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The importance of ion-induced nucleation in the lower atmosphere has been discussed for a long time. In this article we describe a new instrumental setup – Ion-DMPS – which can be used to detect contribution of ion-induced nucleation on atmospheric new particle formation events. The device measures positively and negatively charged particles with and without a bipolar charger. The ratio between "charger off" to "charger on" describes the charging state of aerosol particle population with respect to equilibrium. Values above one represent more charges than in an equilibrium (overcharged state), and values below unity stand for undercharged situation, when there is less charges in the particles than in the equilibrium. <br><br> We performed several laboratory experiments to test the operation of the instrument. After the laboratory tests, we used the device to observe particle size distributions during atmospheric new particle formation in a boreal forest. We found that some of the events were clearly dominated by neutral nucleation but in some cases also ion-induced nucleation contributed to the new particle formation. We also found that negative and positive ions (charged particles) behaved in a different manner, days with negative overcharging were more frequent than days with positive overcharging.
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This paper gives an overview of the MIPAS Level 1B (L1B) processor whose main objective is to calibrate atmospheric measurements radiometrically, spectrally and geo-located. It presents also the results of instrument characterization done on ground and during the first years in-flight. An accurate calibration is mandatory for high quality atmospheric retrievals. MIPAS has shown very good performance and stability. The noise equivalent spectral radiance ranges from 3 to 50 nW/(cm<sup>2</sup> sr cm<sup>−1</sup>) and is well within the requirements over nearly the whole spetral range. The systematic radiometric error is estimated to be within 1 or 2% in most situations.
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The speciation of iodine in atmospheric aerosol is currently poorly understood. Models predict negligible iodide concentrations but accumulation of iodate in aerosol, both of which is not confirmed by recent measurements. We present an updated aqueous phase iodine chemistry scheme for use in atmospheric chemistry models and discuss sensitivity studies with the marine boundary layer model MISTRA. These studies show that iodate can be reduced in acidic aerosol by inorganic reactions, i.e., iodate does not necessarily accumulate in particles. Furthermore, the transformation of particulate iodide to volatile iodine species likely has been overestimated in previous model studies due to negligence of collision-induced upper limits for the reaction rates. However, inorganic reaction cycles still do not seem to be sufficient to reproduce the observed range of iodide – iodate speciation in atmospheric aerosol. Therefore, we also investigate the effects of the recently suggested reaction of HOI with dissolved organic matter to produce iodide. If this reaction is fast enough to compete with the inorganic mechanism, it would not only directly lead to enhanced iodide concentrations but, indirectly via speed-up of the inorganic iodate reduction cycles, also to a decrease in iodate concentrations. Hence, according to our model studies, organic iodine chemistry, combined with inorganic reaction cycles, is able to reproduce observations. The presented chemistry cycles are highly dependent on pH and thus offer an explanation for the large observed variability of the iodide – iodate speciation in atmospheric aerosol.
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The recent observation of ultrafine aerosol particles in cirrus clouds has raised the question whether aerosol formation within cirrus clouds is possible, and if so, what mechanisms are involved. We have developed an aerosol parcel model of neutral and charged H<sub>2</sub>SO<sub>4</sub>/H<sub>2</sub>O aerosol processes, including nucleation from the gas phase and loss onto cirrus ice particles. Laboratory thermodynamic data for sulfuric acid uptake and loss by small neutral and charged clusters are used, allowing for a reliable description of both neutral and charged nucleation down to the very low temperatures occurring in the upper troposphere and lower stratosphere. The model implements a first order scheme for resolving the aerosol size distribution within its geometric size sections, which efficiently suppresses numerical diffusion. We operate the model offline on trajectories generated with a detailed 1D cirrus model which describes ice crystal nucleation, deposition growth, vertical advection of ice crystals and water vapor, and ice crystal sedimentation. In this paper we explore the possibility of aerosol formation within non-convective cirrus clouds and draw conclusions for aerosol formation in anvil cirrus. We find that sulfate aerosol formation within cirrus clouds can proceed even at high ice surface area concentrations, and depends strongly on the size of the cirrus ice crystals and on the surface area concentration of preexisting aerosol particles.
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This paper presents a comparison of lidar ratios and volume extinction coefficients in tropical ice clouds, retrieved using observations from two instruments: the 532-nm <it>Cloud Physics Lidar</it> (CPL), and the in-situ <it>Cloud Integrating Nephelometer</it> (CIN) probe. Both instruments were mounted on airborne platforms during the CRYSTAL-FACE campaign and took measurements up to 17 km. Coincident observations from two cases of ice clouds located on top of deep convective systems are compared. First, lidar ratios are retrieved from CPL observations of attenuated backscatter, using a retrieval algorithm for opaque cloud similar to one used in the recently launched CALIPSO mission, and compared to results from the regular CPL algorithm. These lidar ratios are used to retrieve extinction coefficient profiles, which are compared to actual observations from the CIN in-situ probe, putting the emphasis on their vertical variability. When observations coincide, retrievals from both instruments are very similar, in the limits of colocation. Differences are generally variations around the average profiles, and general trends on larger spatial scales are well reproduced. The two instruments agree well, with an average difference of less than 11% on optical depth retrievals. Results suggest the CALIPSO Deep Convection algorithm can be trusted to deliver realistic estimates of the lidar ratio, leading to good retrievals of extinction coefficients.
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The use of SAGE III multiwavelength aerosol extinction coefficient measurements to infer PSC type is contingent on the robustness of both the extinction magnitude and its spectral variation. Past validation with SAGE II and other similar measurements has shown that the SAGE III extinction coefficient measurements are reliable though the comparisons have been greatly weighted toward measurements made at mid-latitudes. Some aerosol comparisons made in the Arctic winter as a part of SOLVE II suggested that SAGE III values, particularly at longer wavelengths, are too small with the implication that both the magnitude and the wavelength dependence are not reliable. Comparisons with POAM III have also suggested a similar discrepancy. Herein, we use SAGE II data as a common standard for comparison of SAGE III and POAM III measurements in the Arctic winters of 2002/2003 through 2004/2005. During the winter, SAGE II measurements are made infrequently at the same latitudes as these instruments. We have mitigated this problem through the use of potential vorticity as a spatial coordinate and thus greatly increased of the number of coincident events. We find that SAGE II and III extinction coefficient measurements show a high degree of compatibility at both 1020 nm and 450 nm except a 10–20% bias at both wavelengths. In addition, the 452 to 1020 nm extinction ratio shows a consistent bias of ~30% throughout the lower stratosphere. We also find that SAGE II and POAM III are on average consistent though the comparisons show a much higher variability and larger bias than SAGE II/III comparisons. In addition, we find that SAGE II and POAM III data sets are not well correlated at and below 18 km. Overall, we find both the extinction values and the spectral dependence from SAGE III are robust and we find no evidence of a significant defect within the Arctic vortex.
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The retrieval of concentration vertical profiles of atmospheric constituents from spectroscopic measurements is often an ill-conditioned problem and regularization methods are frequently used to improve its stability. Recently a new method, that provides a good compromise between precision and vertical resolution, was proposed to determine analytically the value of the regularization parameter. This method is applied for the first time to real measurements with its implementation in the operational retrieval code of the satellite limb-emission measurements of the MIPAS instrument and its performances are quantitatively analyzed. The adopted regularization improves the stability of the retrieval providing smooth profiles without major degradation of the vertical resolution. In the analyzed measurements the retrieval procedure provides a vertical resolution that, in the troposphere and low stratosphere, is smaller than the vertical field of view of the instrument.
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In this study, we evaluate the ability of the BRAMS (Brazilian Regional Atmospheric Modeling System) mesoscale model compared to ECMWF global analysis to simulate the observed vertical variations of water vapour in the tropical upper troposphere and lower stratosphere (UTLS). The observations are balloon-borne measurements of water vapour mixing ratio and temperature from micro-SDLA (Tunable Diode Laser Spectrometer) instrument. Data from two balloon flights performed during the 2004 HIBISCUS field campaign are used to compare with the mesoscale simulations and to the ECMWF analysis. <br><br> The observations exhibit fine scale vertical structures of water vapour of a few hundred meters height. The ECMWF vertical resolution (~1 km) is too coarse to capture these vertical structures in the UTLS. With a vertical resolution similar to ECMWF, the mesoscale model performs better than ECMWF analysis for water vapour in the upper troposphere and similarly or slightly worse for temperature. The BRAMS model with 250 m vertical resolution is able to capture more of the observed fine scale vertical variations of water vapour compared to runs with a coarser vertical resolution. This is mainly related to: (i) the enhanced vertical resolution in the UTLS and (ii) to the more detailed microphysical parameterization providing ice supersaturations as in the observations. In near saturated or supersaturated layers, the mesoscale model predicted relative humidity with respect to ice saturation is close to observations provided that the temperature profile is realistic. For temperature, the ECMWF analysis gives good results partly attributed to data assimilation. The analysis of the mesoscale model results showed that the vertical variations of the water vapour profile depends on the dynamics in unsaturated layer while the microphysical processes play a major role in saturated/supersaturated layers. <br><br> In the lower stratosphere, the ECMWF model and the BRAMS model give very similar water vapour profiles that are significantly drier than micro-SDLA measurements. This similarity comes from the fact that BRAMS is initialised using ECMWF analysis and that no mesoscale process acts in the stratosphere leading to no modification of the BRAMS results with respect to ECMWF analysis.
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Submicron ambient aerosol was characterized in summer 2005 at an urban background site in Zurich, Switzerland, during a three-week measurement campaign. Highly time-resolved samples of non-refractory aerosol components were analyzed with an Aerodyne aerosol mass spectrometer (AMS). Positive matrix factorization (PMF) was used for the first time for aerosol mass spectra to identify the main components of the total organic aerosol and their sources. The PMF retrieved factors were compared to measured reference mass spectra and were correlated with tracer species of the aerosol and gas phase measurements from collocated instruments. Six factors were found to explain virtually all variance in the data and could be assigned either to sources or to aerosol components such as oxygenated organic aerosol (OOA). Our analysis suggests that at the measurement site only a small (<10%) fraction of organic PM<sub>1</sub> originates from freshly emitted fossil fuel combustion. Other primary sources identified to be of similar or even higher importance are charbroiling (10–15%) and wood burning (~10%). The fraction of all identified primary sources is considered as primary organic aerosol (POA). This interpretation is supported by calculated ratios of the modelled POA and measured primary pollutants such as elemental carbon (EC), NO<sub>x</sub>, and CO, which are in good agreement to literature values. A high fraction (60–69%) of the measured organic aerosol mass is OOA which is interpreted mostly as secondary organic aerosol (SOA). This oxygenated organic aerosol can be separated into a highly aged fraction, OOA I, (40–50%) with low volatility and a mass spectrum similar to fulvic acid, and a more volatile and probably less processed fraction, OOA II (on average 20%). This is the first publication of a multiple component analysis technique to AMS organic spectral data and also the first report of the OOA II component.
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Application of cavity ring down (CRD) spectrometry for measuring the optical properties of pure and mixed laboratory-generated aerosols is presented. The extinction coefficient (α<sub>ext</sub>), extinction cross section (σ<sub>ext</sub>) and extinction efficiency (Q<sub>ext</sub>) were measured for polystyrene spheres (PSS), ammonium sulphate ((NH<sub>4</sub>)<sub>2</sub>(SO<sub>4</sub>), sodium chloride (NaCl), glutaric acid (GA), and Rhodamine-590 aerosols. The refractive indices of the different aerosols were retrieved by comparing the measured extinction efficiency of each aerosol type to the extinction predicted by Mie theory. Aerosols composed of sodium chloride and glutaric acid in different mixing ratios were used as model for mixed aerosols of two non-absorbing materials, and their extinction and complex refractive index were derived. Aerosols composed of Rhodamine-590 and ammonium sulphate in different mixing ratios were used as model for mixing of absorbing and non-absorbing species, and their optical properties were derived. The refractive indices of the mixed aerosols were also calculated by various optical mixing rules. We found that for non-absorbing mixtures, the linear rule, Maxwell-Garnett rule, and extended effective medium approximation (EEMA), give comparable results, with the linear mixing rule giving a slightly better fit than the others. Overall, calculations for the mixed aerosols are not as good as for single component aerosols. For absorbing mixtures, the differences between the refractive indices calculated using the mixing rules and those retrieved by CRD are generally higher.
