Items

Advanced search

Shortwave direct radiative effects of above-cloud aerosols over global oceans derived from 8 years of CALIOP and MODIS observations

In this paper, we studied the frequency of occurrence and shortwave direct radiative effects (DREs) of above-cloud aerosols (ACAs) over global oceans using 8 years (2007–2014) of collocated CALIOP and MODIS observations. Similar to previous work, we found high ACA occurrence in four regions: southeastern (SE) Atlantic region, where ACAs are mostly light-absorbing aerosols, i.e., smoke and polluted dust according to CALIOP classification, originating from biomass burning over the African Savanna; tropical northeastern (TNE) Atlantic and the Arabian Sea, where ACAs are predominantly windblown dust from the Sahara and Arabian deserts, respectively; and the northwestern (NW) Pacific, where ACAs are mostly transported smoke and polluted dusts from Asian. From radiative transfer simulations based on CALIOP–MODIS observations and a set of the preselected aerosol optical models, we found the DREs of ACAs at the top of atmosphere (TOA) to be positive (i.e., warming) in the SE Atlantic and NW Pacific regions, but negative (i.e., cooling) in the TNE Atlantic Ocean and the Arabian Sea. The cancellation of positive and negative regional DREs results in a global ocean annual mean diurnally averaged cloudy-sky DRE of 0.015 W m−2 (range of −0.03 to 0.06 W m−2) at TOA. The DREs at surface and within the atmosphere are −0.15 W m−2 (range of −0.09 to −0.21 W m−2), and 0.17 W m−2 (range of 0.11 to 0.24 W m−2), respectively. The regional and seasonal mean DREs are much stronger. For example, in the SE Atlantic region, the JJA (July–August) seasonal mean cloudy-sky DRE is about 0.7 W m−2 (range of 0.2 to 1.2 W m−2) at TOA. All our DRE computations are publicly available1. The uncertainty in our DRE computations is mainly caused by the uncertainties in the aerosol optical properties, in particular aerosol absorption, the uncertainties in the CALIOP operational aerosol optical thickness retrieval, and the ignorance of cloud and potential aerosol diurnal cycle. In situ and remotely sensed measurements of ACA from future field campaigns and satellite missions and improved lidar retrieval algorithm, in particular vertical feature masking, would help reduce the uncertainty. 1 <a href="https://drive.google.com/folderview?id=0B6gKx4dgNY0GMVYzcEd0bkZmRmc&usp=sharing" target="_blank">https://drive.google.com/folderview?id=0B6gKx4dgNY0GMVYzcEd0bkZmRmc&usp=sharing</a>
SOA formation from the photooxidation of α-pinene: systematic exploration of the simulation of chamber data

Chemical mechanisms play an important role in simulating the atmospheric chemistry of volatile organic compound oxidation. Comparison of mechanism simulations with laboratory chamber data tests our level of understanding of the prevailing chemistry as well as the dynamic processes occurring in the chamber itself. α-Pinene photooxidation is a well-studied system experimentally, for which detailed chemical mechanisms have been formulated. Here, we present the results of simulating low-NO α-pinene photooxidation experiments conducted in the Caltech chamber with the Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A) under varying concentrations of seed particles and OH levels. Unexpectedly, experiments conducted at low and high OH levels yield the same secondary organic aerosol (SOA) growth, whereas GECKO-A predicts greater SOA growth under high OH levels. SOA formation in the chamber is a result of a competition among the rates of gas-phase oxidation to low-volatility products, wall deposition of these products, and condensation into the aerosol phase. Various processes – such as photolysis of condensed-phase products, particle-phase dimerization, and peroxy radical autoxidation – are explored to rationalize the observations. In order to explain the observed similar SOA growth at different OH levels, we conclude that vapor wall loss in the Caltech chamber is likely of order 10−5 s−1, consistent with previous experimental measurements in that chamber. We find that GECKO-A tends to overpredict the contribution to SOA of later-generation oxidation products under high-OH conditions. Moreover, we propose that autoxidation may alternatively resolve some or all of the measurement–model discrepancy, but this hypothesis cannot be confirmed until more explicit mechanisms are established for α-pinene autoxidation. The key role of the interplay among oxidation rate, product volatility, and vapor–wall deposition in chamber experiments is illustrated.
Climatic impacts of stratospheric geoengineering with sulfate, black carbon and titania injection

In this paper, we examine the potential climatic effects of geoengineering by sulfate, black carbon and titania injection against a baseline RCP8.5 scenario. We use the HadGEM2-CCS model to simulate scenarios in which the top-of-the-atmosphere radiative imbalance due to rising greenhouse gas concentrations is offset by sufficient aerosol injection throughout the 2020–2100 period. We find that the global-mean temperature is effectively maintained at historical levels for the entirety of the period for all three aerosol-injection scenarios, though there is a wide range of side-effects which are discussed in detail. The most prominent conclusion is that although the BC injection rate necessary to produce an equivalent global mean temperature response is much lower, the severity of stratospheric temperature changes (> +70 °C) and precipitation impacts effectively exclude BC from being a viable option for geoengineering. Additionally, while it has been suggested that titania would be an effective particle because of its high scattering efficiency, it also efficiently absorbs solar ultraviolet radiation producing a significant stratospheric warming (> +20 °C). As injection rates and climatic impacts for titania are close to those for sulfate, there appears to be little benefit in terms of climatic influence of using titania when compared to the injection of sulfur dioxide, which has the added benefit of being well-modeled through extensive research that has been carried out on naturally occurring explosive volcanic eruptions.
Temporal consistency of lidar observations during aerosol transport events in the framework of the ChArMEx/ADRIMED campaign at Minorca in June 2013

We performed synergetic daytime and nighttime active and passive remote-sensing observations at Minorca (Balearic Islands, Spain), over more than 3 weeks during the Chemistry-Aerosol Mediterranean Experiment/Aerosol Direct Radiative Effect in the Mediterranean (ChArMEx/ADRIMED) special observation period (SOP 1a, June–July 2013). We characterized the aerosol optical properties and type in the low and middle troposphere using an automated procedure combining Rayleigh–Mie–Raman lidar (355, 387 and 407 nm) with depolarization (355 nm) and AERONET Cimel® sun-photometer data. Results show a high variability due to varying dynamical forcing. The mean column-averaged lidar backscatter-to-extinction ratio (BER) was close to 0.024 sr−1 (lidar ratio of ∼ 41.7 sr), with a large dispersion of ±33 % over the whole observation period due to changing atmospheric transport regimes and aerosol sources. The ground-based remote-sensing measurements, coupled with satellite observations, allowed the documentation of (i) dust particles up to 5 km (above sea level) in altitude originating from Morocco and Algeria from 15 to 18 June with a peak in aerosol optical thickness (AOT) of 0.25 ± 0.05 at 355 nm, (ii) a long-range transport of biomass burning aerosol (AOT  =  0.18 ± 0.16) related to North American forest fires detected from 26 to 28 June 2013 by the lidar between 2 and 7 km and (iii) mixture of local sources including marine aerosol particles and pollution from Spain. During the biomass burning event, the high value of the particle depolarization ratio (8–14 %) may imply the presence of dust-like particles mixed with the biomass burning aerosols in the mid-troposphere. For the field campaign period, we also show linearity with SEVIRI retrievals of the aerosol optical thickness despite 35 % relative bias, which is discussed as a function of aerosol type.
Global dimming and urbanization: did stronger negative SSR trends collocate with regions of population growth?

Global dimming refers to the decrease in surface solar radiation (SSR) observed from the 1960s to the 1980s at different measurement sites all around the world. It is under debate whether anthropogenic aerosols emitted from urban areas close to the measurement sites are mainly responsible for the dimming. In order to assess this urbanization impact on SSR, we use spatially explicit population density data of 0.08° resolution to construct population indices (PI) at 157 high data quality sites. Our study extends previous population-based studies by incorporating distance-weighting as a simple aerosol diffusion model. We measured urbanization in the surrounding of a site as the PI change from 1960 to 1990 and found no negative correlation with the corresponding SSR trends from 1964 to 1989 for the 92 sites in Europe and Japan. For the 39 sites in China the correlation coefficients are significant at the 5 % level and reach around −0.35, while for the 26 remaining Asian, mostly Russian sites the correlation coefficients reach around −0.55 at the 1 % significance level. Results are similar, when the absolute levels of PIs are taken as an indicator for urbanization. Our findings call into question the existence of an urbanization effect for the sites in Europe and Japan, while such an effect cannot be ruled out for the sites in Asia, especially in Russia.
Estimates of free-tropospheric NO2 and HCHO mixing ratios derived from high-altitude mountain MAX-DOAS observations at midlatitudes and in the tropics

In this study, mixing ratios of NO2 (XNO2) and HCHO (XHCHO) in the free troposphere are derived from two multi-axis differential optical absorption spectroscopy (MAX-DOAS) data sets collected at Zugspitze (2650 m a.s.l., Germany) and Pico Espejo (4765 m a.s.l., Venezuela). The estimation of NO2 and HCHO mixing ratios is based on the modified geometrical approach, which assumes a single-scattering geometry and a scattering point altitude close to the instrument altitude. Firstly, the horizontal optical path length (hOPL) is obtained from O4 differential slant column densities (DSCDs) in the horizontal (0°) and vertical (90°) viewing directions. Secondly, XNO2 and XHCHO are estimated from the NO2 and HCHO DSCDs at the 0° and 90° viewing directions and averaged along the obtained hOPLs. As the MAX-DOAS instrument was performing measurements in the ultraviolet region, wavelength ranges of 346–372 and 338–357 nm are selected for the DOAS analysis to retrieve NO2 and HCHO DSCDs, respectively. In order to compare the measured O4 DSCDs and moreover to perform some sensitivity tests, the radiative transfer model SCIATRAN with adapted altitude settings for mountainous terrain is operated to simulate synthetic spectra, on which the DOAS analysis is also applied. The overall agreement between measured and synthetic O4 DSCDs is better for the higher Pico Espejo station than for Zugspitze. Further sensitivity analysis shows that a change in surface albedo (from 0.05 to 0.7) can influence the O4 DSCDs, with a larger absolute difference observed for the horizontal viewing direction. Consequently, the hOPL can vary by about 5 % throughout the season, for example when winter snow cover fully disappears in summer. Typical values of hOPLs during clear-sky conditions are 19 km (14 km) at Zugspitze and 34 km (26.5 km) at Pico Espejo when using the 346–372 (338–357 nm) fitting window. The estimated monthly values of XNO2 (XHCHO), averaged over these hOPLs during clear-sky conditions, are in the range of 60–100 ppt (500–950 ppt) at Zugspitze and 8.5–15.5 ppt (255–385 ppt) at Pico Espejo. Interestingly, multi-year-averaged monthly means of XNO2 and XHCHO increase towards the end of the dry season at the Pico Espejo site, suggesting that both trace gases are frequently lifted above the boundary layer as a result of South American biomass burning.
Urban stress-induced biogenic VOC emissions and SOA-forming potentials in Beijing

Trees can significantly impact the urban air chemistry by the uptake and emission of reactive biogenic volatile organic compounds (BVOCs), which are involved in ozone and particle formation. Here we present the emission potentials of "constitutive" (cBVOCs) and "stress-induced" BVOCs (sBVOCs) from the dominant broadleaf woody plant species in the megacity of Beijing. Based on the municipal tree census and cuvette BVOC measurements on leaf level, we built an inventory of BVOC emissions, and assessed the potential impact of BVOCs on secondary organic aerosol (SOA) formation in 2005 and 2010, i.e., before and after realizing the large tree-planting program for the 2008 Olympic Games. We found that sBVOCs, such as fatty acid derivatives, benzenoids, and sesquiterpenes, constituted a significant fraction ( ∼  40 %) of the total annual BVOC emissions, and we estimated that the overall annual BVOC budget may have doubled from ∼  4.8  ×  109 g C year−1 in 2005 to ∼  10.3  ×  109 g C year−1 in 2010 due to the increase in urban greening, while at the same time the emission of anthropogenic VOCs (AVOCs) decreased by 24 %. Based on the BVOC emission assessment, we estimated the biological impact on SOA mass formation potential in Beijing. Constitutive and stress-induced BVOCs might produce similar amounts of secondary aerosol in Beijing. However, the main contributors of SOA-mass formations originated from anthropogenic sources (> 90 %). This study demonstrates the general importance to include sBVOCs when studying BVOC emissions. Although the main problems regarding air quality in Beijing still originate from anthropogenic activities, the present survey suggests that in urban plantation programs, the selection of low-emitting plant species has some potential beneficial effects on urban air quality.
In situ secondary organic aerosol formation from ambient pine forest air using an oxidation flow reactor

An oxidation flow reactor (OFR) is a vessel inside which the concentration of a chosen oxidant can be increased for the purpose of studying SOA formation and aging by that oxidant. During the BEACHON-RoMBAS (Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H2O, Organics & Nitrogen–Rocky Mountain Biogenic Aerosol Study) field campaign, ambient pine forest air was oxidized by OH radicals in an OFR to measure the amount of SOA that could be formed from the real mix of ambient SOA precursor gases, and how that amount changed with time as precursors changed. High OH concentrations and short residence times allowed for semicontinuous cycling through a large range of OH exposures ranging from hours to weeks of equivalent (eq.) atmospheric aging. A simple model is derived and used to account for the relative timescales of condensation of low-volatility organic compounds (LVOCs) onto particles; condensational loss to the walls; and further reaction to produce volatile, non-condensing fragmentation products. More SOA production was observed in the OFR at nighttime (average 3 µg m−3 when LVOC fate corrected) compared to daytime (average 0.9 µg m−3 when LVOC fate corrected), with maximum formation observed at 0.4–1.5 eq. days of photochemical aging. SOA formation followed a similar diurnal pattern to monoterpenes, sesquiterpenes, and toluene+p-cymene concentrations, including a substantial increase just after sunrise at 07:00 local time. Higher photochemical aging (> 10 eq. days) led to a decrease in new SOA formation and a loss of preexisting OA due to heterogeneous oxidation followed by fragmentation and volatilization. When comparing two different commonly used methods of OH production in OFRs (OFR185 and OFR254-70), similar amounts of SOA formation were observed. We recommend the OFR185 mode for future forest studies. Concurrent gas-phase measurements of air after OH oxidation illustrate the decay of primary VOCs, production of small oxidized organic compounds, and net production at lower ages followed by net consumption of terpenoid oxidation products as photochemical age increased. New particle formation was observed in the reactor after oxidation, especially during times when precursor gas concentrations and SOA formation were largest. Approximately 4.4 times more SOA was formed in the reactor from OH oxidation than could be explained by the VOCs measured in ambient air. To our knowledge this is the first time that this has been shown when comparing VOC concentrations with SOA formation measured at the same time, rather than comparing measurements made at different times. Several recently developed instruments have quantified ambient semivolatile and intermediate-volatility organic compounds (S/IVOCs) that were not detected by a proton transfer reaction time-of-flight mass spectrometer (PTR-TOF-MS). An SOA yield of 18–58 % from those compounds can explain the observed SOA formation. S/IVOCs were the only pool of gas-phase carbon that was large enough to explain the observed SOA formation. This work suggests that these typically unmeasured gases play a substantial role in ambient SOA formation. Our results allow ruling out condensation sticking coefficients much lower than 1. These measurements help clarify the magnitude of potential SOA formation from OH oxidation in forested environments and demonstrate methods for interpretation of ambient OFR measurements.
Source apportionment and dynamic changes of carbonaceous aerosols during the haze bloom-decay process in China based on radiocarbon and organic molecular tracers

Fine carbonaceous aerosols (CAs) is the key factor influencing the currently filthy air in megacities in China, yet few studies simultaneously focus on the origins of different CAs species using specific and powerful source tracers. Here, we present a detailed source apportionment for various CAs fractions, including organic carbon (OC), water-soluble OC (WSOC), water-insoluble OC (WIOC), elemental carbon (EC) and secondary OC (SOC) in the largest cities of North (Beijing, BJ) and South China (Guangzhou, GZ), using the measurements of radiocarbon and anhydrosugars. Results show that non-fossil fuel sources such as biomass burning and biogenic emission make a significant contribution to the total CAs in Chinese megacities: 56 ± 4 in BJ and 46 ± 5 % in GZ, respectively. The relative contributions of primary fossil carbon from coal and liquid petroleum combustions, primary non-fossil carbon and secondary organic carbon (SOC) to total carbon are 19, 28 and 54 % in BJ, and 40, 15 and 46 % in GZ, respectively. Non-fossil fuel sources account for 52 in BJ and 71 % in GZ of SOC, respectively. These results suggest that biomass burning has a greater influence on regional particulate air pollution in North China than in South China. We observed an unabridged haze bloom-decay process in South China, which illustrates that both primary and secondary matter from fossil sources played a key role in the blooming phase of the pollution episode, while haze phase is predominantly driven by fossil-derived secondary organic matter and nitrate.
Sensitivity of modeled atmospheric nitrogen species and nitrogen deposition to variations in sea salt emissions in the North Sea and Baltic Sea regions

Coarse sea salt particles are emitted ubiquitously from the ocean surface by wave-breaking and bubble-bursting processes. These particles impact the atmospheric chemistry by affecting the condensation of gas-phase species and, thus, indirectly the nucleation of new fine particles, particularly in regions with significant air pollution. In this study, atmospheric particle concentrations are modeled for the North Sea and Baltic Sea regions in northwestern Europe using the Community Multiscale Air Quality (CMAQ) modeling system and are compared to European Monitoring and Evaluation Programme (EMEP) measurement data. The sea salt emission module is extended by a salinity-dependent scaling of the sea salt emissions because the salinity in large parts of the Baltic Sea is very low, which leads to considerably lower sea salt mass emissions compared to other oceanic regions. The resulting improvement in predicted sea salt concentrations is assessed. The contribution of surf zone emissions is considered separately. Additionally, the impacts of sea salt particles on atmospheric nitrate and ammonium concentrations and on nitrogen deposition are evaluated. The comparisons with observational data show that sea salt concentrations are commonly overestimated at coastal stations and partly underestimated farther inland. The introduced salinity scaling improves the predicted Baltic Sea sea salt concentrations considerably. The dates of measured peak concentrations are appropriately reproduced by the model. The impact of surf zone emissions is negligible in both seas. Nevertheless, they might be relevant because surf zone emissions were cut at an upper threshold in this study. Deactivating sea salt leads to minor increases in NH3 +  NH4+ and HNO3 +  NO3− and a decrease in NO3− concentrations. However, the overall effect on NH3 +  NH4+ and HNO3 +  NO3− concentrations is smaller than the deviation from the measurements. Nitrogen wet deposition is underestimated by the model at most stations. In coastal regions, the total nitrogen deposition (wet and dry) is considerably affected by sea salt particles. Approximately 3–7 % of atmospheric nitrogen deposition into the North Sea is caused by sea salt particles. The contribution is lower in the Baltic Sea region. The stations in the EMEP network provide a solid basis for model evaluation and validation. However, for a more detailed analysis of the impact of sea salt particles on atmospheric nitrogen species, size-resolved measurements of Na+, NH4+, and NO3− are needed.