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In this study, the influence of radiative cooling and small eddies on cirrus formation is investigated. For this purpose the non-hydrostatic, anelastic model EULAG is used with a recently developed and validated ice microphysics scheme (Spichtinger and Gierens, 2009a). Additionally, we implemented a fast radiative transfer code (Fu et al., 1998). Using idealized profiles with high ice supersaturations up to 144% and weakly stable stratifications with Brunt-Vaisala frequencies down to 0.0018 s<sup>−1</sup> within a supersaturated layer, the influence of radiation on the formation of cirrus clouds is remarkable. Due to the radiative cooling at the top of the ice supersaturated layer with cooling rates down to −3.5 K/d, the stability inside the ice supersaturated layer decreases with time. During destabilization, small eddies induced by Gaussian temperature fluctuations start to grow and trigger first nucleation. These first nucleation events then induce the growth of convective cells due to the radiative destabilization. The effects of increasing the local relative humidity by cooling due to radiation and adiabatic lifting lead to the formation of a cirrus cloud with IWC up to 33 mg/m<sup>3</sup> and mean optical depths up to 0.36. In a more stable environment, radiative cooling is not strong enough to destabilize the supersaturated layer within 8 h; no nucleation occurs in this case. <br><br> Overall triggering of cirrus clouds via radiation works only if the supersaturated layer is destabilized by radiative cooling such that small eddies can grow in amplitude and finally initialize ice nucleation. Both processes on different scales, small-scale eddies and large-scale radiative cooling are necessary.
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In view of the proposed geostationary satellite missions to monitor air quality from space, it is important to first assess the capability of the current suite of satellite instruments to provide information on the urban scale pollution. We explore the possibility of detecting urban signatures in the tropospheric column ozone data derived from Total Ozone Mapping Spectrometer (TOMS)/Solar Backscattered Ultraviolet (SBUV) and Ozone Monitoring Instrument (OMI)/Microwave Limb Sounder (MLS) satellite data. We find that distinct isolated plumes of tropospheric ozone near several large and polluted cities around the world may be detected in these data sets. The ozone plumes generally correspond with the tropospheric column NO<sub>2</sub> plumes around these cities as observed by the Scanning Imaging Absorption Spectrometer for Atmospheric Chartography (SCIAMACHY) instrument. Similar plumes are also seen in tropospheric mean ozone mixing ratio distribution after accounting for the surface and tropopause pressure variations. The total column ozone retrievals indicate fairly significant sensitivity to the lower troposphere over the polluted land areas, which might help explain these detections. These results indicate that ultraviolet (UV) measurements may, in principle, be able to capture the urban signatures and may have implications for future missions using geostationary satellites.
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The NASA Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) mission was conducted in two 3-week deployments based in Alaska (April 2008) and western Canada (June–July 2008). Its goal was to better understand the factors driving current changes in Arctic atmospheric composition and climate, including (1) influx of mid-latitude pollution, (2) boreal forest fires, (3) aerosol radiative forcing, and (4) chemical processes. The June–July deployment was preceded by one week of flights over California (ARCTAS-CARB) focused on (1) improving state emission inventories for greenhouse gases and aerosols, (2) providing observations to test and improve models of ozone and aerosol pollution. ARCTAS involved three aircraft: a DC-8 with a detailed chemical payload, a P-3 with an extensive aerosol and radiometric payload, and a B-200 with aerosol remote sensing instrumentation. The aircraft data augmented satellite observations of Arctic atmospheric composition, in particular from the NASA A-Train. The spring phase (ARCTAS-A) revealed pervasive Asian pollution throughout the Arctic as well as significant European pollution below 2 km. Unusually large Siberian fires in April 2008 caused high concentrations of carbonaceous aerosols and also affected ozone. Satellite observations of BrO column hotspots were found not to be related to Arctic boundary layer events but instead to tropopause depressions, suggesting the presence of elevated inorganic bromine (5–10 pptv) in the lower stratosphere. Fresh fire plumes from Canada and California sampled during the summer phase (ARCTAS-B) indicated low NO<sub>x</sub> emission factors from the fires, rapid conversion of NO<sub>x</sub> to PAN, no significant secondary aerosol production, and no significant ozone enhancements except when mixed with urban pollution.
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Field blanks (bQF) and backup filters (quartz-fiber behind quartz-fiber filter; QBQ) have been adopted by US long-term air quality monitoring networks to estimate PM<sub>2.5</sub> organic carbon (OC) sampling artifacts. This study documents bQF and QBQ carbon levels for the: 1) Interagency Monitoring of Protected Visual Environments (IMPROVE); 2) Speciation Trends Network (STN; part of the Chemical Speciation Network [CSN]); and 3) Southeastern Aerosol Research and Characterization (SEARCH) networks and examines the similarities/differences associated with network-specific sampling protocols. A higher IMPROVE sample volume and smaller filter deposit area results in PM<sub>2.5</sub> areal density (μg/cm<sup>2</sup> on filter) 3–11 times those of STN/CSN and SEARCH samples for the same ambient PM<sub>2.5</sub> concentrations, thus reducing the relative contribution of sampling artifacts from passive OC adsorption. A relatively short (1–15 min) passive exposure period of STN/CSN and SEARCH bQF OC (0.8–1 μg/cm<sup>2</sup>) underestimates positive and negative OC artifacts resulting from passive adsorption or evaporation of semi-volatile organic compounds on quartz-fiber filters. This is supported by low STN/CSN and SEARCH bQF levels and lack of temporal or spatial variability among the sites within the networks. With a much longer period, ~7 days of ambient passive exposure, average IMPROVE bQF and QBQ OC are comparable (2.4±0.5 and 3.1±0.8 μg/cm<sup>2</sup>, respectively) and more than twice levels found in the STN/CSN and SEARCH networks. Sampling artifacts in STN/CSN were estimated from collocated IMPROVE samples based on linear regression. At six of the eight collocated sites in this study, STN/CSN bQFs underestimated OC artifacts by 11–34%. Using a preceding organic denuder in the SEARCH network minimized passive adsorption on QBQ, but OC on QBQ may not be attributed entirely to the negative sampling artifact (e.g., evaporated or volatilized OC from the front filter deposits after sample collection).
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Organic aerosol (OA) represents approximately half of the submicron aerosol in Mexico City and the Central Mexican Plateau. This study uses the high time resolution measurements performed onboard the NCAR/NSF C-130 aircraft during the MILAGRO/MIRAGE-Mex field campaign in March 2006 to investigate the sources and chemical processing of the OA in this region. An examination of the OA/ΔCO ratio evolution as a function of photochemical age shows distinct behavior in the presence or absence of substantial open biomass burning (BB) influence, with the latter being consistent with other studies in polluted areas. In addition, we present results from Positive Matrix Factorization (PMF) analysis of 12-s High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) OA spectra. Four components were resolved. Three of the components contain substantial organic oxygen and are termed semivolatile oxygenated OA (SV-OOA), low-volatility OOA (LV-OOA), and biomass burning OA (BBOA). A reduced "hydrocarbon-like OA" (HOA) component is also resolved. LV-OOA is highly oxygenated (atomic O/C~1) and is aged organic aerosol linked to regional airmasses, with likely contributions from pollution, biomass burning, and other sources. SV-OOA is strongly correlated with ammonium nitrate, O<sub>x</sub>, and the Mexico City Basin. We interpret SV-OOA as secondary OA which is nearly all (>90%) anthropogenic in origin. In the absence of biomass burning it represents the largest fraction of OA over the Mexico City basin, consistent with other studies in this region. BBOA is identified as arising from biomass burning sources due to a strong correlation with HCN, and the elevated contribution of the ion C<sub>2</sub>H<sub>4</sub>O<sub>2</sub><sup>+</sup> (<i>m/z</i> 60, a marker for levoglucosan and other primary BB species). WRF-FLEXPART calculated fire impact factors (FIF) show good correlation with BBOA mass concentrations within the basin, but show location offsets in the far field due to model transport errors. This component is small or absent when forest fires are suppressed by precipitation. Since PMF factors represent organic species grouped by chemical similarity, additional postprocessing is needed to more directly apportion OA amounts to sources, which is done here based on correlations to different tracers. The postprocessed AMS results are similar to those from an independent source apportionment based on multiple linear regression with gas-phase tracers. During a flight with very high forest fire intensity near the basin OA arising from open BB represents ~66% of the OA mass in the basin and contributes similarly to OA mass in the outflow. Aging and SOA formation of BB emissions is estimated to add OA mass equivalent to about ~32–42% of the primary BBOA over several hours to a day.
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Submicron aerosol was analyzed during the MILAGRO field campaign in March 2006 at the T0 urban supersite in Mexico City with a High-Resolution Aerosol Mass Spectrometer (AMS) and complementary instrumentation. Positive Matrix Factorization (PMF) of high resolution AMS spectra identified a biomass burning organic aerosol (BBOA) component, which includes several large plumes that appear to be from forest fires within the region. Here, we show that the AMS BBOA concentration at T0 correlates with fire counts in the vicinity of Mexico City and that most of the BBOA variability is captured when the FLEXPART model is used for the dispersion of fire emissions as estimated from satellite fire counts. The resulting FLEXPART fire impact factor (FIF) correlates well with the observed BBOA, acetonitrile (CH<sub>3</sub>CN), levoglucosan, and potassium, indicating that wildfires in the region surrounding Mexico City are the dominant source of BBOA at T0 during MILAGRO. The impact of distant BB sources such as the Yucatan is small during this period. All fire tracers are correlated, with BBOA and levoglucosan showing little background, acetonitrile having a well-known tropospheric background of ~100–150 pptv, and PM<sub>2.5</sub> potassium having a background of ~160 ng m<sup>−3</sup> (two-thirds of its average concentration), which does not appear to be related to BB sources. <br><br> We define two high fire periods based on satellite fire counts and FLEXPART-predicted FIFs. We then compare these periods with a low fire period when the impact of regional fires is about a factor of 5 smaller. Fire tracers are very elevated in the high fire periods whereas tracers of urban pollution do not change between these periods. Dust is also elevated during the high BB period but this appears to be coincidental due to the drier conditions and not driven by direct dust emission from the fires. The AMS oxygenated organic aerosol (OA) factor (OOA, mostly secondary OA or SOA) does not show an increase during the fire periods or a correlation with fire counts, FLEXPART-predicted FIFs or fire tracers, indicating that it is dominated by urban and/or regional sources and not by the fires near the MCMA. <br><br> A new <sup>14</sup>C aerosol dataset is presented. Both this new and a previously published dataset of <sup>14</sup>C analysis suggest a similar BBOA contribution as the AMS and chemical mass balance (CMB), resulting in 13% higher non-fossil carbon during the high vs. low regional fire periods. The new dataset has ~15% more fossil carbon on average than the previously published one, and possible reasons for this discrepancy are discussed. During the low regional fire period, 38% of organic carbon (OC) and 28% total carbon (TC) are from non-fossil sources, suggesting the importance of urban and regional non-fossil carbon sources other than the fires, such as food cooking and regional biogenic SOA. The ambient BBOA/ΔCH<sub>3</sub>CN ratio is much higher in the afternoon when the wildfires are most intense than during the rest of the day. Also, there are large differences in the contributions of the different OA components to the surface concentrations vs. the integrated column amounts. Both facts may explain some apparent disagreements between BB impacts estimated from afternoon aircraft flights vs. those from 24-h ground measurements. <br><br> We show that by properly accounting for the non-BB sources of K, all of the BB PM estimates from MILAGRO can be reconciled. Overall, the fires from the region near the MCMA are estimated to contribute 15–23% of the OA and 7–9% of the fine PM at T0 during MILAGRO, and 2–3% of the fine PM as an annual average. The 2006 MCMA emissions inventory contains a substantially lower impact of the forest fire emissions, although a fraction of these emissions occur just outside of the MCMA inventory area.
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Formaldehyde of known, near-natural isotopic composition was photolyzed in the SAPHIR atmosphere simulation chamber under ambient conditions. The isotopic composition of the product H<sub>2</sub> was used to determine the isotope effects in formaldehyde photolysis. The experiments are sensitive to the molecular photolysis channel, and the radical channel has only an indirect effect and cannot be effectively constrained. The molecular channel kinetic isotope effect KIE<sub>mol</sub>, the ratio of photolysis frequencies <i>j</i>(HCHO→CO+H<sub>2</sub>)/<i>j</i>(HCDO→CO+HD) at surface pressure, is determined to be KIE<sub>mol</sub>=1.63<sub>−0.046</sub><sup>+0.038</sup>. This is similar to the kinetic isotope effect for the total removal of HCHO from a recent relative rate experiment (KIE<sub>tot</sub>=1.58±0.03), which indicates that the KIEs in the molecular and radical photolysis channels at surface pressure (≈100 kPa) may not be as different as described previously in the literature.
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In this paper we describe measurements of volatile organic compounds (VOC) made using a Proton Transfer Reaction Mass Spectrometer (PTR-MS) aboard the UK Facility for Atmospheric Airborne Measurements during the African Monsoon Multidisciplinary Analyses (AMMA) campaign. Observations were made during approximately 85 h of flying time between 17 July and 17 August 2006, above an area between 4° N and 18° N and 3° W and 4° E, encompassing ocean, mosaic forest, and the Sahel desert. High time resolution observations of counts at mass to charge (<i>m/z</i>) ratios of 42, 59, 69, 71, and 79 were used to calculate mixing ratios of acetonitrile, acetone, isoprene, the sum of methyl vinyl ketone and methacrolein, and benzene respectively using laboratory-derived humidity-dependent calibration factors. Strong spatial associations between vegetation and isoprene and its oxidation products were observed in the boundary layer, consistent with biogenic emissions followed by rapid atmospheric oxidation. Acetonitrile, benzene, and acetone were all enhanced in airmasses which had been heavily influenced by biomass burning. Benzene and acetone were also elevated in airmasses with urban influence from cities such as Lagos, Cotonou, and Niamey. The observations provide evidence that both deep convection and mixing associated with fair-weather cumulus were responsible for vertical redistribution of VOC emitted from the surface. Profiles over the ocean showed a depletion of acetone in the marine boundary layer, but no significant decrease for acetonitrile.
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Energy security and climate change concerns have led to the promotion of biomass-derived ethanol, an oxygenated volatile organic compound (OVOC), as a substitute for fossil fuels. Although ethanol is ubiquitous in the troposphere, our knowledge of its current atmospheric budget and distribution is limited. Here, for the first time we use a global chemical transport model in conjunction with atmospheric observations to place constraints on the ethanol budget, noting that additional measurements of ethanol (and its precursors) are still needed to enhance confidence in our estimated budget. Global sources of ethanol in the model include 5.0 Tg yr<sup>−1</sup> from industrial sources and biofuels, 9.2 Tg yr<sup>−1</sup> from terrestrial plants, ~0.5 Tg yr<sup>−1</sup> from biomass burning, and 0.05 Tg yr<sup>−1</sup> from atmospheric reactions of the ethyl peroxy radical (C<sub>2</sub>H<sub>5</sub>O<sub>2</sub>) with itself and with the methyl peroxy radical (CH<sub>3</sub>O<sub>2</sub>). The resulting atmospheric lifetime of ethanol in the model is 2.8 days. Gas-phase oxidation by the hydroxyl radical (OH) is the primary global sink of ethanol in the model (65%), followed by dry deposition (25%), and wet deposition (10%). Over continental areas, ethanol concentrations predominantly reflect direct anthropogenic and biogenic emission sources. Uncertainty in the biogenic ethanol emissions, estimated at a factor of three, may contribute to the 50% model underestimate of observations in the North American boundary layer. Current levels of ethanol measured in remote regions are an order of magnitude larger than those in the model, suggesting a major gap in understanding. Stronger constraints on the budget and distribution of ethanol and OVOCs are a critical step towards assessing the impacts of increasing the use of ethanol as a fuel.
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