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Developing a western Siberia reference site for tropospheric water vapour isotopologue observations obtained by different techniques (in situ and remote sensing)

Water stable isotopologues provide integrated tracers of the atmospheric water cycle, affected by changes in air mass origin, non-convective and convective processes and continental recycling. Novel remote sensing and in situ measuring techniques have recently offered opportunities for monitoring atmospheric water vapour isotopic composition. Recently developed infrared laser spectrometers allow for continuous in situ measurements of surface water vapour δDv and δ18Ov. So far, very few intercomparisons of measurements conducted using different techniques have been achieved at a given location, due to difficulties intrinsic to the comparison of integrated with local measurements. Nudged simulations conducted with high-resolution isotopically enabled general circulation models (GCMs) provide a consistent framework for comparison with the different types of observations. Here, we compare simulations conducted with the ECHAM5-wiso model with two types of water vapour isotopic data obtained during summer 2012 at the forest site of Kourovka, western Siberia: hourly ground-based FTIR total atmospheric columnar δDv amounts, and in situ hourly Picarro δDv measurements. There is an excellent correlation between observed and predicted δDv at surface while the comparison between water column values derived from the model compares well with FTIR estimates.
Estimation of aerosol water and chemical composition from AERONET Sun–sky radiometer measurements at Cabauw, the Netherlands

Remote sensing of aerosols provides important information on atmospheric aerosol abundance. However, due to the hygroscopic nature of aerosol particles observed aerosol optical properties are influenced by atmospheric humidity, and the measurements do not unambiguously characterize the aerosol dry mass and composition, which complicates the comparison with aerosol models. In this study we derive aerosol water and chemical composition by a modeling approach that combines individual measurements of remotely sensed aerosol properties (e.g., optical thickness, single-scattering albedo, refractive index and size distribution) from an AERONET (Aerosol Robotic Network) Sun–sky radiometer with radiosonde measurements of relative humidity. The model simulates water uptake by aerosols based on the chemical composition (e.g., sulfates, ammonium, nitrate, organic matter and black carbon) and size distribution. A minimization method is used to calculate aerosol composition and concentration, which are then compared to in situ measurements from the Intensive Measurement Campaign At the Cabauw Tower (IMPACT, May 2008, the Netherlands). Computed concentrations show good agreement with campaign-average (i.e., 1–14 May) surface observations (mean bias is 3% for PM10 and 4–25% for the individual compounds). They follow the day-to-day (synoptic) variability in the observations and are in reasonable agreement for daily average concentrations (i.e., mean bias is 5% for PM10 and black carbon, 10% for the inorganic salts and 18% for organic matter; root-mean-squared deviations are 26% for PM10 and 35–45% for the individual compounds). The modeled water volume fraction is highly variable and strongly dependent on composition. During this campaign we find that it is >0.5 at approximately 80% relative humidity (RH) when the aerosol composition is dominated by hygroscopic inorganic salts, and <0.1 when RH is below 40%, especially when the composition is dominated by less hygroscopic compounds such as organic matter. The scattering enhancement factor (f(RH), the ratio of the scattering coefficient at 85% RH and its dry value at 676 nm) during 1–14 May is 2.6 ± 0.5. The uncertainty in AERONET (real) refractive index (0.025–0.05) is the largest source of uncertainty in the modeled aerosol composition and leads to an uncertainty of 0.1–0.25 (50–100%) in aerosol water volume fraction. Our methodology performs relatively well at Cabauw, but a better performance may be expected for regions with higher aerosol loading where the uncertainties in the AERONET inversions are smaller.
Heterogeneous reaction of N2O5 with airborne TiO2 particles and its implication for stratospheric particle injection

Injection of aerosol particles (or their precursors) into the stratosphere to scatter solar radiation back into space has been suggested as a solar-radiation management scheme for the mitigation of global warming. TiO2 has recently been highlighted as a possible candidate particle because of its high refractive index, but its impact on stratospheric chemistry via heterogeneous reactions is as yet unknown. In this work the heterogeneous reaction of airborne sub-micrometre TiO2 particles with N2O5 has been investigated for the first time, at room temperature and different relative humidities (RH), using an atmospheric pressure aerosol flow tube. The uptake coefficient of N2O5 onto TiO2, γ(N2O5), was determined to be ~1.0 × 10−3 at low RH, increasing to ~3 × 10−3 at 60% RH. The uptake of N2O5 onto TiO2 is then included in the UKCA chemistry–climate model to assess the impact of this reaction on stratospheric chemistry. While the impact of TiO2 on the scattering of solar radiation is chosen to be similar to the aerosol from the Mt Pinatubo eruption, the impact of TiO2 injection on stratospheric N2O5 is much smaller.
Cloud condensation nucleus activity comparison of dry- and wet-generated mineral dust aerosol: the significance of soluble material

This study examines the interaction of clay mineral particles and water vapor for determining the conditions required for cloud droplet formation. Droplet formation conditions are investigated for two common clay minerals, illite and sodium-rich montmorillonite, and an industrially derived sample, Arizona Test Dust. Using wet and dry particle generation coupled to a differential mobility analyzer (DMA) and cloud condensation nuclei counter, the critical activation of the clay mineral particles as cloud condensation nuclei is characterized. Electron microscopy (EM) is used in order to determine non-sphericity in particle shape. It is also used in order to determine particle surface area and account for transmission of multiply charged particles by the DMA. Single particle mass spectrometry and ion chromatography are used to investigate soluble material in wet-generated samples and demonstrate that wet and dry generation yield compositionally different particles. Activation results are analyzed in the context of both κ-Köhler theory (κ-KT) and Frenkel–Halsey–Hill (FHH) adsorption activation theory. This study has two main results: (1) κ-KT is the suitable framework to describe clay mineral nucleation activity. Apparent differences in κ with respect to size arise from an artifact introduced by improper size-selection methodology. For dust particles with mobility sizes larger than ~300 nm, i.e., ones that are within an atmospherically relevant size range, both κ-KT and FHH theory yield similar critical supersaturations. However, the former requires a single hygroscopicity parameter instead of the two adjustable parameters required by the latter. For dry-generated particles, the size dependence of κ is likely an artifact of the shape of the size distribution: there is a sharp drop-off in particle concentration at ~300 nm, and a large fraction of particles classified with a mobility diameter less than ~300 nm are actually multiply charged, resulting in a much lower critical supersaturation for droplet activation than expected. For wet-generated particles, deviation from κ-KT is likely a result of the dissolution and redistribution of soluble material. (2) Wet generation is found to be unsuitable for simulating the lofting of fresh dry dust because it changes the size-dependent critical supersaturations by fractionating and re-partitioning soluble material.
Solar irradiance in the heterogeneous albedo environment of the Arctic coast: measurements and a 3-D model study

We present a unique case study of the solar global irradiance in a highly heterogeneous albedo environment at the Arctic coast. Diodearray spectroradiometers were deployed at three sites around Ny Ålesund, Svalbard, and spectral irradiances were simultaneously measured under clear-sky conditions during a 24 h period. The 3-D radiative transfer model MYSTIC is applied to simulate the measurements in various model scenarios. First, we model the effective albedos of ocean and snow and consequently around each measurement site. The effective albedos at 340 nm increase from 0.57 to 0.75, from the coastal site in the west towards the site 20 km east, away from the coast. The observed ratios of the global irradiance indicate a 15% higher average irradiance, at 340 nm east relative to west, due to the higher albedo. The comparison of our model scenarios suggest a snow albedo of > 0.9 and confirm the observation that drift ice has moved into the Fjord during the day. The local time shift between the locations causes a hysteresis-like behavior of these east–west ratios with solar zenith angle (SZA). The observed hysteresis, however, is larger and, at 340 nm, can be explained by the drift ice. At 500 nm, a plausible explanation is a detector tilt of about 1°. The ratios between afternoon and morning irradiances at the same SZA are investigated, which confirm the above conclusions. At the coastal site, the measured irradiance is significantly higher in the afternoon than in the morning. Besides the effect of changing drift ice and detector tilt, the small variations of the aerosol optical depth have to be considered also at the other stations to reduce the discrepancies between model and observations. Remaining discrepancies are possibly due to distant high clouds.
The effect of local sources on particle size and chemical composition and their role in aerosol–cloud interactions at Puijo measurement station

Interactions between aerosols and liquid water clouds were studied during autumns 2010–2011 at a semiurban measurement station on Puijo tower in Kuopio, Finland. Cloud interstitial and total aerosol size distributions, particle chemical composition and hygroscopicity and cloud droplet size distribution were measured, with a focus on comparing clean air masses with those affected by local sources. On average, the polluted air contained more particles than the clean air masses, and generally the concentrations decreased during cloud events. Cloud processing was found to take place, especially in the clean air masses, and to a lesser extent in the polluted air. Some, mostly minor, differences in the average particle chemical composition between the air masses were observed. The average size and number concentration of activating particles were quite similar for both air masses, producing average droplet populations with only minor distinctions. As a case study, a long cloud event was analyzed in detail, with a special focus on the emissions from local sources, including a paper mill and a heating plant. This revealed larger variations in particle and cloud properties than the analysis of the whole data set. Clear differences in the total (between 214 and 2200 cm−3) and accumulation mode particle concentrations (between 62 and 169 cm−3) were observed. Particle chemical composition, especially the concentrations of organics (between 0.42 and 1.28 μg m−3) and sulfate (between 0.16 and 4.43 μg m−3), varied considerably. This affected the hygroscopic growth factor: for example, for 100 nm particles the range was from 1.21 to 1.45 at 90% relative humidity. Particularly, large particles, high hygroscopicities and elevated amounts of inorganics were linked with the pollutant plumes. Moreover, the particle hygroscopicity distributions in the polluted air were clearly bimodal, indicating externally mixed aerosol. The variable conditions also had an impact on cloud droplet formation, with the droplet concentration varying between 138 and 240 cm−3 and mean diameter between 9.2 and 12.4 μm.
The Pagami Creek smoke plume after long-range transport to the upper troposphere over Europe – aerosol properties and black carbon mixing state

During the CONCERT 2011 field experiment with the DLR research aircraft Falcon, an enhanced aerosol layer with particle linear depolarization ratios of 6–8% at 532 nm was observed at altitudes above 10 km over northeast Germany on 16 September 2011. Dispersion simulations with HYSPILT suggest that the elevated aerosol layer originated from the Pagami Creek forest fire in Minnesota, USA, which caused pyro-convective uplift of particles and gases. The 3–4 day-old smoke plume had high total refractory black carbon (rBC) mass concentrations of 0.03–0.35 μg m−3 at standard temperature and pressure (STP) with rBC mass equivalent diameter predominantly smaller than 130 nm. Assuming a core-shell particle structure, the BC cores exhibit very thick (median: 105–136 nm) BC-free coatings. A large fraction of the BC-containing particles disintegrated into a BC-free fragment and a BC fragment while passing through the laser beam of the Single Particle Soot Photometer (SP2). In this study, the disintegration is a result of very thick coatings around the BC cores. This is in contrast to a previous study in a forest-fire plume, where it was hypothesized to be a result of BC cores being attached to a BC-free particle. For the high-altitude forest-fire aerosol layer observed in this study, increased mass specific light-absorption cross sections of BC can be expected due to the very thick coatings around the BC cores, while this would not be the case for the attached-type morphology. We estimate the BC mass import from the Pagami Creek forest fire into the upper troposphere/lower stratosphere (UTLS) region (best estimate: 25 Mg rBC). A comparison to black carbon emission rates from aviation underlines the importance of pyro-convection on the BC load in the UTLS region. Our study provides detailed information on the microphysics and the mixing state of BC in the forest-fire aerosol layer in the upper troposphere that can be used to better understand and investigate the radiative impact of such upper tropospheric aerosol layers.
On the link between Amazonian forest properties and shallow cumulus cloud fields

During the dry season the Amazon forest is frequently covered by shallow cumulus clouds fields, referred to here as forest cumulus (FCu). These clouds are shown to be sensitive to land cover and exhibit a high level of spatial organization. In this study we use satellite data to perform a morphological classification and examine the link between FCu cloud field occurrence and the enhanced vegetation index (EVI), which is commonly used as a measure for forest density and productivity. Although weaker than first-order effects of meteorology, a clear positive linear relation between EVI (i.e., surface properties) and FCu field occurrence is seen over forest land cover, implying a strong coupling between forest surface fluxes and the cloud organization above. Over non-forest land cover the relationship between EVI and FCu occurrence is nonlinear, showing a reduction of FCu for high EVI values. We find that forest to non-forest transition zones display a superposition of the two different land cover dependencies.
Functional characterization of the water-soluble organic carbon of size-fractionated aerosol in the southern Mississippi Valley

The chemical content of water-soluble organic carbon (WSOC) as a function of particle size was characterized in Little Rock, Arkansas in winter and spring 2013. The objectives of this study were to (i) compare the functional characteristics of coarse, fine and ultrafine WSOC and (ii) reconcile the sources of WSOC for periods when carbonaceous aerosol was the most abundant particulate component. The WSOC accounted for 5% of particle mass for particles with dp > 0.96 μm and 10% of particle mass for particles with dp < 0.96 μm. Non-exchangeable aliphatic (H–C), unsaturated aliphatic (H–C–C=), oxygenated saturated aliphatic (H–C–O), acetalic (O–CH–O) and aromatic (Ar–H) protons were determined by proton nuclear magnetic resonance (1H-NMR). The total non-exchangeable organic hydrogen concentrations varied from 4.1 ± 0.1 nmol m−3 for particles with 1.5 < dp < 3.0 μm to 73.9 ± 12.3 nmol m−3 for particles with dp < 0.49 μm. The molar H / C ratios varied from 0.48 ± 0.05 to 0.92 ± 0.09, which were comparable to those observed for combustion-related organic aerosol. The R–H was the most abundant group, representing about 45% of measured total non-exchangeable organic hydrogen concentrations, followed by H–C–O (27%) and H–C–C= (26%). Levoglucosan, amines, ammonium and methanesulfonate were identified in NMR fingerprints of fine particles. Sucrose, fructose, glucose, formate and acetate were associated with coarse particles. These qualitative differences of 1H-NMR profiles for different particle sizes indicated the possible contribution of biological aerosols and a mixture of aliphatic and oxygenated compounds from biomass burning and traffic exhausts. The concurrent presence of ammonium and amines also suggested the presence of ammonium/aminium nitrate and sulfate secondary aerosol. The size-dependent origin of WSOC was further corroborated by the increasing δ13C abundance from −26.81 ± 0.18&permil; for the smallest particles to −25.93 ± 0.31&permil; for the largest particles and the relative distribution of the functional groups as compared to those previously observed for marine, biomass burning and secondary organic aerosol. The latter also allowed for the differentiation of urban combustion-related aerosol and biological particles. The five types of organic hydrogen accounted for the majority of WSOC for particles with dp > 3.0 μm and dp < 0.96 μm.
Effect of water vapor on the determination of aerosol direct radiative effect based on the AERONET fluxes

The aerosol direct radiative effect (ADRE) is defined as the change in the solar radiation flux, F, due to aerosol scattering and absorption. The difficulty in determining ADRE stems mainly from the need to estimate F without aerosols, F0, with either radiative transfer modeling and knowledge of the atmospheric state, or regression analysis of radiation data down to zero aerosol optical depth (AOD), if only F and AOD are observed. This paper examines the regression analysis method by using modeled surface data products provided by the Aerosol Robotic Network (AERONET). We extrapolated F0 by two functions: a straight linear line and an exponential nonlinear decay. The exponential decay regression is expected to give a better estimation of ADRE with a few percent larger extrapolated F0 than the linear regression. We found that, contrary to the expectation, in most cases the linear regression gives better results than the nonlinear. In such cases the extrapolated F0 represents an unrealistically low water vapor column (WVC), resulting in underestimation of attenuation caused by the water vapor, and hence too large F0 and overestimation of the magnitude of ADRE. The nonlinear ADRE is generally 40–50% larger in magnitude than the linear ADRE due to the extrapolated F0 difference. Since for a majority of locations, AOD and WVC have a positive correlation, the extrapolated F0 with the nonlinear regression fit represents an unrealistically low WVC, and hence too large F0. The systematic underestimation of F0 with the linear regression is compensated by the positive correlation between AOD and water vapor, providing the better result.