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Although it is well known that air enters the stratosphere preferentially through upwelling in the tropics, the exact mechanisms of troposphere-to-stratosphere transport (TST) are still unknown. Previously proposed mechanisms have been found either to be too slow (e.g., clear sky upwelling) to provide agreement with in situ tracer measurements, or to be insufficient in mass flux to act as a major supply for the Brewer-Dobson circulation (e.g., convective overshooting). In this study we evaluate whether the lofting of air via cirrus cloud-radiation interaction might offer an alternative path for TST, which is responsible for a significant fraction of the observed air mass transport. We find that a combination of deep convection and subsequent upwelling associated with cirrus clouds and clear sky can explain the supply of air for the Brewer-Dobson circulation. Thus, upwelling associated with cirrus clouds offers a mechanism for the missing second stage, which links the first stage of TST, deep convection, to the third stage, the Brewer-Dobson circulation.
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The partitioning of reactive nitrogen compounds between the gas and the aerosol phase, as observed during the MINOS (Mediterranean INtensive Oxidant Study) campaign in Crete, Greece, in July and August 2001, has been studied with three thermodynamic gas-aerosol equilibrium models (EQMs) of different chemical complexity: ISORROPIA, which is limited to the ammonium-sulfate-nitrate-sodium-chloride-water-system; SCAPE2, which also includes mineral elements (calcium, magnesium and potassium); and EQSAM2, which additionally accounts for organic acids. The different EQMs are constrained by measured gas (g) and aerosol (a) concentrations: Total ammonia (NH<sub>3(g)</sub> and NH<sub>4(a)</sub><sup>+</sup>), total nitrate (HNO<sub>3(g)</sub> and NO<sub>3(a)</sub><sup>-</sup>), total sulfate (H<sub>2</sub>SO<sub>4(g)</sub> and SO<sub>4(a)</sub><sup>2-</sup>), total chloride (HCl<sub>(g)</sub> and Cl<sup>-</sup><sub>(a)</sub>), sodium (Na<sup>+</sup><sub>(a)</sub>), calcium (Ca<sup>2+</sup><sub>(a)</sub>), magnesium (Mg<sup>2+</sup><sub>(a)</sub>), potassium (K<sup>+</sup><sub>(a)</sub>) and organic acids (a). Although the three EQMs differ considerably in particular aspects, their application at the same level of complexity yields comparable results for the equilibrium composition and phase partitioning of ammonia and nitric acid, i.e. within the range of measurement uncertainties (~10%). Their application at different levels of complexity, however, gives rise to substantial differences for the gas-aerosol partitioning of reactive nitrogen compounds. Our results show that only if (soluble) mineral components and (lumped) organic acids are accounted for, the observed gas-aerosol partitioning of ammonia and nitric acid can be accurately reproduced for air pollution episodes characterized by a complex chemical mixture, typical for the Mediterranean lower atmosphere.
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Diiodomethane (CH<sub>2</sub>I<sub>2</sub>) has recently become a molecule of significant atmospheric interest as it can contribute to coastal IO formation. As part of the PNNL database of gas-phase infrared spectra, the quantitative absorption spectrum of CH<sub>2</sub>I<sub>2</sub> has been acquired at 0.1 cm<sup>-1</sup> resolution. Two strong b<sub>2</sub> symmetry A-type bands at 584 and 1114 cm<sup>-1</sup> are observed, but are not resolved when broadened to 760 Torr with nitrogen and appear as B-type. In contrast, the b<sub>1</sub> symmetry C-type bands near 5953, 4426 and 3073 cm<sup>-1</sup> are resolved with rotational structure, including Q-branches with widths ≤1 cm<sup>-1</sup>. The quantitative infrared and near-infrared vapor-phase spectra (600–10 000 cm<sup>-1</sup>) are reported for the first time. Some bands are discussed in terms of their potential for atmospheric monitoring and theoretical detection limits on a selected basis. FT-Raman spectra and ab initio calculations are used to complete vibrational assignments in the C<sub>2<i>v</i></sub> point group.
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An important part of extra-tropical stratosphere-to-troposphere transport occurs in association with baroclinic wave breaking and cut-off decay at the tropopause. In the last decade many studies have attempted to estimate stratosphere-troposphere exchange (STE) in such synoptic events with various methods, and more recently efforts have been made to inter-compare these methods. These inter-comparisons show large variations between estimates from different methods. This large uncertainty points to a need to thoroughly evaluate such methods, assess the realism of the resulting STE estimates and determine the sensitivities to intrinsic parameters of the methods. The present study focuses on a trajectory-based Lagrangian method which has been applied in the past to climatological studies. This method is applied here to the quantification of STE in the context of a typical baroclinic wave breaking event. The analysis sheds light on (i) the complex three-dimensional temporal and spatial structures that are associated with the rapid inflow of stratospheric air into the troposphere, (ii) the variation of STE mass flux with the choice of the dynamical tropopause definition within 1.5 to 5 PVU, (iii) the sensitivity of the results to resolution, and in particular the minimum spatial resolution of 1°×1° required to reasonably capture STE fluxes in this wave breaking event, (iv) the effective removal of spurious exchange events using a threshold residence time larger than 8 h.
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Nocturnal chemistry in the atmospheric boundary layer plays a key role in determining the initial chemical conditions for photochemistry during the following morning as well as influencing the budgets of O<sub>3</sub> and NO<sub>2</sub>. Despite its importance, chemistry in the nocturnal boundary layer (NBL), especially in heavily polluted urban areas, has received little attention so far, which greatly limits the current understanding of the processes involved. In particular, the influence of vertical mixing on chemical processes gives rise to complex vertical profiles of various reactive trace gases and makes nocturnal chemistry altitude-dependent. The processing of pollutants is thus driven by a complicated, and not well quantified, interplay between chemistry and vertical mixing. In order to gain a better understanding of the altitude-dependent nocturnal chemistry in the polluted urban environment, a field study was carried out in the downtown area of Phoenix, AZ, in summer 2001. Vertical profiles of reactive species, such as O<sub>3</sub>, NO<sub>2</sub>, and NO<sub>3</sub>, were observed in the lowest 140 m of the troposphere throughout the night. The disappearance of these trace gas vertical gradients during the morning coincided with the morning transition from a stable NBL to a well-mixed convective layer. The vertical gradients of trace gas levels were found to be dependent on both surface NO<sub>x</sub> emission strength and the vertical stability of the NBL. The vertical gradients of O<sub>x</sub>, the sum of O<sub>3</sub> and NO<sub>2</sub>, were found to be much smaller than those of O<sub>3</sub> and NO<sub>2</sub>, revealing the dominant role of NO emissions followed by the O<sub>3</sub>+NO reaction for the altitude-dependence of nocturnal chemistry in urban areas. Dry deposition, direct emissions, and other chemical production pathways of NO<sub>2</sub> also play a role for the O<sub>x</sub> distribution. Strong positive vertical gradients of NO<sub>3</sub>, that are predominantly determined by NO<sub>3</sub> loss near the ground, were observed. The vertical profiles of NO<sub>3</sub> and the calculated vertical profiles of its reservoir species (N<sub>2</sub>O<sub>5</sub>) confirm earlier model results suggesting complex vertical distributions of atmospheric denoxification processes during the night.
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The three carbon gases carbon monoxide (CO), carbon dioxide (CO<sub>2</sub>), and methane (CH<sub>4</sub>) are important atmospheric constituents affecting air quality and climate. The near-infrared nadir spectra measured by SCIAMACHY on ENVISAT contain information on the vertical columns of these gases which we retrieve using a modified DOAS algorithm (WFM-DOAS or WFMD). Our main data products are CO vertical columns and dry-air column averaged mixing ratios of methane (CH<sub>4</sub>) and CO<sub>2</sub> (denoted XCH<sub>4</sub> and XCO<sub>2</sub>). For CO and CH<sub>4</sub> we present new results for the year 2003 obtained with an improved version of WFM-DOAS (WFMDv0.5) retrieved from Level 1 version 4 (Lv1v4) spectra. This data set has recently been compared with a network of ground based FTIR stations. Here we describe the WFMDv0.5 algorithm, present global and regional maps, and comparisons with global reference data. We show that major problems of the previous versions (v0.4 and v0.41) related to the varying ice-layer on the SCIAMACHY channel 8 detector have been solved. Compared to MOPITT the SCIAMACHY CO columns are on average higher by about 10–20%. Regionally, however, especially over central South America, differences can be much larger. For methane we present global and regional maps which are compared to TM5 model simulations performed using standard methane emission inventories. We show that methane source regions can be clearly detected with SCIAMACHY. We also show that the methane data product can be significantly further improved using Lv1v5 spectra with improved calibration. For CO<sub>2</sub> we present three years of SCIAMACHY CO<sub>2</sub> measurements over Park Falls, Wisconsin, USA, retrieved from Lv1v5. We show that the quality of CO<sub>2</sub> retrieved from these spectra is significantly higher compared to WFMDv0.4 XCO<sub>2</sub> retrieved from Lv1v4.
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Ambient formaldehyde concentrations are reported from the North Atlantic Marine Boundary Layer Experiment (NAMBLEX) campaign at Mace Head on the west coast of Eire during August 2002. The results from two techniques, using direct determination via gas chromatography and the Hantzsch technique, show similar trends but a significant off set in concentrations. For westerly air flows characteristic of the marine boundary layer, formaldehyde concentrations from the gas chromatographic and Hantzsch technique ranged from 0.78–1.15 ppb and 0.13–0.43 ppb, respectively. Possible reasons for the discrepancy have been investigated and are discussed, however, no satisfactory explanation has yet been found. In a subsequent laboratory intercomparison the two techniques were in good agreement. The observed concentrations have been compared with previous formaldehyde measurements in the North Atlantic marine boundary layer and with other measurements from the NAMBLEX campaign. The measurements from the Hantzsch technique and the GC results lie at the lower and upper ends respectively of previous measurements. In contrast to some previous measurements, both techniques show distinct diurnal profiles with day maxima and with an amplitude of approximately 0.15 ppb. Strong correlations were observed with ethanal concentrations measured during NAMBLEX and the ratio of ethanal to formaldehyde determined by the gas chromatographic technique is in good agreement with previous measurements. Some simple box modelling has been undertaken to investigate possible sources of formaldehyde. Such models are not able to predict absolute formaldehyde concentrations as they do not include transport processes, but the results show that oxygenated VOCs such as ethanal and methanol are very significant sources of formaldehyde in the air masses reaching Mace Head.
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The Gas and Aerosol Measurement Sensor (GAMS) was deployed aboard the NASA DC-8 aircraft during the second SAGE III Ozone Loss and Validation Experiment (SOLVE II). GAMS acquired line-of-sight (LOS) direct solar irradiance spectra during the sunlit portions of ten science flights of the DC-8 between 12 January and 4 February 2003. Differential line-of-sight (DLOS) optical depth spectra are produced from the GAMS raw solar irradiance spectra. Then, DLOS ozone number densities are retrieved from the GAMS spectra using a multiple linear regression spectral fitting technique. Both the DLOS optical depth spectra and retrieved ozone data are compared with coincident measurements from two other solar instruments aboard the DC-8 platform to demonstrate the robustness and stability of the GAMS data. The GAMS ozone measurements are then utilized to evaluate the quality of the Wulf band ozone cross sections, a critical component of the SAGE III aerosol, water vapor, and temperature/pressure retrievals. Results suggest the ozone cross section compilation of Shettle and Anderson currently used operationally in SAGE III data processing may be in error by as much as 10–20% in the Wulf bands, and their lack of reported temperature dependence is a significant deficiency. A second, more recent, cross section database compiled for the SCIAMACHY satellite mission appears to be of much better quality in the Wulf bands, but still may have errors as large as 5% near the Wulf band absorption peaks, which is slightly larger than their stated uncertainty. Additional laboratory measurements of the Wulf band cross sections should be pursued to further reduce their uncertainty and better quantify their temperature dependence.
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We report on the dependence of ozone volume mixing ratio profiles, retrieved from limb emission infrared spectra of the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS), on different retrieval setups such as the treatment of the background continuum, cloud filtering, spectral regions used for analysis and a series of further more technical parameter choices. The purpose of this investigation is to better understand the error sources of the ozone retrieval, to optimize the current retrieval setup and to document changes in the data versions. It was shown that the cloud clearing technique used so far (cloud index 1.8) does not reliably exclude all cloud-contaminated spectra from analysis. Through analysis of spectra calculated for cloudy atmospheres we found that the cloud index should be increased to a value of 3.0 or higher. Further, it was found that assignment of a common background continuum to adjacent microwindows within 5 cm<sup>−1</sup> is advantageous, because it sufficiently represents the continuum emission by aerosols, clouds and gases as reported in the literature, and is computationally more efficient. For ozone retrieval we use ozone lines from MIPAS band A (685–970 cm<sup>−1</sup>) and band AB (1020–1170 cm<sup>−1</sup>) as well. Therefore we checked ozone retrievals with lines from bands A or AB only for a systematic difference. Such a difference was indeed found and could, to a major part, be attributed to the spectroscopic data used in these two bands, and to a minor part to neglection of modelling of non-local thermodynamic (non-LTE) emissions. Another potential explanation, a bias in the radiance calibration of level-1B spectra of bands A and AB, could largely be ruled out by correlation analysis and inspection of broadband spectra. Further upgrades in the ozone retrieval consist of application of an all-zero a-priori profile and a weaker regularization. Finally, the ozone distribution obtained with the new retrieval setup (data versions V3o_O3_7) was compared to the data version used before (V2_O3_2). Differences are smaller than ±0.4 ppmv in the altitude region 15–50 km. Further, differences to ozone measured by the HALogen Occultation Experiment (HALOE) on the Upper Atmospheric Research Satellite (UARS) are partly reduced with the new MIPAS data version.
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This study covers four years of aerosol number size distribution data from Pallas and Värriö sites 250 km apart from each other in Northern Finland and compares new particle formation events between these sites. In air masses of eastern origin almost all events were observed to start earlier at the eastern station Värriö, whereas in air masses of western origin most of the events were observed to start earlier at the western station Pallas. This demonstrates that particle formation in a certain air mass type depends not only on the diurnal variation of the parameters causing the phenomenon (such as photochemistry) but also on some properties carried by the air mass itself. The correlation in growth rates between the two sites was relatively good, which suggests that the amount of condensable vapour causing the growth must have been at about the same level in both sites. The condensation sink was frequently much higher at the downwind station. It seems that secondary particle formation related to biogenic sources dominate in many cases over the particle sinks during the air mass transport between the sites. Two cases of transport from Pallas to Värriö were further analysed with an aerosol dynamics model. The model was able to reproduce the observed nucleation events 250 km down-wind at Värriö but revealed some differences between the two cases. The simulated nucleation rates were in both cases similar but the organic concentration profiles that best reproduced the observations were different in the two cases indicating that divergent formation reactions may dominate under different conditions. The simulations also suggested that organic compounds were the main contributor to new particle growth, which offers a tentative hypothesis to the distinct features of new particles at the two sites: Air masses arriving from the Atlantic Ocean typically spent approximately only ten hours over land before arriving at Pallas, and thus the time for the organic vapours to accumulate in the air and to interact with the particles is relatively short. This can lead to low nucleation mode growth rates and even to suppression of detectable particle formation event due to efficient scavenging of newly formed clusters, as was observed in the case studies.
