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Influence of aerosol acidity on the chemical composition of secondary organic aerosol from β-caryophyllene

The secondary organic aerosol (SOA) yield of β-caryophyllene photooxidation is enhanced by aerosol acidity. In the present study, the influence of aerosol acidity on the chemical composition of β-caryophyllene SOA is investigated using ultra performance liquid chromatography/electrospray ionization-time-of-flight mass spectrometry (UPLC/ESI-TOFMS). A number of first-, second- and higher-generation gas-phase products having carbonyl and carboxylic acid functional groups are detected in the particle phase. Particle-phase reaction products formed via hydration and organosulfate formation processes are also detected. Increased acidity leads to different effects on the abundance of individual products; significantly, abundances of organosulfates are correlated with aerosol acidity. To our knowledge, this is the first detection of organosulfates and nitrated organosulfates derived from a sesquiterpene. The increase of certain particle-phase reaction products with increased acidity provides chemical evidence to support the acid-enhanced SOA yields. Based on the agreement between the chromatographic retention times and accurate mass measurements of chamber and field samples, three β-caryophyllene products (i.e., β-nocaryophyllon aldehyde, β-hydroxynocaryophyllon aldehyde, and β-dihydroxynocaryophyllon aldehyde) are suggested as chemical tracers for β-caryophyllene SOA. These compounds are detected in both day and night ambient samples collected in downtown Atlanta, GA and rural Yorkville, GA during the 2008 August Mini-Intensive Gas and Aerosol Study (AMIGAS).
Technical Note: VUV photodesorption rates from water ice in the 120–150 K temperature range – significance for Noctilucent Clouds

Laboratory studies have been carried out with the aim to improve our understanding of physicochemical processes which take place at the water ice/air interface initiated by solar irradiation with a wavelength of 121.6 nm. It was intended to mimic the processes of ice particles characteristic of Noctilucent Clouds (NLCs). The experimental set-up used includes a high-vacuum chamber, a gas handling system, a cryostat with temperature controller, an FTIR spectrometer, a vacuum ultraviolet hydrogen lamp, and a microwave generator. We report the first results of measurements of the absolute photodesorption rate (loss of substance due to the escape of photoproducts into gas phase) from thin (20–100 nm) water ice samples kept in the temperature range of 120–150 K. The obtained results show that a flow of photoproducts into the gas phase is considerably lower than presumed in the recent study by Murray and Plane (2005). The experiments indicate that almost all photoproducts remain in the solid phase, and the principal chemical reaction between them is the recombination reaction H + OH → H2O which is evidently very fast. This means that direct photolysis of mesospheric ice particles seems to have no significant impact on the gas phase chemistry of the upper mesosphere.
Dependence of SOA oxidation on organic aerosol mass concentration and OH exposure: experimental PAM chamber studies

The oxidation of secondary organic aerosol (SOA) is studied with mass spectra analysis of SOA formed in a Potential Aerosol Mass (PAM) chamber, a small flow-through photo-oxidation chamber with extremely high OH and ozone levels. The OH exposure from a few minutes in the PAM chamber is similar to that from days to weeks in the atmosphere. The mass spectra were measured with a Quadrupole Aerosol Mass Spectrometer (Q-AMS) for SOA formed from oxidation of α-pinene, m-xylene, p-xylene, and a mixture of the three. The organic mass fractions of m/z 44 (CO2+) and m/z 43 (mainly C2H3O+), named f44 and f43 respectively, are used as indicators of the degree of organic aerosol (OA) oxidation that occurs as the OA mass concentration or the OH exposure are varied. The degree of oxidation is sensitive to both. For a fixed OH exposure, the degree of oxidation initially decreases rapidly and then more slowly as the OA mass concentration increases. For fixed initial precursor VOC amounts, the degree of oxidation increases linearly with OH exposure, with f44 increasing and f43 decreasing. In this study, the degree of SOA oxidation spans much of the range observed in the atmosphere. These results, while sensitive to the determination of f44 and f43, provide evidence that some characteristics of atmospheric OA oxidation can be generated in a PAM chamber. For all measurements in this study, the sum of f44 and f43 is 0.25 ± 0.03, so that the slope of a linear regression is approximately −1 on an f44 vs. f43 plot. This constancy of the sum suggests that these ions are complete proxies for organic mass in the OA studied.
Influence of meteorology on PM10 trends and variability in Switzerland from 1991 to 2008

Measurements of airborne particles with aerodynamic diameter of 10 μm or less (PM10) and meteorological observations are available from 13 stations distributed throughout Switzerland and representing different site types. The effect of all available meteorological variables on PM10 concentrations was estimated using Generalized Additive Models. Data from each season were treated separately. The most important variables affecting PM10 concentrations in winter, autumn and spring were wind gust, the precipitation rate of the previous day, the precipitation rate of the current day and the boundary layer depth. In summer, the most important variables were wind gust, Julian day and afternoon temperature. In addition, temperature was important in winter. A "weekend effect" was identified due to the selection of variable "day of the week" for some stations. Thursday contributes to an increase of 13% whereas Sunday contributes to a reduction of 12% of PM10 concentrations compared to Monday on average over 9 stations for the yearly data. The estimated effects of meteorological variables were removed from the measured PM10 values to obtain the PM10 variability and trends due to other factors and processes, mainly PM10 emissions and formation of secondary PM10 due to trace gas emissions. After applying this process, the PM10 variability was much lower, especially in winter where the ratio of adjusted over measured mean squared error was 0.27 on average over all considered sites. Moreover, PM10 trends in winter were more negative after the adjustment for meteorology and they ranged between −1.25 μg m−3 yr−1 and 0.07 μg m−3 yr−1. The adjusted trends for the other seasons ranged between −1.34 μg m−3 yr−1 and −0.26 μg m−3 yr−1 in spring, −1.40 μg m−3 yr−1 and −0.28 μg m−3 yr−1 in summer and −1.28 μg m−3 yr−1 and −0.11 μg m−3 yr−1 in autumn. The estimated trends of meteorologically adjusted PM10 were in general non-linear. The two urban street sites considered in the study, Bern and Lausanne, experienced the largest reduction in measured and adjusted PM10 concentrations. This indicates a verifiable effect of traffic emission reduction strategies implemented during the past two decades. The average adjusted yearly trends for rural, urban background and urban street stations were −0.37, −0.53 and −1.2 μg m−3 yr−1 respectively. The adjusted yearly trends for all stations range from −0.15 μg m−3 yr−1 to −1.2 μg m−3 yr−1 or −1.2% yr−1 to −3.3% yr−1.
Radiative impact of mineral dust on monsoon precipitation variability over West Africa

The radiative forcing of dust and its impact on precipitation over the West Africa monsoon (WAM) region is simulated using a coupled meteorology and aerosol/chemistry model (WRF-Chem). During the monsoon season, dust is a dominant contributor to aerosol optical depth (AOD) over West Africa. In the control simulation, on 24-h domain average, dust has a cooling effect (−6.11 W m−2) at the surface, a warming effect (6.94 W m−2) in the atmosphere, and a relatively small TOA forcing (0.83 W m−2). Dust modifies the surface energy budget and atmospheric diabatic heating. As a result, atmospheric stability is increased in the daytime and reduced in the nighttime, leading to a reduction of late afternoon precipitation by up to 0.14 mm/h (25%) and an increase of nocturnal and early morning precipitation by up to 0.04 mm/h (45%) over the WAM region. Dust-induced reduction of diurnal precipitation variation improves the simulated diurnal cycle of precipitation when compared to measurements. However, daily precipitation is only changed by a relatively small amount (−0.17 mm/day or −4%). The dust-induced change of WAM precipitation is not sensitive to interannual monsoon variability. On the other hand, sensitivity simulations with weaker to stronger absorbing dust (in order to represent the uncertainty in dust solar absorptivity) show that, at the lower atmosphere, dust longwave warming effect in the nighttime surpasses its shortwave cooling effect in the daytime; this leads to a less stable atmosphere associated with more convective precipitation in the nighttime. As a result, the dust-induced change of daily WAM precipitation varies from a significant reduction of −0.52 mm/day (−12%, weaker absorbing dust) to a small increase of 0.03 mm/day (1%, stronger absorbing dust). This variation originates from the competition between dust impact on daytime and nighttime precipitation, which depends on dust shortwave absorption. Dust reduces the diurnal variation of precipitation regardless of its absorptivity, but more reduction is associated with stronger absorbing dust.
Characterization of submicron aerosols at a rural site in Pearl River Delta of China using an Aerodyne High-Resolution Aerosol Mass Spectrometer

The Pearl River Delta (PRD) region in South China is one of the most economically developed regions in China, but it is also noted for its severe air pollution due to industrial/metropolitan emissions. In order to continuously improve the understanding and quantification of air pollution in this region, an intensive campaign was executed in PRD during October–November 2008. Here, we report and analyze Aerodyne High-Resolution Aerosol Mass Spectrometer measurements at Kaiping, a rural site downwind of the highly-polluted central PRD area, to characterize the general features of submicron particulate pollution in the regional air. The mean measured PMsub>1 mass concentration was 33.1±18.1 μg m−3 during the campaign and composed of organic matter (33.8%), sulfate (33.7%), ammonium (14.0%), nitrate (10.7%), black carbon (6.7%), and chloride (1.1%), which is characterized by high fractions of inorganic ions due to huge emissions of SO2 and NOx in PRD. The average size distributions of the species (except BC) were all dominated by an accumulation mode peaking at ~450 nm in vacuum aerodynamic diameter. Calculations based on high-resolution organic mass spectra indicate that C, H, O, and N on average contributed 56.6, 7.0, 35.1, and 1.3% to the total organic mass, respectively, corresponding to an organic matter mass to organic carbon mass ratio (OM/OC) of 1.77±0.08. Based on the high-resolution organic mass spectral dataset observed, Positive Matrix Factorization (PMF) analysis differentiated the organic aerosol into three components, i.e., biomass burning (BBOA) and two oxygenated (LV-OOA and SV-OOA) organic aerosols, which on average accounted for 24.5, 39.6 and 35.8% of the total organic mass, respectively. The BBOA showed strong features of biomass burning emissions and has been mainly attributed to the open field burning of crop residues after the harvest in PRD rural areas. The LV-OOA and SV-OOA were found to correspond to more aged (and thus less-volatile) and fresher (and semi-volatile) secondary organic aerosol (SOA), respectively. Analysis of meteorological influence supported that regional transport from the central PRD area was the major origin of the PM1 observed at the Kaiping site.
Length and time scales of atmospheric moisture recycling

It is difficult to quantify the degree to which terrestrial evaporation supports the occurrence of precipitation within a certain study region (i.e. regional moisture recycling) due to the scale- and shape-dependence of regional moisture recycling ratios. In this paper we present a novel approach to quantify the spatial and temporal scale of moisture recycling, independent of the size and shape of the region under study. In contrast to previous studies, which essentially used curve fitting, the scaling laws presented by us follow directly from the process equation. thus allowing a fair comparison between regions and seasons. The calculation is based on ERA-Interim reanalysis data for the period 1999 to 2008. It is shown that in the tropics or in mountainous terrain the length scale of recycling can be as low as 500 to 2000 km. In temperate climates the length scale is typically between 3000 to 5000 km whereas it amounts to more than 7000 km in desert areas. The time scale of recycling ranges from 3 to 20 days, with the exception of deserts, where it is much longer. The most distinct seasonal differences can be observed over the Northern Hemisphere: in winter, moisture recycling is insignificant, whereas in summer it plays a major role in the climate. The length and time scales of atmospheric moisture recycling can be useful metrics to quantify local climatic effects of land use change.
Evolution of organic aerosol mass spectra upon heating: implications for OA phase and partitioning behavior

Vacuum Ultraviolet (VUV) photoionization mass spectrometry has been used to measure the evolution of chemical composition for two distinct organic aerosol types as they are passed through a thermodenuder at different temperatures. The two organic aerosol types considered are primary lubricating oil (LO) aerosol and secondary aerosol from the α-pinene + O3 reaction (αP). The evolution of the VUV mass spectra for the two aerosol types with temperature are observed to differ dramatically. For LO particles, the spectra exhibit distinct changes with temperature in which the lower m/z peaks, corresponding to compounds with higher vapor pressures, disappear more rapidly than the high m/z peaks. In contrast, the αP aerosol spectrum is essentially unchanged by temperature even though the particles experience significant mass loss due to evaporation. The variations in the LO spectra are found to be quantitatively in agreement with expectations from absorptive partitioning theory whereas the αP spectra suggest that the evaporation of αP derived aerosol appears to not be governed by partitioning theory. We postulate that this difference arises from diffusivity within the αP particles being sufficiently slow that they do not exhibit the expected liquid-like behavior and perhaps exist in a glassy state. To reconcile these observations with decades of aerosol growth measurements, which indicate that OA formation is described by equilibrium partitioning, we present a conceptual model wherein the secondary OA is formed and then rapidly converted from an absorbing form to a non-absorbing form. The results suggest that, although OA growth may be describable by equilibrium partitioning theory, the properties of organic aerosol once formed may differ significantly from the properties determined in the equilibrium framework.
Enhancement and depletion of lower/middle tropospheric ozone in Senegal during pre-monsoon and monsoon periods of summer 2008: observations and model results

During the summer (8 June through 3 September) of 2008, nine ozonesondes are launched from Dakar, Senegal (14.75° N, 17.49° W) to investigate the impact of the Saharan Dust Layer (SAL) on ozone (O3) concentrations in the lower troposphere. Results during June (pre-monsoon period) show a reduction in O3, especially in the 850–700 hPa layer with SAL events. However, O3 concentrations are increased in the 950–900 hPa layer where the peak of the inversion is found and presumably the highest dust concentrations. We use the WRF-CHEM model to explore the causes of elevated O3 concentrations that appear to have a stratospheric contribution. During July and August (monsoon period), with the exception of one SAL outbreak, vertical profiles of O3 are well mixed with concentrations not exceeding 55 ppb between the surface and 550 hPa. In the transition period between 26 June and 2 July lower tropospheric (925–600 hPa) O3 concentrations are likely enhanced by enhanced biogenic NOx emissions from the Saharan desert and Sahelian soils following several rain events on 28 June and 1 July.
Sensitivity studies on the impacts of Tibetan Plateau snowpack pollution on the Asian hydrological cycle and monsoon climate

The Tibetan Plateau (TP) has long been identified to be critical in regulating the Asian monsoon climate and hydrological cycle. In this modeling study a series of numerical experiments with a global climate model are designed to simulate radiative effect of black carbon (BC) and dust in snow, and to assess the relative impacts of anthropogenic CO2 and carbonaceous particles in the atmosphere and snow on the snowpack over the TP and subsequent impacts on the Asian monsoon climate and hydrological cycle. Simulations results show a large BC content in snow over the TP, especially the southern slope. Because of the high aerosol content in snow and large incident solar radiation in the low latitude and high elevation, the TP exhibits the largest surface radiative flux changes induced by aerosols (e.g. BC, Dust) in snow compared to any other snow-covered regions in the world. Simulation results show that the aerosol-induced snow albedo perturbations generate surface radiative flux changes of 5–25 W m−2 during spring, with a maximum in April or May. BC-in-snow increases the surface air temperature by around 1.0 °C averaged over the TP and reduces spring snowpack over the TP more than pre-industrial to present CO2 increase and carbonaceous particles in the atmosphere. As a result, runoff increases during late winter and early spring but decreases during late spring and early summer (i.e. a trend toward earlier melt dates). The snowmelt efficacy, defined as the snowpack reduction per unit degree of warming induced by the forcing agent, is 1–4 times larger for BC-in-snow than CO2 increase during April–July, indicating that BC-in-snow more efficiently accelerates snowmelt because the increased net solar radiation induced by reduced albedo melts the snow more efficiently than snow melt due to warming in the air. The TP also influences the South (SAM) and East (EAM) Asian monsoon through its dynamical and thermal forcing. Simulation results show that during boreal spring aerosols are transported by southwesterly, causing some particles to reach higher altitude and deposit to the snowpack over the TP. While BC and Organic Matter (OM) in the atmosphere directly absorb sunlight and warm the air, the darkened snow surface polluted by BC absorbs more solar radiation and increases the skin temperature, which warms the air above through sensible heat flux. Both effects enhance the upward motion of air and spur deep convection along the TP during the pre-monsoon season, resulting in earlier onset of the SAM and increase of moisture, cloudiness and convective precipitation over northern India. BC-in-snow has a more significant impact on the EAM in July than CO2 increase and carbonaceous particles in the atmosphere. Contributed by the significant increase of both sensible heat flux associated with the warm skin temperature and latent heat flux associated with increased soil moisture with long memory, the role of the TP as a heat pump is elevated from spring through summer as the land-sea thermal contrast increases to strengthen the EAM. As a result, both southern China and northern China become wetter, but central China (i.e. Yangtze River Basin) becomes drier – a near-zonal anomaly pattern that is consistent with the dominant mode of precipitation variability in East Asia. The snow impurity effects reported in this study likely represent some upper limits as snowpack is remarkably overestimated over the TP due to excessive precipitation. Improving the simulation of precipitation and snowpack will be important for improved estimates of the effects of snowpack pollution in future work.