, the same dust lifting schemes work in models for Asian and Saharan dust. The magnitudes of dust lifted in Africa and Asia differ significantly over the year. In our model the yearly horizontal dust flux just downwind of the African dust source is about 1088 Tg (10° S–40° N, 10° W) and from the Asian dust source it is about 355 Tg (25° N–55° N, 105° E) in 2007, which is comparable to previous studies. We find the difference in dust flux is mainly due to the larger area over which dust is lifted in Africa than Asia. However, Africa also has stronger winds in some seasons. Once lifted, the Saharan dust layers generally move toward the west and descend in altitude from about 7 km to the surface over several days in the cases studied. Asian dust often has multiple layers (two layers in the cases studied) during transport largely to the east. One layer stays well above boundary layer during transport and shows little descent, while the other, lower, layer descends with time. This observation contrasts with studies suggesting the descent of Saharan dust is due to sedimentation of the particles, and suggests instead it is dominated by meteorology. We find the size distributions of Asian and African dust are similar when the dust is lifted, but the mode size can differ and secondary size modes can develop probably due to differences in vertical wind velocities during transport. The single scattering albedo of African and Asian dust does differ, due primarily to the imaginary parts of the refractive indexes being different, which in turn is likely due to different dust composition. This study is a step towards a global understanding of dust and its properties.
Atmospheric degradation of 3-methylfuran: kinetic and products study

A study of the kinetics and products obtained from the reactions of 3-methylfuran with the main atmospheric oxidants has been performed. The rate coefficients for the gas-phase reaction of 3-methylfuran with OH and NO3 radicals have been determined at room temperature and atmospheric pressure (air and N2 as bath gases), using a relative method with different experimental techniques. The rate coefficients obtained for these reactions were (in units cm3 molecule−1 s−1) kOH = (1.13 ± 0.22) × 10−10 and kNO3 = (1.26 ± 0.18) × 10−11. Products from the reaction of 3-methylfuran with OH, NO3 and Cl atoms in the absence and in the presence of NO have also been determined. The main reaction products obtained were chlorinated methylfuranones and hydroxy-methylfuranones in the reaction of 3-methylfuran with Cl atoms, 2-methylbutenedial, 3-methyl-2,5-furanodione and hydroxy-methylfuranones in the reaction of 3-methylfuran with OH and NO3 radicals and also nitrated compounds in the reaction with NO3 radicals. The results indicate that, in all cases, the main reaction path is the addition to the double bond of the aromatic ring followed by ring opening in the case of OH and NO3 radicals. The formation of 3-furaldehyde and hydroxy-methylfuranones (in the reactions of 3-methylfuran with Cl atoms and NO3 radicals) confirmed the H-atom abstraction from the methyl group and from the aromatic ring, respectively. This study represents the first product determination for Cl atoms and NO3 radicals in reactions with 3-methylfuran. The reaction mechanisms and atmospheric implications of the reactions under consideration are also discussed.
Initiation of coalescence in a cumulus cloud: a beneficial influence of entrainment and mixing

Although rain has been observed to form in warm cumulus clouds within about twenty minutes, calculations that represent condensation and coalescence accurately in such clouds have had difficulty producing rainfall in such a short time except via processes involving giant cloud condensation nuclei (with diameters larger than 2 μm). This model-based study explores a different possible mechanism for accelerating the production of warm rain, one that depends on the variability in droplet trajectories arriving at a given location and time in a cumulus cloud. In the presence of entrainment such droplets experience different growth histories, and the result is broadening of the droplet size distribution. That broadening favours coalescence, leading to embryos that grow to raindrops. These calculations do lead to production of rain that is within the lower range of observations for clouds of Florida, USA, the location on which the input conditions were based. The process emphasized in this study, the formation of drizzle via collisions among droplets in the main peak of the droplet size distribution, complements the growth of precipitation on giant nuclei, which is also an important source of the first rain in the case studied. The results indicate that the mechanism developed here should be considered an important influence on the formation of rain in warm clouds.
The Smithsonian solar constant data revisited: no evidence for a strong effect of solar activity in ground-based insolation data

Apparent evidence for a strong signature of solar activity in ground-based insolation data was recently reported. In particular, a strong increase of the irradiance of the direct solar beam with sunspot number as well as a decline of the brightness of the solar aureole and the measured precipitable water content of the atmosphere with solar activity were presented. The latter effect was interpreted as evidence for cosmic-ray-induced aerosol formation. Here I show that these spurious results are due to a failure to correct for seasonal variations and the effects of volcanic eruptions and local pollution in the data. After correcting for these biases, neither the atmospheric water content nor the brightness of the solar aureole show any significant change with solar activity, and the variations of the solar-beam irradiance with sunspot number are in agreement with previous estimates. Hence there is no evidence for the influence of solar activity on the climate being stronger than currently thought.
Analysis on the impact of aerosol optical depth on surface solar radiation in the Shanghai megacity, China

This study investigated the decadal variation of the direct surface solar radiation (DiSR) and the diffuse surface solar radiation (DfSR) during 1961–2008 in the Shanghai megacity as well as their relationships to Aerosol Optical Depth (AOD) under clear-sky conditions. Three successive periods with unique features of long term variation of DiSR were identified for both clear-sky and all-sky conditions: a "dimming" period from the late 1960s to the mid 1980s, a "stabilization"/"slight brightening" period from the mid 1980s to the mid 1990s, and a "renewed dimming" period thereafter. During the two dimming periods of DiSR, DfSR brightened significantly under clear-sky conditions, indicating that change in atmospheric transparency resulting from aerosol emission has an important role on decadal variation of surface solar radiation (SSR) over this area. The analysis on the relationship between the Moderate-resolution Imaging Spectroradiometer (MODIS) retrieved AOD and the corresponding hourly measurements of DiSR and DfSR under clear-sky conditions clearly revealed that AOD is significantly correlated and anti-correlated with DfSR and DiSR, respectively, both above 99% confidence in all seasons, indicating the great impact of aerosols on SSR through absorption and/or scattering in the atmosphere. In addition, both AOD and the corresponding DiSR and DfSR measured during the satellite passage over Shanghai show obvious weekly cycles. On weekends, AOD is lower than the weekly average, corresponding to higher DiSR and lower DfSR, while the opposite pattern was true for weekdays. Less AOD on weekends due to the reduction of transportation and industrial activities results in enhancement of atmospheric transparency under cloud free conditions so as to increase DiSR and decrease DfSR simultaneously. Results show that aerosol loading from the anthropogenic emissions is an important modulator for the long term variation of SSR in Shanghai.
New particle formation events in semi-clean South African savannah

This study is based on 18 months (20 July 2006–5 February 2008) of continuous measurements of aerosol particle size distributions, air ion size distributions, trace gas concentrations and basic meteorology in a semi-clean savannah environment in Republic of South Africa. New particle formation and growth was observed on 69% of the days and bursts of non-growing ions/sub-10 nm particles on additional 14% of the days. This new particle formation frequency is the highest reported from boundary layer so far. Also the new particle formation and growth rates were among the highest reported in the literature for continental boundary layer locations; median 10 nm formation rate was 2.2 cm−3 s−1 and median 10–30 nm growth rate 8.9 nm h−1. The median 2 nm ion formation rate was 0.5 cm−3 s−1 and the median ion growth rates were 6.2, 8.0 and 8.1 nm h−1 for size ranges 1.5–3 nm, 3–7 nm and 7–20 nm, respectively. The growth rates had a clear seasonal dependency with minimum during winter and maxima in spring and late summer. The relative contribution of estimated sulphuric acid to the growth rate was decreasing with increasing particle size and could explain more than 20% of the observed growth rate only for the 1.5–3 nm size range. Also the air mass history analysis indicated the highest formation and growth rates to be associated with the area of highest VOC (Volatile Organic Compounds) emissions following from biological activity rather than the highest estimated sulphuric acid concentrations. The frequency of new particle formation, however, increased nearly monotonously with the estimated sulphuric acid reaching 100% at H2SO4 concentration of 6 · 107 cm−3, which suggests the formation and growth to be independent of each other.
A two-dimensional volatility basis set: 1. organic-aerosol mixing thermodynamics

We develop the thermodynamic underpinnings of a two-dimensional volatility basis set (2D-VBS) employing saturation mass concentration (Co) and the oxygen content (O:C) to describe volatility, mixing thermodynamics, and chemical evolution of organic aerosol. The work addresses a simple question: "Can we reasonably constrain organic-aerosol composition in the atmosphere based on only two measurable organic properties, volatility and the extent of oxygenation?" This is an extension of our earlier one-dimensional approach employing volatility only (C* = γ Co, where γ is an activity coefficient). Using available constraints on bulk organic-aerosol composition, we argue that one can reasonably predict the composition of organics (carbon, oxygen and hydrogen numbers) given a location in the Co – O:C space. Further, we argue that we can constrain the activity coefficients at various locations in this space based on the O:C of the organic aerosol.