Items

Advanced search

Secondary aerosol formation from stress-induced biogenic emissions and possible climate feedbacks

Atmospheric aerosols impact climate by scattering and absorbing solar radiation and by acting as ice and cloud condensation nuclei. Biogenic secondary organic aerosols (BSOAs) comprise an important component of atmospheric aerosols. Biogenic volatile organic compounds (BVOCs) emitted by vegetation are the source of BSOAs. Pathogens and insect attacks, heat waves and droughts can induce stress to plants that may impact their BVOC emissions, and hence the yield and type of formed BSOAs, and possibly their climatic effects. This raises questions of whether stress-induced changes in BSOA formation may attenuate or amplify effects of climate change. In this study we assess the potential impact of stress-induced BVOC emissions on BSOA formation for tree species typical for mixed deciduous and Boreal Eurasian forests. We studied the photochemical BSOA formation for plants infested by aphids in a laboratory setup under well-controlled conditions and applied in addition heat and drought stress. The results indicate that stress conditions substantially modify BSOA formation and yield. Stress-induced emissions of sesquiterpenes, methyl salicylate, and C17-BVOCs increase BSOA yields. Mixtures including these compounds exhibit BSOA yields between 17 and 33%, significantly higher than mixtures containing mainly monoterpenes (4–6% yield). Green leaf volatiles suppress SOA formation, presumably by scavenging OH, similar to isoprene. By classifying emission types, stressors and BSOA formation potential, we discuss possible climatic feedbacks regarding aerosol effects. We conclude that stress situations for plants due to climate change should be considered in climate–vegetation feedback mechanisms.
Chemical insights, explicit chemistry, and yields of secondary organic aerosol from OH radical oxidation of methylglyoxal and glyoxal in the aqueous phase

Atmospherically abundant, volatile water-soluble organic compounds formed through gas-phase chemistry (e.g., glyoxal (C2), methylglyoxal (C3), and acetic acid) have great potential to form secondary organic aerosol (SOA) via aqueous chemistry in clouds, fogs, and wet aerosols. This paper (1) provides chemical insights into aqueous-phase OH-radical-initiated reactions leading to SOA formation from methylglyoxal and (2) uses this and a previously published glyoxal mechanism (Lim et al., 2010) to provide SOA yields for use in chemical transport models. Detailed reaction mechanisms including peroxy radical chemistry and a full kinetic model for aqueous photochemistry of acetic acid and methylglyoxal are developed and validated by comparing simulations with the experimental results from previous studies (Tan et al., 2010, 2012). This new methylglyoxal model is then combined with the previous glyoxal model (Lim et al., 2010), and is used to simulate the profiles of products and to estimate SOA yields. At cloud-relevant concentrations (~ 10−6 − ~ 10−3 M; Munger et al., 1995) of glyoxal and methylglyoxal, the major photooxidation products are oxalic acid and pyruvic acid, and simulated SOA yields (by mass) are ~ 120% for glyoxal and ~ 80% for methylglyoxal. During droplet evaporation oligomerization of unreacted methylglyoxal/glyoxal that did not undergo aqueous photooxidation could enhance yields. In wet aerosols, where total dissolved organics are present at much higher concentrations (~ 10 M), the major oxidation products are oligomers formed via organic radical–radical reactions, and simulated SOA yields (by mass) are ~ 90% for both glyoxal and methylglyoxal. Non-radical reactions (e.g., with ammonium) could enhance yields.
VOC emissions, evolutions and contributions to SOA formation at a receptor site in eastern China

Volatile organic compounds (VOCs) were measured by two online instruments (GC-FID/MS and PTR-MS) at a receptor site on Changdao Island (37.99° N, 120.70° E) in eastern China. Reaction with OH radical dominated chemical losses of most VOC species during the Changdao campaign. A photochemical-age-based parameterization method is used to calculate VOC emission ratios and to quantify the evolution of ambient VOCs. The calculated emission ratios of most hydrocarbons agree well with those obtained from emission inventory data, but determined emission ratios of oxygenated VOCs (OVOCs) are significantly higher than those from emission inventory data. The photochemical-age-based parameterization method is also used to investigate primary emissions and secondary formation of organic aerosol. The primary emission ratio of organic aerosol (OA) to CO is determined to be 14.9 μg m−3 ppm−1, and secondary organic aeorosols (SOA) are produced at an enhancement ratio of 18.8 μg m−3 ppm−1 to CO after 50 h of photochemical processing in the atmosphere. SOA formation is significantly higher than the level determined from VOC oxidation under both high-NOx (2.0 μg m−3 ppm−1 CO) and low-NOx conditions (6.5 μg m−3 ppm−1 CO). Polycyclic aromatic hydrocarbons (PAHs) and higher alkanes (> C10) account for as high as 17.4% of SOA formation, which suggests semi-volatile organic compounds (SVOCs) may be a large contributor to SOA formation during the Changdao campaign. The SOA formation potential of primary VOC emissions determined from field campaigns in Beijing and Pearl River Delta (PRD) is lower than the measured SOA levels reported in the two regions, indicating SOA formation is also beyond explainable by VOC oxidation in the two city clusters.
Corrigendum to "Dimethylsulphide (DMS) emissionsfrom the West Pacific Ocean: a potential marine source for stratospheric sulphur?" published in Atmos. Chem. Phys., 13, 8427–8437, 2013
Kinetic study of esterification of sulfuric acid with alcohols in aerosol bulk phase

In this study, we hypothesize that the formation of organosulfates through the reactions between sulfuric acid and alcohols in the aerosol bulk phase is more efficient than that in solution chemistry. To prove this hypothesis, the kinetics of the organosulfate formation was investigated for both aliphatic alcohol with single OH group (e.g., 1-heptanol) and the multialcohols ranging from semivolatiles (e.g., hydrated-glyoxal and glycerol) to nonvolatiles (e.g., sucrose) using analytical techniques directly monitoring aerosol bulk phase. Both the forward (k1) and the backward (k−1) reaction rate constants of organosulfate formation via the particle phase esterification of 1-heptanol with sulfuric acid were estimated using a Fourier Transform Infrared (FTIR) spectrometer equipped with a flow chamber under varying humidities. Both k1 and k−1 are in orders of 10−3 L mol−1 min−1, which are three orders of magnitude higher than the reported values obtained in solution chemistry. The formation of organosulfate in the H2SO4 aerosol internally mixed with multialcohols was studied by measuring the proton concentration of the aerosol collected on the filter using a newly developed Colorimetry integrated with a Reflectance UV-Visible spectrometer (C-RUV). The formation of organosulfate significantly decreases aerosol acidity due to the transformation of H2SO4 into dialkylsulfates. The forward reaction rate constants for the dialkylsulfate formation in the multialcohol-H2SO4 aerosols were also three orders of magnitude greater than the reported values in solution chemistry. The water content (MH2O) in the multialcohol-H2SO4 particle was monitored using the FTIR spectrometer. A large reduction of MH2O accords with the high yield of organosulfate in aerosol. Based on this study, we conclude that organosulfate formation in atmospheric aerosol, where both alcohols and sulfuric acid are found together, is significant.
The magnitude and causes of uncertainty in global model simulations of cloud condensation nuclei

Aerosol–cloud interaction effects are a major source of uncertainty in climate models so it is important to quantify the sources of uncertainty and thereby direct research efforts. However, the computational expense of global aerosol models has prevented a full statistical analysis of their outputs. Here we perform a variance-based analysis of a global 3-D aerosol microphysics model to quantify the magnitude and leading causes of parametric uncertainty in model-estimated present-day concentrations of cloud condensation nuclei (CCN). Twenty-eight model parameters covering essentially all important aerosol processes, emissions and representation of aerosol size distributions were defined based on expert elicitation. An uncertainty analysis was then performed based on a Monte Carlo-type sampling of an emulator built for each model grid cell. The standard deviation around the mean CCN varies globally between about ±30% over some marine regions to ±40–100% over most land areas and high latitudes, implying that aerosol processes and emissions are likely to be a significant source of uncertainty in model simulations of aerosol–cloud effects on climate. Among the most important contributors to CCN uncertainty are the sizes of emitted primary particles, including carbonaceous combustion particles from wildfires, biomass burning and fossil fuel use, as well as sulfate particles formed on sub-grid scales. Emissions of carbonaceous combustion particles affect CCN uncertainty more than sulfur emissions. Aerosol emission-related parameters dominate the uncertainty close to sources, while uncertainty in aerosol microphysical processes becomes increasingly important in remote regions, being dominated by deposition and aerosol sulfate formation during cloud-processing. The results lead to several recommendations for research that would result in improved modelling of cloud–active aerosol on a global scale.
Satellite-based estimate of aerosol direct radiative effect over the South-East Atlantic

The net effect of aerosol Direct Radiative Forcing (DRF) is the balance between the scattering effect that reflects solar radiation back to space (cooling), and the absorption that decreases the reflected sunlight (warming). The amplitude of these two effects and their balance depends on the aerosol load, its absorptivity, the cloud fraction and the respective position of aerosol and cloud layers. In this study, we use the information provided by CALIOP (CALIPSO satellite) and MODIS (AQUA satellite) instruments as input data to a Rapid Radiative Transfer Model (RRTM) and quantify the shortwave (SW) aerosol direct atmospheric forcing, over the South-East Atlantic. The combination of the passive and active measurements allows estimates of the horizontal and vertical distributions of the aerosol and cloud parameters. We use a parametrization of the Single Scattering Albedo (SSA) based on the satellite-derived Angstrom coefficient. The South East Atlantic is a particular region, where bright stratocumulus clouds are often topped by absorbing smoke particles. Results from radiative transfer simulations confirm the similar amplitude of the cooling effect, due to light scattering by the aerosols, and the warming effect, due to the absorption by the same particles. Over six years of satellite retrievals, from 2005 to 2010, the South-East Atlantic all-sky SW DRF is −0.03 W m−2, with a spatial standard deviation of 8.03 W m−2. In good agreement with previous estimates, statistics show that a cloud fraction larger than 0.5 is generally associated with positive all-sky DRF. In case of cloudy-sky and aerosol located only above the cloud top, a SSA larger than 0.91 and cloud optical thickness larger than 4 can be considered as threshold values, beyond which the resulting radiative forcing becomes positive.
Black carbon in the Arctic: the underestimated role of gas flaring and residential combustion emissions

Arctic haze is a seasonal phenomenon with high concentrations of accumulation-mode aerosols occurring in the Arctic in winter and early spring. Chemistry transport models and climate chemistry models struggle to reproduce this phenomenon, and this has recently prompted changes in aerosol removal schemes to remedy the modeling problems. In this paper, we show that shortcomings in current emission data sets are at least as important. We perform a 3 yr model simulation of black carbon (BC) with the Lagrangian particle dispersion model FLEXPART. The model is driven with a new emission data set ("ECLIPSE emissions") which includes emissions from gas flaring. While gas flaring is estimated to contribute less than 3% of global BC emissions in this data set, flaring dominates the estimated BC emissions in the Arctic (north of 66° N). Putting these emissions into our model, we find that flaring contributes 42% to the annual mean BC surface concentrations in the Arctic. In March, flaring even accounts for 52% of all Arctic BC near the surface. Most of the flaring BC remains close to the surface in the Arctic, so that the flaring contribution to BC in the middle and upper troposphere is small. Another important factor determining simulated BC concentrations is the seasonal variation of BC emissions from residential combustion (often also called domestic combustion, which is used synonymously in this paper). We have calculated daily residential combustion emissions using the heating degree day (HDD) concept based on ambient air temperature and compare results from model simulations using emissions with daily, monthly and annual time resolution. In January, the Arctic-mean surface concentrations of BC due to residential combustion emissions are 150% higher when using daily emissions than when using annually constant emissions. While there are concentration reductions in summer, they are smaller than the winter increases, leading to a systematic increase of annual mean Arctic BC surface concentrations due to residential combustion by 68% when using daily emissions. A large part (93%) of this systematic increase can be captured also when using monthly emissions; the increase is compensated by a decreased BC burden at lower latitudes. In a comparison with BC measurements at six Arctic stations, we find that using daily-varying residential combustion emissions and introducing gas flaring emissions leads to large improvements of the simulated Arctic BC, both in terms of mean concentration levels and simulated seasonality. Case studies based on BC and carbon monoxide (CO) measurements from the Zeppelin observatory appear to confirm flaring as an important BC source that can produce pollution plumes in the Arctic with a high BC / CO enhancement ratio, as expected for this source type. BC measurements taken during a research ship cruise in the White, Barents and Kara seas north of the region with strong flaring emissions reveal very high concentrations of the order of 200–400 ng m−3. The model underestimates these concentrations substantially, which indicates that the flaring emissions (and probably also other emissions in northern Siberia) are rather under- than overestimated in our emission data set. Our results suggest that it may not be "vertical transport that is too strong or scavenging rates that are too low" and "opposite biases in these processes" in the Arctic and elsewhere in current aerosol models, as suggested in a recent review article (Bond et al., Bounding the role of black carbon in the climate system: a scientific assessment, J. Geophys. Res., 2013), but missing emission sources and lacking time resolution of the emission data that are causing opposite model biases in simulated BC concentrations in the Arctic and in the mid-latitudes.
Atmospheric nitric oxide and ozone at the WAIS Divide deep coring site: a discussion of local sources and transport in West Antarctica

The first measurements of atmospheric nitric oxide (NO) along with observations of ozone (O3), hydroperoxides (H2O2 and MHP) and snow nitrate (NO3–) on the West Antarctic Ice Sheet (WAIS) were carried out at the WAIS Divide deep ice-coring site between 10 December 2008 and 11 January 2009. Average ±1σ mixing ratios of NO were 19 ± 31 pptv and confirmed prior model estimates for the summer boundary layer above WAIS. Mean ±1σ mixing ratios of O3 of 14 ± 4 ppbv were in the range of previous measurements from overland traverses across WAIS during summer, while average ±1σ concentrations of H2O2 and MHP revealed higher levels with mixing ratios of 743 ± 362 and 519 ± 238 pptv, respectively. An upper limit for daily average NO2 and NO emission fluxes from snow of 8.6 × 108 and 33.9 × 108 molecule cm–2 s–1, respectively, were estimated based on photolysis of measured NO3– and nitrite (NO2–) in the surface snowpack. The resulting high NOx emission flux may explain the little preservation of NO3– in snow (~ 30%) when compared to Summit, Greenland (75–93%). Assuming rapid and complete mixing into the overlying atmosphere, and steady state of NOx, these snow emissions are equivalent to an average (range) production of atmospheric NOx of 30 (21–566) pptv h–1 for a typical atmospheric boundary-layer depth of 250 (354–13) m. These upper bounds indicate that local emissions from the snowpack are a significant source of short-lived nitrogen oxides above the inner WAIS. The net O3 production of 0.8 ppbv day–1 triggered with NO higher than 2 pptv is too small to explain the observed O3 variability. Thus, the origins of the air masses reaching WAIS Divide during this campaign were investigated with a 4-day back-trajectory analysis every 4 h. The resulting 168 back trajectories revealed that in 75% of all runs air originated from the Antarctic coastal slopes (58%) and the inner WAIS (17%). For these air sources O3 levels were on average 13 ± 3 ppbv. The remaining 25% are katabatic outflows from the East Antarctic Plateau above 2500 m. When near-surface air from the East Antarctic Plateau reaches WAIS Divide through a rapid transport of less than 3 days, O3 levels are on average 19 ± 4 ppbv with maximum mixing ratios of 30 ppbv. Episodes of elevated ozone at WAIS Divide are therefore linked to air mass export off the East Antarctic Plateau, demonstrating that outflows from the highly oxidizing summer atmospheric boundary layer in the interior of the continent can episodically raise the mixing ratios of long-lived atmospheric chemical species such as O3 and enhance the oxidative capacity of the atmosphere above WAIS.
Characterization of ultrafine particle number concentration and new particle formation in an urban environment of Taipei, Taiwan

An intensive aerosol characterization experiment was performed at the Taipei Aerosol and Radiation Observatory (TARO, 25.02° N, 121.53° E) in the urban area of Taipei, Taiwan, during July 2012. Number concentration and size distribution of aerosol particles were measured continuously, which were accompanied by concurrent measurements of mass concentration of submicron particles, PM1 (d ≤ 1 μm), and photolysis rate of ozone, J(O1D). The averaged number concentrations of total (Ntotal), accumulation mode (Nacu), Aitken mode (NAitken), and nucleation mode (Nnuc) particles were 13.9 × 103 cm−3, 1.2 × 103 cm−3, 6.1 × 103 cm−3, and 6.6 × 103 cm−3, respectively. Accordingly, the ultrafine particles (UFPs, d ≤ 100 nm) accounted for 91% of the total number concentration of particles measured in this study (10 ≤ d ≤ 429 nm), indicating the importance of UFPs to the air quality and radiation budget in Taipei and its surrounding areas. An averaged Nnuc / NOx ratio of 192.4 cm−3 ppbv−1 was derived from nighttime measurements, which was suggested to be the characteristic of vehicle emissions that contributed to the "urban background" of nucleation mode particles throughout a day. On the contrary, it was found that the number concentration of nucleation mode particles was independent of NOx and could be elevated up to 10 times of the "urban background" levels during daytime, suggesting a substantial amount of nucleation mode particles produced from photochemical processes. Averages (± 1σ) of the diameter growth rate (GR) and formation rate of nucleation mode particles, J10, were 11.9 ± 10.6 nm h−1 and 6.9 ± 3.0 cm−3 s−1, respectively. Consistency in the time series of the nucleation mode particle concentration and the proxy of H2SO4 production, UVB · SO2/CS, for new particle formation (NPF) events suggested that photooxidation of SO2 was likely one of the major mechanisms for the formation of new particles in our study area. Moreover, it was revealed that the particle growth rate correlated exponentially with the photolysis of ozone, implying that the condensable vapors were produced mostly from photooxidation reactions. In addition, this study also revealed that Nnuc exhibited a quadratic relationship with J10. The quadratic relationship was inferred as a result of aerosol dynamics and featured NPF processes in urban areas.