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In this study we introduce a comparison method for footprint model results by evaluating the performance of conventional Lagrangian stochastic (LS) footprint models that use parameterised flow field characteristics with results of a Lagrangian trajectory model embedded in a large eddy simulation (LES) framework. The two conventional models follow the particles backward and forward in time while the trajectories in LES only evolve forward in time. We assess their performance in two unstably stratified boundary layers at observation levels covering the whole depth of the atmospheric boundary layer. We present a concept for footprint model comparison that can be applied for 2-D footprints and demonstrate that comparison of only cross wind integrated footprints is not sufficient for purposes facilitating two dimensional footprint information. Because the flow field description among the three models is most realistic in LES we use those results as the reference in the comparison. We found that the agreement of the two conventional models against the LES is generally better for intermediate measurement heights and for the more unstable case, whereas the two conventional flux footprint models agree best under less unstable conditions. The model comparison in 2-D was found quite sensitive to the grid resolution.
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In situ measurements of ice crystal concentrations and sizes made with aircraft instrumentation over the past two decades have often indicated the presence of numerous relatively small (< 50 μm diameter) crystals in cirrus clouds. Further, these measurements frequently indicate that small crystals account for a large fraction of the extinction in cirrus clouds. The fact that the instruments used to make these measurements, such as the Forward Scattering Spectrometer Probe (FSSP) and the Cloud Aerosol Spectrometer (CAS), ingest ice crystals into the sample volume through inlets has led to suspicion that the indications of numerous small-crystals could be artifacts of large-crystal shattering on the instrument inlets. We present new aircraft measurements in anvil cirrus sampled during the Tropical Composition, Cloud, and Climate Coupling (TC4) campaign with the 2-Dimensional Stereo (2D-S) probe, which detects particles as small as 10 μm. The 2D-S has detector "arms" instead of an inlet tube. Since the 2D-S probe surfaces are much further from the sample volume than is the case for the instruments with inlets, it is expected that 2D-S will be less susceptible to shattering artifacts. In addition, particle inter-arrival times are used to identify and remove shattering artifacts that occur even with the 2D-S probe. The number of shattering artifacts identified by the 2D-S interarrival time analysis ranges from a negligible contribution to an order of magnitude or more enhancement in apparent ice concentration over the natural ice concentration, depending on the abundance of large crystals and the natural small-crystal concentration. The 2D-S measurements in tropical anvil cirrus suggest that natural small-crystal concentrations are typically one to two orders of magnitude lower than those inferred from CAS. The strong correlation between the CAS/2D-S ratio of small-crystal concentrations and large-crystal concentration suggests that the discrepancy is likely caused by shattering of large crystals on the CAS inlet. We argue that past measurements with CAS in cirrus with large crystals present may contain errors due to crystal shattering, and past conclusions derived from these measurements may need to be revisited. Further, we present correlations between CAS spurious concentration and 2D-S large-crystal mass from spatially uniform anvil cirrus sampling periods as an approximate guide for estimating quantitative impact of large-crystal shattering on CAS concentrations in previous datasets. We use radiative transfer calculations to demonstrate that in the maritime anvil cirrus sampled during TC4, small crystals indicated by 2D-S contribute relatively little cloud extinction, radiative forcing, or radiative heating in the anvils, regardless of anvil age or vertical location in the clouds. While 2D-S ice concentrations in fresh anvil cirrus may often exceed 1 cm<sup>−3</sup>, and are observed to exceed 10 cm<sup>−3</sup> in turrets, they are typically <u>~</u>0.1 cm<sup>−3</sup> and rarely exceed 1 cm<sup>−3</sup> (<1.4% of the time) in aged anvil cirrus. We hypothesize that isolated occurrences of higher ice concentrations in aged anvil cirrus may be caused by ice nucleation driven by either small-scale convection or gravity waves. It appears that the numerous small crystals detrained from convective updrafts do not persist in the anvil cirrus sampled during TC-4.
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To better understand the contribution of biogenic volatile organic compounds to the formation of secondary organic aerosol (SOA) in high mountain regions, ambient aerosols were collected at the summit of Mt. Tai (1534 m, a.s.l.), Central East China (CEC) during the Mount Tai eXperiment 2006 campaign (MTX2006) in early summer. Biogenic SOA tracers of isoprene, monoterpenes, and β-caryophyllene oxidation products were measured using gas chromatography/mass spectrometry. All the biogenic SOA tracers showed no clear diurnal variations, suggesting that they are formed during long-range atmospheric transport. Although isoprene- and monoterpene-derived SOA tracers did not correlate with levoglucosan (a biomass burning tracer), β-caryophyllinic acid showed a good correlation with levoglucosan, indicating that biomass burning may be a source for this compound. Total concentrations of isoprene oxidation products are much higher than those of monoterpene and β-caryophyllene oxidation products. The ratio of isoprene to monoterpene oxidation products (<i>R</i><sub>iso/mono</sub>) was found to co-vary with ozone and NO<sub>x</sub> during the summer campaign. The average <i>R</i><sub>iso/mono</sub> value was 6.94 at daytime and 10.0 at nighttime. These values are among the highest in the aerosols studied in different regions, which may be due to the large isoprene fluxes, high O<sub>3</sub> and NO<sub>x</sub> levels and relatively high OH concentrations in CEC. Using a tracer-based method, we estimated the average concentrations of secondary organic carbon (SOC) derived from isoprene, monoterpenes, and β-caryophyllene to be 1.76 μgC m<sup>−3</sup> at daytime and 1.85 μgC m<sup>−3</sup> at nighttime. These values correspond to 11.2% and 11.0% of the total OC concentrations, in which isoprene-derived SOC are 7.4% and 8.0% at day- and night-time, respectively. This study suggests that isoprene is a more significant precursor for biogenic SOA than monoterpenes and β-caryophyllene in high altitude in CEC.
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We here present the results from mobile measurements using two ground-based zenith viewing Differential Optical Absorption Spectroscopy (DOAS) instruments. The measurement was performed in a cross-section of the plume from the Mexico City Metropolitan Area (MCMA) on 10 March 2006 as part of the MILAGRO field campaign. The two instruments operated in the UV and the visible wavelength region respectively and have been used to derive the differential vertical columns of HCHO and NO<sub>2</sub> above the measurement route. This is the first time the mobile mini-DOAS instrument has been able to measure HCHO, one of the chemically most important and interesting gases in the polluted urban atmosphere. <br><br> Using a mass-averaged wind speed and wind direction from the WRF model the instantaneous flux of HCHO and NO<sub>2</sub> has been calculated from the measurements and the results are compared to the CAMx chemical model. The calculated flux through the measured cross-section was 1.9 (1.5–2.2) kg/s of HCHO and 4.4 (4.0–5.0) kg/s of NO<sub>2</sub> using the UV instrument and 3.66 (3.63–3.73) kg/s of NO<sub>2</sub> using the visible light instrument. The modeled values from CAMx for the outflow of both NO<sub>2</sub> and HCHO, 1.1 and 3.6 kg/s, respectively, show a reasonable agreement with the measurement derived fluxes.
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Recent field studies have found large discrepancies in the measured vs. modeled SOA mass loadings in both urban and regional polluted atmospheres. The reasons for these large differences are unclear. Here we revisit a case study of SOA formation in Mexico City described by Volkamer et al. (2006), during a photochemically active period when the impact of regional biomass burning is minor or negligible, and show that the observed increase in OA/ΔCO is consistent with results from several groups during MILAGRO 2006. Then we use the case study to evaluate three new SOA models: 1) the update of aromatic SOA yields from recent chamber experiments (Ng et al., 2007); 2) the formation of SOA from glyoxal (Volkamer et al., 2007a); and 3) the formation of SOA from primary semivolatile and intermediate volatility species (P-S/IVOC) (Robinson et al., 2007). We also evaluate the effect of reduced partitioning of SOA into POA (Song et al., 2007). Traditional SOA precursors (mainly aromatics) by themselves still fail to produce enough SOA to match the observations by a factor of ~7. The new low-NO<sub>x</sub> aromatic pathways with very high SOA yields make a very small contribution in this high-NO<sub>x</sub> urban environment as the RO<sub>2</sub><sup>·</sup>+NO reaction dominates the fate of the RO<sub>2</sub><sup>·</sup> radicals. Glyoxal contributes several μg m<sup>−3</sup> to SOA formation, with similar timing as the measurements. P-S/IVOC are estimated from equilibrium with emitted POA, and introduce a large amount of gas-phase oxidizable carbon that was not in models before. With the formulation in Robinson et al. (2007) these species have a high SOA yield, and this mechanism can close the gap in SOA mass between measurements and models in our case study. However the volatility of SOA produced in the model is too high and the O/C ratio is somewhat lower than observations. Glyoxal SOA helps to bring the O/C ratio of predicted and observed SOA into better agreement. The sensitivities of the model to some key uncertain parameters are evaluated.
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Laboratory chamber data serve as the basis for constraining models of secondary organic aerosol (SOA) formation. Current models fall into three categories: empirical two-product (Odum), product-specific, and volatility basis set. The product-specific and volatility basis set models are applied here to represent laboratory data on the ozonolysis of α-pinene under dry, dark, and low-NO<sub>x</sub> conditions in the presence of ammonium sulfate seed aerosol. Using five major identified products, the model is fit to the chamber data. From the optimal fitting, SOA oxygen-to-carbon (O/C) and hydrogen-to-carbon (H/C) ratios are modeled. The discrepancy between measured H/C ratios and those based on the oxidation products used in the model fitting suggests the potential importance of particle-phase reactions. Data fitting is also carried out using the volatility basis set, wherein oxidation products are parsed into volatility bins. The product-specific model is most likely hindered by lack of explicit inclusion of particle-phase accretion compounds. While prospects for identification of the majority of SOA products for major volatile organic compounds (VOCs) classes remain promising, for the near future empirical product or volatility basis set models remain the approaches of choice.
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This work presents observations of a series of short-lived species in biomass burning plumes from the Infrared Atmospheric Sounding Interferometer (IASI), launched onboard the MetOp-A platform in October 2006. The strong fires that have occurred in the Mediterranean Basin – and particularly Greece – in August 2007, and those in Southern Siberia and Eastern Mongolia in the early spring of 2008 are selected to support the analyses. We show that the IASI infrared spectra in these fire plumes contain distinctive signatures of ammonia (NH<sub>3</sub>), ethene (C<sub>2</sub>H<sub>4</sub>), methanol (CH<sub>3</sub>OH) and formic acid (HCOOH) in the atmospheric window between 800 and 1200 cm<sup>−1</sup>, with some noticeable differences between the plumes. Peroxyacetyl nitrate (CH<sub>3</sub>COOONO<sub>2</sub>, abbreviated as PAN) was also observed with good confidence in some plumes and a tentative assignment of a broadband absorption spectral feature to acetic acid (CH<sub>3</sub>COOH) is made. For several of these species these are the first reported measurements made from space in nadir geometry. The IASI measurements are analyzed for plume height and concentration distributions of NH<sub>3</sub>, C<sub>2</sub>H<sub>4</sub> and CH<sub>3</sub>OH. The Greek fires are studied in greater detail for the days associated with the largest emissions. In addition to providing information on the spatial extent of the plume, the IASI retrievals allow an estimate of the total mass emissions for NH<sub>3</sub>, C<sub>2</sub>H<sub>4</sub> and CH<sub>3</sub>OH. Enhancement ratios are calculated for the latter relative to carbon monoxide (CO), giving insight in the chemical processes occurring during the transport, the first day after the emission.
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We have performed simulations using a 3-D global chemistry-transport model to investigate the influence that biogenic emissions from the African continent exert on the composition of the troposphere in the tropical region. For this purpose we have applied two recently developed biogenic emission inventories provided for use in large-scale global models (Granier et al., 2005; Lathière et al., 2006) whose seasonality and temporal distribution for biogenic emissions of isoprene, other volatile organic compounds and NO is markedly different. The use of the 12 year average values for biogenic emissions provided by Lathière et al. (2006) results in an increase in the amount of nitrogen sequestrated into longer lived reservoir compounds which contributes to the reduction in the tropospheric ozone burden in the tropics. The associated re-partitioning of nitrogen between PAN, HNO<sub>3</sub> and organic nitrates also results in a ~5% increase in the loss of nitrogen by wet deposition. At a global scale there is a reduction in the oxidizing capacity of the model atmosphere which increases the atmospheric lifetimes of CH<sub>4</sub> and CO by ~1.5% and ~4%, respectively. Comparisons against a range of different measurements indicate that applying the 12 year average of Lathière et al. (2006) improves the performance of TM4_AMMA for 2006 in the tropics. By the use of sensitivity studies we show that the release of NO from soils in Africa accounts for between ~2–45% of tropospheric ozone in the African troposphere, ~10% in the upper troposphere and between ~5–20% of the tropical tropospheric ozone column over the tropical Atlantic Ocean. The subsequent reduction in OH over the source regions allows enhanced transport of CO out of the region. For biogenic volatile organic C1 to C3 species released from Africa, the effects on tropical tropospheric ozone are rather limited, although this source contributes to the global burden of VOC by between ~2–4% and has a large influence on the organic composition of the troposphere over the tropical Atlantic Ocean.
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1-year data sets of monthly averaged nitrous oxide (N<sub>2</sub>O) and ozone (O<sub>3</sub>) derived from satellite measurements were used as a tool for the evaluation of atmospheric photochemical models. Two 1-year data sets, one solar occultation data set derived from the Improved Limb Atmospheric Spectrometer (ILAS and ILAS-II) and one limb sounding data set derived from the Odin Sub-Millimetre Radiometer (Odin/SMR) were employed. Here, these data sets are used for the evaluation of two Chemical Transport Models (CTMs), the Karlsruhe Simulation Model of the Middle Atmosphere (KASIMA) and the Chemical Lagrangian Model of the Stratosphere (CLaMS) as well as for one Chemistry-Climate Model (CCM), the atmospheric chemistry general circulation model ECHAM5/MESSy1 (E5M1) in the lower stratosphere with focus on the Northern Hemisphere. Since the Odin/SMR measurements cover the entire hemisphere, the evaluation is performed for the entire hemisphere as well as for the low latitudes, midlatitudes and high latitudes using the Odin/SMR 1-year data set as reference. To assess the impact of using different data sets for such an evaluation study we repeat the evaluation for the polar lower stratosphere using the ILAS/ILAS-II data set. Only small differences were found using ILAS/ILAS-II instead of Odin/SMR as a reference, thus, showing that the results are not influenced by the particular satellite data set used for the evaluation. The evaluation of CLaMS, KASIMA and E5M1 shows that all models are in agreement with Odin/SMR and ILAS/ILAS-II. Differences are generally in the range of ±20%. Larger differences (up to −40%) are found in all models at 500±25 K for N<sub>2</sub>O mixing ratios greater than 200 ppbv, thus in air masses of tropical character. Generally, the largest differences were found for the tropics and the lowest for the polar regions. However, an underestimation of polar winter ozone loss was found both in KASIMA and E5M1 both in the Northern and Southern Hemisphere.
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This paper analyses a stratospheric injection by deep convection of biomass fire emissions over North America (Alaska, Yukon and Northwest Territories) on 24 June 2004 and its long-range transport over the eastern coast of the United States and the eastern Atlantic. The case study is based on airborne MOZAIC observations of ozone, carbon monoxide, nitrogen oxides and water vapour during the crossing of the southernmost tip of an upper level trough over the Eastern Atlantic on 30 June and on a vertical profile over Washington DC on 30 June, and on lidar observations of aerosol backscattering at Madison (University of Wisconsin) on 28 June. Attribution of the observed CO plumes to the boreal fires is achieved by backward simulations with a Lagrangian particle dispersion model (FLEXPART). A simulation with the Meso-NH model for the source region shows that a boundary layer tracer, mimicking the boreal forest fire smoke, is lofted into the lowermost stratosphere (2–5 pvu layer) during the diurnal convective cycle at isentropic levels (above 335 K) corresponding to those of the downstream MOZAIC observations. It is shown that the order of magnitude of the time needed by the parameterized convective detrainment flux to fill the volume of a model mesh (20 km horizontal, 500 m vertical) above the tropopause with pure boundary layer air would be about 7.5 h, i.e. a time period compatible with the convective diurnal cycle. Over the area of interest, the maximum instantaneous detrainment fluxes deposited about 15 to 20% of the initial boundary layer tracer concentration at 335 K. According to the 275-ppbv carbon monoxide maximum mixing ratio observed by MOZAIC over Eastern Atlantic, such detrainment fluxes would be associated with a 1.4–1.8 ppmv carbon monoxide mixing ratio in the boundary layer over the source region.
