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Atmospheric homogeneous nucleation of H2SO4 and H2O

We report laboratory observations of H2SO4 and H2O homogeneous nucleation made under atmospherically relevant conditions ([H2SO4] of 106 – 107 cm−3 and 287 K). Our observations show that nucleation takes place at [H2SO4] of 106 – 107 cm−3, as observed in the atmosphere. The slope of nucleation rate (J) vs. [H2SO4] ranges between 4–6, consistent with thermodynamic predictions of neutral H2SO4 clusters, but is higher than those observed in the atmosphere. These results indicate that ternary aerosol precursors are needed to reduce the slope to 1–2 in the atmosphere. This study also discusses the effects of experimental parameters on laboratory observation results, in order to properly interpret the experimental data.
Climate impact on airborne particulate matter concentrations in California using seven year analysis periods

The effect of global climate change on the annual average concentration of fine particulate matter (PM2.5) in California was studied using a climate-air quality modeling system composed of global through regional models. Output from the NCAR/DOE Parallel Climate Model (PCM) generated under the "business as usual" global emissions scenario was downscaled using the Weather Research and Forecasting (WRF) model followed by air quality simulations using the UCD/CIT airshed model. The system represents major atmospheric processes acting on gas and particle phase species including meteorological effects on emissions, advection, dispersion, chemical reaction rates, gas-particle conversion, and dry/wet deposition. The air quality simulations were carried out for the entire state of California with a resolution of 8-km for the years 2000–2006 (present climate with present emissions) and 2047–2053 (future climate with present emissions). Each of these 7-year analysis periods was analyzed using a total of 1008 simulated days to span a climatologically relevant time period with a practical computational burden. The 7-year windows were chosen to properly account for annual variability with the added benefit that the air quality predictions under the present climate could be compared to actual measurements. The climate-air quality modeling system successfully predicted the spatial pattern of present climate PM2.5 concentrations in California but the absolute magnitude of the annual average PM2.5 concentrations were under-predicted by ~4–39% in the major air basins. The majority of this under-prediction was caused by excess ventilation predicted by PCM-WRF that should be present to the same degree in the current and future time periods so that the net bias introduced into the comparison is minimized. Surface temperature, relative humidity (RH), rain rate, and wind speed were predicted to increase in the future climate while the ultra violet (UV) radiation was predicted to decrease in major urban areas in the San Joaquin Valley (SJV) and South Coast Air Basin (SoCAB). These changes lead to a predicted decrease in PM2.5 mass concentrations of ~0.3–0.7 μg m−3 in the southern portion of the SJV and ~0.3–1.1 μg m−3 along coastal regions of California including the heavily populated San Francisco Bay Area and the SoCAB surrounding Los Angeles. Annual average PM2.5 concentrations were predicted to increase at certain locations within the SJV and the Sacramento Valley (SV) due to the effects of climate change, but a corresponding analysis of the annual variability showed that these predictions are not statistically significant (i.e. the choice of a different 7-year period could produce a different outcome for these regions). Overall, virtually no region in California outside of coastal + central Los Angeles, and a small region around the port of Oakland in the San Francisco Bay Area experienced a statistically significant change in annual average PM2.5 concentrations due to the effects of climate change in the present~study. The present study employs the highest spatial resolution (8 km) and the longest analysis windows (7 years) of any climate-air quality analysis conducted for California to date, but the results still have some degree of uncertainty. Most significantly, GCM calculations have inherent uncertainty that is not fully represented in the current study since a single GCM was used as the starting point for all calculations. The PCM results used in the current study predicted greater wintertime increases in air temperature over the Pacific Ocean than over land, further motivating comparison to other GCM results. Ensembles of GCM results are usually employed to build confidence in climate calculations. The current results provide a first data-point for the climate-air quality analysis that simultaneously employ the fine spatial resolution and long time scales needed to capture the behavior of climate-PM2.5 interactions in California. Future downscaling studies should follow up with a full ensemble of GCMs as their starting point, and include aerosol feedback effects on local meteorology.
Atmospheric pollutant outflow from southern Asia: a review

Southern Asia, extending from Pakistan and Afghanistan to Indonesia and Papua New Guinea, is one of the most heavily populated regions of the world. Biofuel and biomass burning play a disproportionately large role in the emissions of most key pollutant gases and aerosols there, in contrast to much of the rest of the Northern Hemisphere, where fossil fuel burning and industrial processes tend to dominate. This results in polluted air masses which are enriched in carbon-containing aerosols, carbon monoxide, and hydrocarbons. The outflow and long-distance transport of these polluted air masses is characterized by three distinct seasonal circulation patterns: the winter monsoon, the summer monsoon, and the monsoon transition periods. During winter, the near-surface flow is mostly northeasterly, and the regional pollution forms a thick haze layer in the lower troposphere which spreads out over millions of square km between southern Asia and the Intertropical Convergence Zone (ITCZ), located several degrees south of the equator over the Indian Ocean during this period. During summer, the heavy monsoon rains effectively remove soluble gases and aerosols. Less soluble species, on the other hand, are lifted to the upper troposphere in deep convective clouds, and are then transported away from the region by strong upper tropospheric winds, particularly towards northern Africa and the Mediterranean in the tropical easterly jet. Part of the pollution can reach the tropical tropopause layer, the gateway to the stratosphere. During the monsoon transition periods, the flow across the Indian Ocean is primarily zonal, and strong pollution plumes originating from both southeastern Asia and from Africa spread across the central Indian Ocean. This paper provides a review of the current state of knowledge based on the many observational and modeling studies over the last decades that have examined the southern Asian atmospheric pollutant outflow and its large scale effects. An outlook is provided as a guideline for future research, pointing out particularly critical issues such as: resolving discrepancies between top down and bottom up emissions estimates; assessing the processing and aging of the pollutant outflow; developing a better understanding of the observed elevated pollutant layers and their relationship to local sea breeze and large scale monsoon circulations; and determining the impacts of the pollutant outflow on the Asian monsoon meteorology and the regional hydrological cycle, in particular the mountain cryospheric reservoirs and the fresh water supply, which in turn directly impact the lives of over a billion inhabitants of southern Asia.
Observations of ozone production in a dissipating tropical convective cell during TC4

From 13 July–9 August 2007, 25 ozonesondes were launched from Las Tablas, Panama as part of the Tropical Composition, Cloud, and Climate Coupling (TC4) mission. On 5 August, a strong convective cell formed in the Gulf of Panama. World Wide Lightning Location Network (WWLLN) data indicated 563 flashes (09:00–17:00 UTC) in the Gulf. NO2 data from the Ozone Monitoring Instrument (OMI) show enhancements, suggesting lightning production of NOx. At 15:05 UTC, an ozonesonde ascended into the southern edge of the now dissipating convective cell as it moved west across the Azuero Peninsula. The balloon oscillated from 2.5–5.1 km five times (15:12–17:00 UTC), providing a unique examination of ozone (O3) photochemistry on the edge of a convective cell. Ozone increased at a rate of ~1.6–4.6 ppbv/hr between the first and last ascent, resulting cell wide in an increase of ~(2.1–2.5) × 106 moles of O3. This estimate agrees to within a factor of two of our estimates of photochemical lightning O3 production from the WWLLN flashes, from the radar-inferred lightning flash data, and from the OMI NO2 data (~1.2, ~1.0, and ~1.7 × 106 moles, respectively), though all estimates have large uncertainties. Examination of DC-8 in situ and lidar O3 data gathered around the Gulf that day suggests 70–97% of the O3 change occurred in 2.5–5.1 km layer. A photochemical box model initialized with nearby TC4 aircraft trace gas data suggests these O3 production rates are possible with our present understanding of photochemistry.
Sunphotometry of the 2006–2007 aerosol optical/radiative properties at the Himalayan Nepal Climate Observatory-Pyramid (5079 m a.s.l.)

In spite of being located at the heart of the highest mountain range in the world, the Himalayan Nepal Climate Observatory (5079 m a.s.l.) at the Ev-K2-CNR Pyramid is shown to be affected by the advection of pollution aerosols from the populated regions of southern Nepal and the Indo-Gangetic plains. Such an impact is observed along most of the period April 2006–March 2007 addressed here, with a minimum in the monsoon season. Backtrajectory-analysis indicates long-range transport episodes occurring in this year to originate mainly in the west Asian deserts. At this high altitude site, the measured aerosol optical depth is observed to be about one order of magnitude lower than the one measured at Ghandi College (60 m a.s.l.), in the Indo-Gangetic basin. As for Ghandi College, and in agreement with the in situ ground observations at the Pyramid, the fine mode aerosol optical depth maximizes during winter and minimizes in the monsoon season. Conversely, total optical depth maximizes during the monsoon due to the occurrence of elevated, coarse particle layers. Possible origins of these particles are wind erosion from the surrounding peaks and hydrated/cloud-processed aerosols. Assessment of the aerosol radiative forcing is then expected to be hampered by the presence of these high altitude particle layers, which impede an effective, continuous measurement of anthropogenic aerosol radiative properties from sky radiance inversions and/or ground measurements alone. Even though the retrieved absorption coefficients of pollution aerosols were rather large (single scattering albedo of the order of 0.6–0.9 were observed in the month of April 2006), the corresponding low optical depths (~0.03 at 500 nm) are expected to limit the relevant radiative forcing. Still, the high specific forcing of this aerosol and its capability of altering snow surface albedo provide good reasons for continuous monitoring.
Multi sensor reanalysis of total ozone

A single coherent total ozone dataset, called the Multi Sensor Reanalysis (MSR), has been created from all available ozone column data measured by polar orbiting satellites in the near-ultraviolet Huggins band in the last thirty years. Fourteen total ozone satellite retrieval datasets from the instruments TOMS (on the satellites Nimbus-7 and Earth Probe), SBUV (Nimbus-7, NOAA-9, NOAA-11 and NOAA-16), GOME (ERS-2), SCIAMACHY (Envisat), OMI (EOS-Aura), and GOME-2 (Metop-A) have been used in the MSR. As first step a bias correction scheme is applied to all satellite observations, based on independent ground-based total ozone data from the World Ozone and Ultraviolet Data Center. The correction is a function of solar zenith angle, viewing angle, time (trend), and effective ozone temperature. As second step data assimilation was applied to create a global dataset of total ozone analyses. The data assimilation method is a sub-optimal implementation of the Kalman filter technique, and is based on a chemical transport model driven by ECMWF meteorological fields. The chemical transport model provides a detailed description of (stratospheric) transport and uses parameterisations for gas-phase and ozone hole chemistry. The MSR dataset results from a 30-year data assimilation run with the 14 corrected satellite datasets as input, and is available on a grid of 1× 1 1/2° with a sample frequency of 6 h for the complete time period (1978–2008). The Observation-minus-Analysis (OmA) statistics show that the bias of the MSR analyses is less than 1% with an RMS standard deviation of about 2% as compared to the corrected satellite observations used.
Atmospheric OH reactivities in the Pearl River Delta – China in summer 2006: measurement and model results

Total atmospheric OH reactivities (kOH) have been measured as reciprocal OH lifetimes by a newly developed instrument at a rural site in the densely populated Pearl River Delta (PRD) in Southern China in summer 2006. The deployed technique, LP-LIF, uses laser flash photolysis (LP) for artificial OH generation and laser-induced fluorescence (LIF) to measure the time-dependent OH decay in samples of ambient air. The reactivities observed at PRD covered a range from 10 s−1 to 120 s−1, indicating a large load of chemical reactants. On average, kOH exhibited a pronounced diurnal profile with a mean maximum value of 50 s−1 at daybreak and a mean minimum value of 20 s−1 at noon. The comparison of reactivities calculated from measured trace gases with measured kOH reveals a missing reactivity of about a factor of 2 at day and night. The reactivity explained by measured trace gases was dominated by anthropogenic pollutants (e.g., CO, NOx, light alkenes and aromatic hydrocarbons) at night, while it was strongly influenced by local, biogenic emissions of isoprene during the day. Box model calculations initialized by measured parameters reproduce the observed OH reactivity well and suggest that the missing reactivity is contributed by unmeasured, secondary chemistry products (mainly aldehydes and ketones) that were photochemically formed by hydrocarbon oxidation. Overall, kOH was dominated by organic compounds, which had a maximum contribution of 85% in the afternoon. The paper demonstrates the usefulness of direct reactivity measurements, emphasizes the need for direct measurements of oxygenated organic compounds in atmospheric chemistry studies, and discusses uncertainties of the modelling of OVOC reactivities.
On the roles of sulphuric acid and low-volatility organic vapours in the initial steps of atmospheric new particle formation

Sulphuric acid and organic vapours have been identified as the key components in the ubiquitous secondary new particle formation in the atmosphere. In order to assess their relative contribution and spatial variability, we analysed altogether 36 new particle formation events observed at four European measurement sites during EUCAARI campaigns in 2007–2009. We tested models of several different nucleation mechanisms coupling the formation rate of neutral particles (J) with the concentration of sulphuric acid ([H2SO4]) or low-volatility organic vapours ([org]) condensing on sub-4 nm particles, or with a combination of both concentrations. Furthermore, we determined the related nucleation coefficients connecting the neutral nucleation rate J with the vapour concentrations in each mechanism. The main goal of the study was to identify the mechanism of new particle formation and subsequent growth that minimizes the difference between the modelled and measured nucleation rates. At three out of four measurement sites – Hyytiälä (Finland), Melpitz (Germany) and San Pietro Capofiume (Italy) – the nucleation rate was closely connected to squared sulphuric acid concentration, whereas in Hohenpeissenberg (Germany) the low-volatility organic vapours were observed to be dominant. However, the nucleation rate at the sulphuric acid dominant sites could not be described with sulphuric acid concentration and a single value of the nucleation coefficient, as K in J=K [H2SO4]2, but the median coefficients for different sites varied over an order of magnitude. This inter-site variation was substantially smaller when the heteromolecular homogenous nucleation between H2SO4 and organic vapours was assumed to take place in addition to homogenous nucleation of H2SO4 alone, i.e., J=KSA1[H2SO4]2+KSA2[H2SO4][org]. By adding in this equation a term describing homomolecular organic vapour nucleation, Ks3[org]2, equally good results were achieved. In general, our results suggest that organic vapours do play a role, not only in the condensational growth of the particles, but also in the nucleation process, with a site-specific degree.
Spectrally-invariant behavior of zenith radiance around cloud edges simulated by radiative transfer

In a previous paper, we discovered a surprising spectrally-invariant relationship in shortwave spectrometer observations taken by the Atmospheric Radiation Measurement (ARM) program. The relationship suggests that the shortwave spectrum near cloud edges can be determined by a linear combination of zenith radiance spectra of the cloudy and clear regions. Here, using radiative transfer simulations, we study the sensitivity of this relationship to the properties of aerosols and clouds, to the underlying surface type, and to the finite field-of-view (FOV) of the spectrometer. Overall, the relationship is mostly sensitive to cloud properties and has little sensitivity to other factors. At visible wavelengths, the relationship primarily depends on cloud optical depth regardless of cloud phase function, thermodynamic phase and drop size. At water-absorbing wavelengths, the slope of the relationship depends primarily on cloud optical depth; the intercept, by contrast, depends primarily on cloud absorbing and scattering properties, suggesting a new retrieval method for cloud drop effective radius. These results suggest that the spectrally-invariant relationship can be used to infer cloud properties near cloud edges even with insufficient or no knowledge about spectral surface albedo and aerosol properties.
Global modeling of organic aerosol: the importance of reactive nitrogen (NOx and NO3)

Reactive nitrogen compounds, specifically NOx and NO3, likely influence global organic aerosol levels. To assess these interactions, GEOS-Chem, a chemical transport model, is updated to include improved biogenic emissions (following MEGAN v2.1/2.04), a new organic aerosol tracer lumping scheme, aerosol from nitrate radical (NO3) oxidation of isoprene, and NOx-dependent monoterpene and sesquiterpene aerosol yields. As a result of significant nighttime terpene emissions, fast reaction of monoterpenes with the nitrate radical, and relatively high aerosol yields from NO3 oxidation, biogenic hydrocarbon-NO3 reactions are expected to be a major contributor to surface level aerosol concentrations in anthropogenically influenced areas such as the United States. By including aerosol from nitrate radical oxidation in GEOS-Chem, terpene (monoterpene + sesquiterpene) aerosol approximately doubles and isoprene aerosol is enhanced by 30 to 40% in the Southeast United States. In terms of the global budget of organic aerosol, however, aerosol from nitrate radical oxidation is somewhat minor (slightly more than 3 Tg/yr) due to the relatively high volatility of organic-NO3 oxidation products in the yield parameterization. Globally, 69 to 88 Tg/yr of organic aerosol is predicted to be produced annually, of which 14–15 Tg/yr is from oxidation of monoterpenes and sesquiterpenes and 8–9 Tg/yr from isoprene.