ALBERT

Description: Influence of biomass burning on CCN number and hygroscopicity during summertime in the eastern Mediterranean Atmospheric Chemistry and Physics Discussions, 15, 21539-21582, 2015 Author(s): A. Bougiatioti, S. Bezantakos, I. Stavroulas, N. Kalivitis, P. Kokkalis, G. Biskos, N. Mihalopoulos, A. Papayannis, and A. Nenes This study investigates the CCN activity and hygroscopic properties of particles influenced by biomass burning in the eastern Mediterranean. Air masses sampled were subject to a range of atmospheric processing (several hours up to 3 days). Values of the hygroscopicity parameter, κ, were derived from cloud condensation nuclei (CCN) measurements and a Hygroscopic Tandem Differential Mobility Analyzer (HTDMA). An Aerosol Chemical Speciation Monitor (ACSM) was also used to determine the chemical composition and mass concentration of non-refractory components of the submicron aerosol fraction. During fire events, the increased organic content (and lower inorganic fraction) of the aerosol decreases the hygroscopicity parameter, κ, for all particle sizes. The reason, however, for this decrease was not the same for all size modes; smaller particle sizes appeared to be richer in less hygroscopic, less CCN-active components due to coagulation processes while larger particles become less hygroscopic during the biomass burning events due to condensation of less hygroscopic gaseous compounds. In addition, smaller particles exhibited considerable chemical dispersion (where hygroscopicity varied up to 100 % for particles of same size); larger particles, however, exhibited considerably less dispersion owing to the effects of aging and retained high levels of CCN activity. These conclusions are further supported by the observed mixing state determined by the HTDMA measurements. ACSM measurements indicate that the bulk composition reflects the hygroscopicity and chemical nature of the largest particles and a large fraction of the CCN concentrations sampled. Based on Positive Matrix Factorization (PMF) analysis of the organic ACSM spectra, CCN concentrations follow a similar trend with the BBOA component, with enhancements of CCN in biomass burning plumes ranging between 65 and 150 %, for supersaturations ranging between 0.2 and 0.7 %. Using multilinear regression, we determine the hygroscopicity of the prime organic aerosol components (BBOA, OOA-BB and OOA); it is found that the total organic hygroscopicity is very close to the inferred hygroscopicity of the oxygenated organic aerosol components. Finally, the transformation of freshly-emitted biomass burning (BBOA) to more oxidized organic aerosol (OOA-BB) can result in a two-fold increase of the inferred organic hygroscopicity. Almost 10 % of the total aerosol hygroscopicity is related to the two biomass burning components (BBOA and OOA-BB), which in turn contribute almost 35 % to the fine-particle organic water of the aerosol. This is important as organic water can contribute to the atmospheric chemistry and the direct radiative forcing.

Description: Measurement-based direct radiative effect by brown carbon over Indo-Gangetic Plain Atmospheric Chemistry and Physics Discussions, 15, 21583-21606, 2015 Author(s): A. Arola, G. L. Schuster, M. R. A. Pitkänen, O. Dubovik, H. Kokkola, A. V. Lindfors, T. Mielonen, T. Raatikainen, S. Romakkaniemi, S. N. Tripathi, and H. Lihavainen The importance of light absorbing organic aerosols, often called brown carbon (BrC), has become evident in recent years. However, there are relatively few measurement-based estimates for the direct radiative effect of BrC so far. In those earlier studies, the AErosol RObotic NETwork (AERONET) measured Aerosol Absorption Optical Depth (AAOD) and Absorption Angstrom Exponent (AAE) have been exploited. However, these two pieces of information are clearly not sufficient to separate properly carbonaceous aerosols from dust, while imaginary indices of refraction would contain more and better justified information for this purpose. This is first time that the direct radiative effect (DRE) of BrC is estimated by exploiting the AERONET-retrieved imaginary indices. We estimated it for four sites in Indo-Gangetic Plain (IGP), Karachi, Lahore, Kanpur and Gandhi College. We found a distinct seasonality, which was generally similar among all the sites, but with slightly different strengths. The monthly warming effect up to 0.5 W m -2 takes place during spring season. On the other hand, BrC results in overall cooling effect in the winter season, which can reach levels close to −1W m -2 . We then estimated similarly also DRE of black carbon and total aerosol, in order to assess the relative significance of BrC radiative effect in the radiative effects of other components. Even though BrC impact seems minor in this context, we demonstrated that it is not insignificant and moreover that it is crucial to perform spectrally resolved radiative transfer calculations to obtain good estimates for DRE of BrC.

Description: Size distribution and optical properties of mineral dust aerosols transported in the western Mediterranean Atmospheric Chemistry and Physics Discussions, 15, 21607-21669, 2015 Author(s): C. Denjean, F. Cassola, A. Mazzino, S. Triquet, S. Chevaillier, N. Grand, T. Bourrianne, G. Momboisse, K. Sellegri, A. Schwarzenbock, E. Freney, M. Mallet, and P. Formenti This study presents in situ aircraft measurements of Saharan mineral dust transported over the western Mediterranean basin in June–July 2013 during the ChArMEx/ADRIMED (the Chemistry-Aerosol Mediterranean Experiment/Aerosol Direct Radiative Impact on the regional climate in the MEDiterranean region) airborne campaign. Dust events differing in terms of source region (Algeria, Tunisia and Morocco), time of tranport (1–5 days) and height of transport were sampled. Mineral dust were transported above the marine boundary layer, which conversely was dominated by pollution and marine aerosols. The dust vertical structure was extremely variable and characterized by either a single layer or a more complex and stratified structure with layers originating from different source regions. Mixing of mineral dust with pollution particles was observed depending on the height of transport of the dust layers. Dust layers carried higher concentration of pollution particles at intermediate altitude (1–3 km) than at elevated altitude (〉 3 km), resulting in scattering Angstrom exponent up to 2.2 within the intermediate altitude. However, the optical properties of the dust plumes remained practically unchanged with respect to values previously measured over source regions, regardless of the altitude. Moderate light absorption of the dust plumes was observed with values of aerosol single scattering albedo at 530 nm ranging from 0.90 to 1.00 ± 0.04. Concurrent calculations from the aerosol chemical composition revealed a negligible contribution of pollution particles to the absorption properties of the dust plumes that was due to a low contribution of refractory black carbon in regards to the fraction of dust and sulfate particles. This suggests that, even in the presence of moderate pollution, likely a persistent feature in the Mediterranean, the optical properties of the dust plumes could be assimilated to those of native dust in radiative transfer simulations, modeling studies and satellite retrievals over the Mediterranean. Measurements also showed that the coarse mode of mineral dust was conserved even after 5 days of transport in the Mediterranean, which contrasts with the gravitational depletion of large particles observed during the transport of dust plumes over the Atlantic. Simulations with the WRF mesoscale meteorological model highlighted a strong vertical turbulence within the dust layers that could prevent deposition of large particles during their atmospheric transport. This has important implications for the dust radiative effects due to surface dimming, atmospheric heating and cloud formation. The results presented here add to the observational dataset necessary for evaluating the role of mineral dust on the regional climate and rainfall patterns in the western Mediterranean basin.

Description: Identification of particulate organosulfates in three megacities at the middle and lower reaches of the Yangtze River Atmospheric Chemistry and Physics Discussions, 15, 21415-21448, 2015 Author(s): X. K. Wang, S. Rossignol, Y. Ma, L. Yao, M. Y. Wang, J. M. Chen, C. George, and L. Wang PM 2.5 filter samples have been collected in three megacities i.e., Wuhan (WH), Nanjing (NJ), and Shanghai (SH) at the middle and lower reaches of the Yangtze River, respectively. Analysis of those samples using an ultra-high performance liquid chromatography (UHPLC) coupled to an orbitrap mass spectrometer (MS) allowed detection of about two hundred particulate organosulfates (OSs), including dozens of nitrooxy-organosulfates, at each location. While aliphatic OSs represented more than 78 % of the detected OSs at the three locations, aromatic OSs were much less abundant. OSs with two to four isomers accounted for about 50 % of the total OSs on average in these megacities, and the percentage of OSs with six and more isomers in WH was more significant than those in SH and NJ. The average molecular weight, and the degrees of oxidation and saturation of OSs in the WH summer samples were greater than those in WH winter samples. In SH, the average molecular weight and the degree of oxidation of OSs in summer samples were greater than those in winter samples, but the degree of saturation was similar between the two seasons. In summer, the average molecular weight, and the degrees of oxidation and unsaturation of OSs were smallest in WH among the three cities. Between NJ and SH, the average molecular weight and the degree of saturation of OSs were close and the degree of oxidation of OSs in NJ was smaller. Kendrick mass defect diagrams and Van Krevelen diagrams indicated that the characteristics of identified OSs between in NJ and in SH shared better similarity. In addition, the identity and abundance of OSs in SH showed clear seasonal and diurnal variations. OSs in summer were more abundant than they were in winter due to stronger photochemical reactions in summer. The relative abundance of OSs at night was greater than that in the daytime and more nitrooxy-OSs existed at night, probably because of active NO 3 radical chemistry at night. In SH summer samples, OSs with 5 and 10 carbons (C 5 and C 10 ) were the most abundant, indicating the importance of isoprene and monoterpenes as precursors of OSs, whereas the relative abundances of OSs with 8, 9, and more than 14 carbons (C 8 , C 9 , and C 14+ ) were also high in SH winter samples, urging the need to further understand the precursors of OSs.

Description: The tropopause inversion layer in baroclinic life cycles experiments: the role of diabatic and mixing processes Atmospheric Chemistry and Physics Discussions, 15, 21495-21537, 2015 Author(s): D. Kunkel, P. Hoor, and V. Wirth Recent studies on the formation of a quasi-permanent layer of enhanced static stability above the thermal tropopause revealed the contributions of dynamical and radiative processes. Dry dynamics lead to the evolution of a tropopause inversion layer (TIL) which is, however, too weak compared to observations and thus diabatic contributions are required. In this study we aim to assess the importance of diabatic as well as mixing processes in the understanding of TIL formation at midlatitudes. The non-hydrostatic model COSMO is applied in an idealized mid-latitude channel configuration to simulate baroclinic life cycles. The effect of individual diabatic, i.e. related to humidity and radiation, and turbulent processes is studied first to estimate the additional contribution of these processes to dry dynamics. In a second step these processes are stepwise included in the model to increase the complexity and finally estimate the relative importance of each process. The results suggest that including turbulence leads to a weaker TIL than in a dry reference simulation. In contrast, the TIL evolves stronger when radiation is included but the temporal occurrence is still comparable to the reference. Using various cloud schemes in the model shows that latent heat release and consecutive increased vertical motions foster an earlier and stronger appearance of the TIL than in all other life cycles. Furthermore, updrafts moisten the upper troposphere and as such increase the radiative effect from water vapor. Particularly, this process becomes more relevant for maintaining the TIL during later stages of the life cycles. Increased convergence of the vertical wind induced by updrafts and by propagating and potentially dissipating inertia-gravity waves further contributes to the enhanced stability of the lower stratosphere. Furthermore, radiative feedback of ice clouds reaching up to the tropopause is identified to potentially further affect the strength of the TIL in the region of the cloud.

Description: Radiative and climate impacts of a large volcanic eruption during stratospheric sulfur geoengineering Atmospheric Chemistry and Physics Discussions, 15, 21837-21881, 2015 Author(s): A. Laakso, H. Kokkola, A.-I. Partanen, U. Niemeier, C. Timmreck, K. E. J. Lehtinen, H. Hakkarainen, and H. Korhonen Both explosive volcanic eruptions, which emit sulfur dioxide into the stratosphere, and stratospheric geoengineering via sulfur injections can potentially cool the climate by increasing the amount of scattering particles in the atmosphere. Here we employ a global aerosol-climate model and an earth system model to study the radiative and climate impacts of an erupting volcano during solar radiation management (SRM). According to our simulations, the radiative impacts of an eruption and SRM are not additive: in the simulated case of concurrent eruption and SRM, the peak increase in global forcing is about 40 % lower compared to a corresponding eruption into a clean background atmosphere. In addition, the recovery of the stratospheric sulfate burden and forcing was significantly faster in the concurrent case since the sulfate particles grew larger and thus sedimented faster from the stratosphere. In our simulation where we assumed that SRM would be stopped immediately after a volcano eruption, stopping SRM decreased the overall stratospheric aerosol load. For the same reasons, a volcanic eruption during SRM lead to only about 1/3 of the peak global ensemble-mean cooling compared to an eruption under unperturbed atmospheric conditions. Furthermore, the global cooling signal was seen only for 12 months after the eruption in the former scenario compared to over 40 months in the latter. In terms of the global precipitation rate, we obtain a 36 % smaller decrease in the first year after the eruption and again a clearly faster recovery in the concurrent eruption and SRM scenario. We also found that an explosive eruption could lead to significantly different regional climate responses depending on whether it takes place during geoengineering or into an unperturbed background atmosphere. Our results imply that observations from previous large eruptions, such as Mt Pinatubo in 1991, are not directly applicable when estimating the potential consequences of a volcanic eruption during stratospheric geoengineering.

Description: Validation of farm-scale methane emissions using nocturnal boundary layer budgets Atmospheric Chemistry and Physics Discussions, 15, 21765-21802, 2015 Author(s): J. Stieger, I. Bamberger, N. Buchmann, and W. Eugster This study provides the first experimental validation of Swiss agricultural methane emission estimates at the farm scale. We measured CH 4 concentrations at a Swiss farmstead during two intensive field campaigns in August 2011 and July 2012 to (1) quantify the source strength of livestock methane emissions using a tethered balloon system, and (2) to validate inventory emission estimates via nocturnal boundary layer (NBL) budgets. Field measurements were performed at a distance of 150 m from the nearest farm buildings with a tethered balloon system in combination with gradient measurements at eight heights on a 10 m tower to better resolve the near-surface concentrations. Vertical profiles of air temperature, relative humidity, CH 4 concentration, wind speed and wind direction showed that the NBL was strongly influenced by local transport processes and by the valley wind system. Methane concentrations showed a pronounced time course, with highest concentrations in the second half of the night. NBL budget flux estimates were obtained via a time–space kriging approach. Main uncertainties of NBL budget flux estimates were associated with instationary atmospheric conditions and the estimate of the inversion height z i (top of volume integration). The mean NBL budget fluxes of 1.60 ± 0.31 μg CH 4 m -2 s -1 (1.40 ± 0.50 and 1.66 ± 0.20 μg CH 4 m -2 s -1 in 2011 and 2012, respectively) were in good agreement with local inventory estimates based on current livestock number and default emission factors, with 1.29 ± 0.47 and 1.74 ± 0.63 μg CH 4 m -2 s -1 for 2011 and 2012, respectively. This indicates that emission factors used for the national inventory reports are adequate, and we conclude that the NBL budget approach is a useful tool to validate emission inventory estimates.

Description: Seasonality of ultrafine and sub-micron aerosols and the inferences on particle formation processes Atmospheric Chemistry and Physics Discussions, 15, 21803-21835, 2015 Author(s): H. C. Cheung, C. C.-K. Chou, M.-J. Chen, W.-R. Huang, S.-H. Huang, C.-Y. Tsai, and C. S.-L. Lee The aim of this study is to investigate the seasonal variations in the physicochemical properties of atmospheric ultrafine particles (UFPs, d ≤ 100nm) and submicron particles (PM 1 , d ≤ 1 μm) in an East-Asian urban area, which are hypothesized to be affected by the interchange of summer and winter monsoons. An observation experiment was conducted at the TARO, an urban aerosol station in Taipei, Taiwan, from October 2012 to August 2013. The measurements included the mass concentration and chemical composition of UFPs and PM 1 , as well as the particle number concentration (PNC) and size distribution (PSD) with size range of 4–736 nm. The results indicate that the mass concentration of PM 1 was elevated during cold seasons with peak level of 18.5 μg m -3 in spring, whereas the highest UFPs concentration was measured in summertime with a seasonal mean of 1.62 μg m -3 . Moreover, chemical analysis revealed that the UFPs and PM 1 were characterized by distinct composition; UFPs were composed mostly of organics, whereas ammonium and sulfate were the major constituents in PM 1 . The seasonal median of total PNCs ranged from 13.9 × 10 3 cm -3 in autumn to 19.4 × 10 3 cm -3 in spring. The PSD information retrieved from the corresponding PNC measurements indicates that the nucleation mode PNC ( N 4–25 ) peaked at 11.6 × 10 3 cm -3 in winter, whereas the Aitken mode ( N 25–100 ) and accumulation mode ( N 100–736 ) exhibited summer maxima at 6.0 × 10 3 and 3.1 × 10 3 cm -3 , respectively. The shift in PSD during summertime is attributed to the enhancement in the photochemical production of condensable organic matter that, in turn, contributes to the growth of aerosol particles in the atmosphere. In addition, remarkable photochemical production of particles was observed in spring and summer seasons, which was characterized with averaged particle growth and formation rates of 4.3 ± 0.8 nm h -1 and 1.6 ± 0.8 cm -3 s -1 , respectively. The prevalence of new particle formation (NPF) in summer is suggested as a result of seasonally enhanced photochemical oxidation of SO 2 , which contributes to the production of H 2 SO 4 , and low level of PM 10 ( d ≤ 10 μm) that serves as the condensation sink. Regarding the sources of aerosol particles, correlation analysis upon the PNCs against NO x revealed that the local vehicular exhaust was the dominant contributor of the UFPs throughout a year. On the contrary, the Asian pollution outbreaks can have significant influence in the PNC of accumulation mode particles during the seasons of winter monsoons. The results of this study underline the significance of secondary organic aerosols in the seasonal variations of UFPs and the influences of continental pollution outbreaks in the downwind areas of Asian outflows.

Description: Biomass burning emissions and potential air quality impacts of volatile organic compounds and other trace gases from temperate fuels common in the United States Atmospheric Chemistry and Physics Discussions, 15, 21713-21763, 2015 Author(s): J. B. Gilman, B. M. Lerner, W. C. Kuster, P. D. Goldan, C. Warneke, P. R. Veres, J. M. Roberts, J. A. de Gouw, I. R. Burling, and R. J. Yokelson A comprehensive suite of instruments was used to quantify the emissions of over 200 organic gases, including methane and volatile organic compounds (VOCs), and 9 inorganic gases from 56 laboratory burns of 18 different biomass fuel types common in the southeastern, southwestern, or northern United States. A gas chromatograph-mass spectrometer (GC-MS) provided extensive chemical detail of discrete air samples collected during a laboratory burn and was complemented by real-time measurements of organic and inorganic species via an open-path Fourier transform infrared spectrometer (OP-FTIR) and 3 different chemical ionization-mass spectrometers. These measurements were conducted in February 2009 at the U.S. Department of Agriculture's Fire Sciences Laboratory in Missoula, Montana. The relative magnitude and composition of the gases emitted varied by individual fuel type and, more broadly, by the 3 geographic fuel regions being simulated. Emission ratios relative to carbon monoxide (CO) were used to characterize the composition of gases emitted by mass; reactivity with the hydroxyl radical, OH; and potential secondary organic aerosol (SOA) precursors for the 3 different US fuel regions presented here. VOCs contributed less than 0.78 ± 0.12 % of emissions by mole and less than 0.95 ± 0.07 % of emissions by mass (on average) due to the predominance of CO 2 , CO, CH 4 , and NO x emissions; however, VOCs contributed 70–90 (±16) % to OH reactivity and were the only measured gas-phase source of SOA precursors from combustion of biomass. Over 82 % of the VOC emissions by mole were unsaturated compounds including highly reactive alkenes and aromatics and photolabile oxygenated VOCs (OVOCs) such as formaldehyde. OVOCs contributed 57–68 % of the VOC mass emitted, 42–57 % of VOC-OH reactivity, and aromatic-OVOCs such as benzenediols, phenols, and benzaldehyde were the dominant potential SOA precursors. In addition, ambient air measurements of emissions from the Fourmile Canyon Fire that affected Boulder, Colorado in September 2010 allowed us to investigate biomass burning (BB) emissions in the presence of other VOC sources (i.e., urban and biogenic emissions) and identify several promising BB markers including benzofuran, 2-furaldehyde, 2-methylfuran, furan, and benzonitrile.

Description: Real-time measurements of secondary organic aerosol formation and aging from ambient air in an oxidation flow reactor in the Los Angeles area Atmospheric Chemistry and Physics Discussions, 15, 21907-21958, 2015 Author(s): A. M. Ortega, P. L. Hayes, Z. Peng, B. B. Palm, W. Hu, D. A. Day, R. Li, M. J. Cubison, W. H. Brune, M. Graus, C. Warneke, J. B. Gilman, W. C. Kuster, J. A. de Gouw, and J. L. Jimenez Field studies in polluted areas over the last decade have observed large formation of secondary organic aerosol (SOA) that is often poorly captured by models. The study of SOA formation using ambient data is often confounded by the effects of advection, vertical mixing, emissions, and variable degrees of photochemical aging. An Oxidation Flow Reactor (OFR) was deployed to study SOA formation in real-time during the CalNex campaign in Pasadena, CA, in 2010. A high-resolution aerosol mass spectrometer (AMS) and a scanning mobility particle sizer (SMPS) alternated sampling ambient and reactor-aged air. The reactor produced OH concentrations up to 4 orders of magnitude higher than in ambient air, achieving equivalent atmospheric aging from hours up to several weeks in 3 min of processing. OH radical concentration was continuously stepped, obtaining measurements of real-time SOA formation and oxidation at multiple equivalent ages from 0.8 days–6.4 weeks. Enhancement of OA from aging showed a maximum net SOA production between 0.8–6 days of aging with net OA mass loss beyond 2 weeks. Reactor SOA mass peaked at night, in the absence of ambient photochemistry, and correlated with trimethylbenzene concentrations. Reactor SOA formation was inversely correlated with ambient SOA and O x , which along with the short-lived VOC correlation, indicates the importance of relatively reactive (τ OH ∼ 0.3 day) SOA precursors in the LA-Basin. Evolution of the elemental composition in the reactor was similar to trends observed in the atmosphere (O : C vs. H : C slope ∼ -0.65). Oxidation state of carbon (OS C ) in reactor SOA increased steeply with age and remained elevated (OS C ∼ 2) at the highest photochemical ages probed. The ratio of OA in the reactor output to excess CO (ΔCO, ambient CO above regional background) vs. photochemical age is similar to previous studies at low to moderate ages and also extends to higher ages where OA loss dominates. The mass added at low-to-intermediate ages is due primarily to condensation of oxidized species, not heterogeneous oxidation. The OA decrease at high photochemical ages is dominated by heterogeneous oxidation followed by fragmentation/evaporation. A comparison of urban SOA formation in this study with a similar study of vehicle SOA in a tunnel supports the dominance of vehicle emissions in urban SOA. Pre-2007 SOA models underpredict SOA formation by an order of magnitude, while a more recent model performs better but overpredicts at higher ages. These results demonstrate the value of the reactor as a tool for in situ evaluation of the SOA formation potential and OA evolution from ambient air.