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Hygroscopic properties of aerosol particles at high relative humidity and their diurnal variations in the North China Plain

The hygroscopic properties of submicron aerosol particles were determined at a suburban site (Wuqing) in the North China Plain among a cluster of cities during the period 17 July to 12 August, 2009. A High Humidity Tandem Differential Mobility Analyser (HH-TDMA) instrument was applied to measure the hygroscopic growth factor (GF) at 90%, 95% and 98.5% relative humidity (RH) for particles with dry diameters between 50 and 250 nm. The probability distribution of GF (GF-PDF) averaged over the period shows a distinct bimodal pattern, namely, a dominant more-hygroscopic (MH) group and a smaller nearly-hydrophobic (NH) group. The MH group particles were highly hygroscopic, and their GF was relatively constant during the period with average values of 1.54 ± 0.02, 1.81 ± 0.04 and 2.45 ± 0.07 at 90%, 95% and 98.5% RH (D0 = 100 nm), respectively. The NH group particles grew very slightly when exposed to high RH, with GF values of 1.08 ± 0.02, 1.13 ± 0.06 and 1.24 ± 0.13 respectively at 90%, 95% and 98.5% RH (D0 = 100 nm). The hygroscopic growth behaviours at different RHs were well represented by a single-parameter Köhler model. Thus, the calculation of GF as a function of RH and dry diameter could be facilitated by an empirical parameterization of κ as function of dry diameter. A strong diurnal pattern in number fraction of different hygroscopic groups was observed. The average number fraction of NH particles during the day was about 8%, while during the nighttime fractions up to 20% were reached. Correspondingly, the state of mixing in terms of water uptake varied significantly during a day. Simulations using a particle-resolved aerosol box model (PartMC-MOSAIC) suggest that the diurnal variations of aerosol hygroscopicity and mixing state were mainly caused by the evolution of the atmospheric mixing layer. The shallow nocturnal boundary layer during the night facilitated the accumulation of freshly emitted carbonaceous particles (mainly hydrophobic) near the surface while in the morning turbulence entrained the more aged and more hygroscopic particles from aloft and diluted the NH particles near the surface resulting in a decrease in the fraction of NH particles.
The impact of anthropogenic emissions on atmospheric sulfate production pathways, oxidants, and ice core Δ17O(SO42–)

We use a global three-dimensional chemical transport model to quantify the influence of anthropogenic emissions on atmospheric sulfate production mechanisms and oxidant concentrations constrained by observations of the oxygen isotopic composition (Δ17O = &delta17O–0.52 × &delta18O) of sulfate in Greenland and Antarctic ice cores and aerosols. The oxygen isotopic composition of non-sea salt sulfate (Δ17O(SO42–)) is a function of the relative importance of each oxidant (e.g. O3, OH, H2O2, and O2) during sulfate formation, and can be used to quantify sulfate production pathways. Due to its dependence on oxidant concentrations, Δ17O(SO42–) has been suggested as a proxy for paleo-oxidant levels. However, the oxygen isotopic composition of sulfate from both Greenland and Antarctic ice cores shows a trend opposite to that expected from the known increase in the concentration of tropospheric O3 since the preindustrial period. The model simulates a significant increase in the fraction of sulfate formed via oxidation by O2 catalyzed by transition metals in the present-day Northern Hemisphere troposphere (from 11% to 22%), offset by decreases in the fractions of sulfate formed by O3 and H2O2. There is little change, globally, in the fraction of tropospheric sulfate produced by gas-phase oxidation (from 23% to 27%). The model-calculated change in Δ17O(SO42–) since preindustrial times (1850 CE) is consistent with Arctic and Antarctic observations. The model simulates a 42% increase in the concentration of global mean tropospheric O3, a 10% decrease in OH, and a 58% increase in H2O2 between the preindustrial period and present. Model results indicate that the observed decrease in the Arctic Δ17O(SO42–) – in spite of increasing tropospheric O3 concentrations – can be explained by the combined effects of increased sulfate formation by O2 catalyzed by anthropogenic transition metals and increased cloud water acidity, rendering Δ17O(SO42–) insensitive to changing oxidant concentrations in the Arctic on this timescale. In Antarctica, the Δ17O(SO42–) is sensitive to relative changes of oxidant concentrations because cloud pH and metal emissions have not varied significantly in the Southern Hemisphere on this timescale, although the response of Δ17O(SO42–) to the modeled changes in oxidants is small. There is little net change in the Δ17O(SO42–) in Antarctica, in spite of increased O3, which can be explained by a compensatory effect from an even larger increase in H2O2. In the model, decreased oxidation by OH (due to lower OH concentrations) and O3 (due to higher H2O2 concentrations) results in little net change in Δ17O(SO42–) due to offsetting effects of Δ17O(OH) and Δ17O(O3). Additional model simulations are conducted to explore the sensitivity of the oxygen isotopic composition of sulfate to uncertainties in the preindustrial emissions of oxidant precursors.
Seasonal and spatial variability of surface ozone over China: contributions from background and domestic pollution

Both observations and a 3-D chemical transport model suggest that surface ozone over populated eastern China features a summertime trough and that the month when surface ozone peaks differs by latitude and region. Source-receptor analysis is used to quantify the contributions of background ozone and Chinese anthropogenic emissions on this variability. Annual mean background ozone over China shows a spatial gradient from 55 ppbv in the northwest to 20 ppbv in the southeast, corresponding with changes in topography and ozone lifetime. Pollution background ozone (annual mean of 12.6 ppbv) shows a minimum in the summer and maximum in the spring. On the monthly-mean basis, Chinese pollution ozone (CPO) has a peak of 20–25 ppbv in June north of the Yangtze River and in October south of it, which explains the peaks of surface ozone in these months. The summertime trough in surface ozone over eastern China can be explained by the decrease of background ozone from spring to summer (by −15 ppbv regionally averaged over eastern China). Tagged simulations suggest that long-range transport of ozone from northern mid-latitude continents (including Europe and North America) reaches a minimum in the summer, whereas ozone from Southeast Asia exhibits a maximum in the summer over eastern China. This contrast in seasonality provides clear evidence that the seasonal switch in monsoonal wind patterns plays a significant role in determining the seasonality of background ozone over China.
The response of precipitation to aerosol through riming and melting in deep convective clouds

We have used a 2-D axisymmetric, non-hydrostatic, bin-resolved cloud model to examine the impact of aerosol changes on the development of mixed-phase convective clouds. We have simulated convective clouds from four different sites (three continental and one tropical marine) with a wide range of realistic aerosol loadings and initial thermodynamic conditions (a total of 93 different clouds). It is found that the accumulated precipitation responds very differently to changing aerosol in the marine and continental environments. For the continental clouds, the scaled total precipitation reaches a maximum for aerosol that produce drop numbers at cloud base between 180–430 cm−3 when other conditions are the same. In contrast, all the tropical marine clouds show an increase in accumulated precipitation and deeper convection with increasing aerosol loading. For continental clouds, drops are rapidly depleted by ice particles shortly after the onset of precipitation. The precipitation is dominantly produced by melting ice particles. The riming rate increases with aerosol when the loading is very low, and decreases when the loading is high. Peak precipitation intensities tend to increase with aerosol up to drop concentrations (at cloud base) of ~500 cm−3 then decrease with further aerosol increases. This behaviour is caused by the initial transition from warm to mixed-phase rain followed by reduced efficiency of mixed-phase rain at very high drop concentrations. The response of tropical marine clouds to increasing aerosol is different to, and larger than, that of continental clouds. In the more humid tropical marine environment with low cloud bases we find that accumulated precipitation increases with increasing aerosol. The increase is driven by the transition from warm to mixed-phase rain. Our study suggests that the response of deep convective clouds to aerosol will be an important contribution to the spatial and temporal variability in cloud microphysics and precipitation.
Aerosol plume transport and transformation in high spectral resolution lidar measurements and WRF-Flexpart simulations during the MILAGRO Field Campaign

The Mexico City Metropolitan Area (MCMA) experiences high loadings of atmospheric aerosols from anthropogenic sources, biomass burning and wind-blown dust. This paper uses a combination of measurements and numerical simulations to identify different plumes affecting the basin and to characterize transformation inside the plumes. The High Spectral Resolution Lidar on board the NASA LaRC B-200 King Air aircraft measured extinction coefficients and extinction to backscatter ratio at 532 nm, and backscatter coefficients and depolarization ratios at 532 and 1064 nm. These can be used to identify aerosol types. The measurement curtains are compared with particle trajectory simulations using WRF-Flexpart for different source groups. The good correspondence between measurements and simulations suggests that the aerosol transport is sufficiently well characterized by the models to estimate aerosol types and ages. Plumes in the basin undergo complex transport, and are frequently mixed together. Urban aerosols are readily identifiable by their low depolarization ratios and high lidar ratios, and dust by the opposite properties. Fresh biomass burning plumes have very low depolarization ratios which increase rapidly with age. This rapid transformation is consistent with the presence of atmospheric tar balls in the fresh plumes.
Measurements of cloud condensation nuclei activity and droplet activation kinetics of fresh unprocessed regional dust samples and minerals

This study reports laboratory measurements of cloud condensation nuclei (CCN) activity and droplet activation kinetics of aerosols dry generated from clays, calcite, quartz, and desert soil samples from Northern Africa, East Asia/China, and Northern America. Based on the observed dependence of critical supersaturation, sc, with particle dry diameter, Ddry, we found that FHH (Frenkel, Halsey and Hill) adsorption activation theory is a far more suitable framework for describing fresh dust CCN activity than Köhler theory. One set of FHH parameters (AFHH &sim; 2.25 ± 0.75, BFHH &sim; 1.20 ± 0.10) can adequately reproduce the measured CCN activity for all species considered, and also explains the large range of hygroscopicities reported in the literature. Based on a threshold droplet growth analysis, mineral dust aerosols were found to display retarded activation kinetics compared to ammonium sulfate. Comprehensive simulations of mineral dust activation and growth in the CCN instrument suggest that this retardation is equivalent to a reduction of the water vapor uptake coefficient (relative to that for calibration ammonium sulfate aerosol) by 30–80%. These results suggest that dust particles do not require deliquescent material to act as CCN in the atmosphere.
Vertical profiles of nitrous acid in the nocturnal urban atmosphere of Houston, TX

Nitrous acid (HONO) often plays an important role in tropospheric photochemistry as a major precursor of the hydroxyl radical (OH) in early morning hours and potentially during the day. However, the processes leading to formation of HONO and its vertical distribution at night, which can have a considerable impact on daytime ozone formation, are currently poorly characterized by observations and models. Long-path differential optical absorption spectroscopy (LP-DOAS) measurements of HONO during the 2006 TexAQS II Radical and Aerosol Measurement Project (TRAMP), near downtown Houston, TX, show nocturnal vertical profiles of HONO, with mixing ratios of up to 2.2 ppb near the surface and below 100 ppt aloft. Three nighttime periods of HONO, NO2 and O3 observations during TRAMP were used to perform model simulations of vertical mixing ratio profiles. By adjusting vertical mixing and NOx emissions the modeled NO2 and O3 mixing ratios showed very good agreement with the observations. Using a simple conversion of NO2 to HONO on the ground, direct HONO emissions, as well as HONO loss at the ground and on aerosol, the observed HONO profiles were reproduced by the model for 1–2 and 7–8 September in the nocturnal boundary layer (NBL). The unobserved increase of HONO to NO2 ratio (HONO/NO2) with altitude that was simulated by the initial model runs was found to be due to HONO uptake being too small on aerosol and too large on the ground. Refined model runs, with adjusted HONO uptake coefficients, showed much better agreement of HONO and HONO/NO2 for two typical nights, except during morning rush hour, when other HONO formation pathways are most likely active. One of the nights analyzed showed an increase of HONO mixing ratios together with decreasing NO2 mixing ratios that the model was unable to reproduce, most likely due to the impact of weak precipitation during this night. HONO formation and removal rates averaged over the lowest 300 m of the atmosphere showed that NO2 to HONO conversion on the ground was the dominant source of HONO, followed by traffic emission. Aerosol did not play an important role in HONO formation. Although ground deposition was also a major removal pathway of HONO, net HONO production at the ground was the main source of HONO in our model studies. Sensitivity studies showed that in the stable NBL, net HONO production at the ground tends to increase with faster vertical mixing and stronger NOx emission. Vertical transport was found to be the dominant source of HONO aloft.
Sources of variations in total column carbon dioxide

Observations of gradients in the total CO2 column, &lang;CO2&rang;, are expected to provide improved constraints on surface fluxes of CO2. Here we use a general circulation model with a variety of prescribed carbon fluxes to investigate how variations in &lang;CO2&rang; arise. On diurnal scales, variations are small and are forced by both local fluxes and advection. On seasonal scales, gradients are set by the north-south flux distribution. On synoptic scales, variations arise due to large-scale eddy-driven disturbances of the meridional gradient. In this case, because variations in &lang;CO2&rang; are tied to synoptic activity, significant correlations exist between &lang;CO2&rang; and dynamical tracers. We illustrate how such correlations can be used to describe the north-south gradients of &lang;CO2&rang; and the underlying fluxes on continental scales. These simulations suggest a novel analysis framework for using column observations in carbon cycle science.
Corrigendum to "Influence of meteorology on PM10 trends and variability in Switzerland from 1991 to 2008" published in Atmos. Chem. Phys., 11, 1813–1835, 2011
Spatial and temporal variability in the ratio of trace gases emitted from biomass burning

Fires are a major source of trace gases and aerosols to the atmosphere. The amount of biomass burned is becoming better known, most importantly due to improved burned area datasets and a better representation of fuel consumption. The spatial and temporal variability in the partitioning of biomass burned into emitted trace gases and aerosols, however, has received relatively little attention. To convert estimates of biomass burned to trace gas and aerosol emissions, most studies have used emission ratios (or emission factors (EFs)) based on the arithmetic mean of field measurement outcomes, stratified by biome. However, EFs vary substantially in time and space, even within a single biome. In addition, it is unknown whether the available field measurement locations provide a representative sample for the various biomes. Here we used the available body of EF literature in combination with satellite-derived information on vegetation characteristics and climatic conditions to better understand the spatio-temporal variability in EFs. While focusing on CO, CH4, and CO2, our findings are also applicable to other trace gases and aerosols. We explored relations between EFs and different measurements of environmental variables that may correlate with part of the variability in EFs (tree cover density, vegetation greenness, temperature, precipitation, and the length of the dry season). Although reasonable correlations were found for specific case studies, correlations based on the full suite of available measurements were lower and explained about 33%, 38%, 19%, and 34% of the variability for respectively CO, CH4, CO2, and the Modified Combustion Efficiency (MCE). This may be partly due to uncertainties in the environmental variables, differences in measurement techniques for EFs, assumptions on the ratio between flaming and smoldering combustion, and incomplete information on the location and timing of EF measurements. We derived new mean EFs, using the relative importance of each measurement location with regard to fire emissions. These weighted averages were relatively similar to the arithmetic mean. When using relations between the environmental variables and EFs to extrapolate to regional and global scales, we found substantial differences, with for savannas 13% and 22% higher CO and CH4 EFs than the arithmetic mean of the field studies, possibly linked to an underrepresentation of woodland fires in EF measurement locations. We argue that from a global modeling perspective, future measurement campaigns could be more beneficial if measurements are made over the full fire season, and if relations between ambient conditions and EFs receive more attention.