ALBERT

Description: Time series of total column abundances of hydrogen chloride (HCl), chlorine nitrate (ClONO2), and hydrogen fluoride (HF) were determined from ground-based Fourier transform infrared (FTIR) spectra recorded at 17 sites belonging to the Network for the Detection of Atmospheric Composition Change (NDACC) and located between 80.05° N and 77.82° S. By providing such a near-global overview on ground-based measurements of the two major stratospheric chlorine reservoir species, HCl and ClONO2, the present study is able to confirm the decrease of the atmospheric inorganic chlorine abundance during the last few years. This decrease is expected following the 1987 Montreal Protocol and its amendments and adjustments, where restrictions and a subsequent phase-out of the prominent anthropogenic chlorine source gases (solvents, chlorofluorocarbons) were agreed upon to enable a stabilisation and recovery of the stratospheric ozone layer. The atmospheric fluorine content is expected to be influenced by the Montreal Protocol, too, because most of the banned anthropogenic gases also represent important fluorine sources. But many of the substitutes to the banned gases also contain fluorine so that the HF total column abundance is expected to have continued to increase during the last few years. The measurements are compared with calculations from five different models: the two-dimensional Bremen model, the two chemistry-transport models KASIMA and SLIMCAT, and the two chemistry-climate models EMAC and SOCOL. Thereby, the ability of the models to reproduce the absolute total column amounts, the seasonal cycles, and the temporal evolution found in the FTIR measurements is investigated and inter-compared. This is especially interesting because the models have different architectures. The overall agreement between the measurements and models for the total column abundances and the seasonal cycles is good. Linear trends of HCl, ClONO2, and HF are calculated from both measurement and model time series data, with a focus on the time range 2000–2009. This period is chosen because from most of the measurement sites taking part in this study, data are available during these years. The precision of the trends is estimated with the bootstrap resampling method. The sensitivity of the trend results with respect to the fitting function, the time of year chosen and time series length is investigated, as well as a bias due to the irregular sampling of the measurements. The measurements and model results investigated here agree qualitatively on a decrease of the chlorine species by around 1% yr−1. The models simulate an increase of HF of around 1% yr−1. This also agrees well with most of the measurements, but some of the FTIR series in the Northern Hemisphere show a stabilisation or even a decrease in the last few years. In general, for all three gases, the measured trends vary more strongly with latitude and hemisphere than the modelled trends. Relative to the FTIR measurements, the models tend to underestimate the decreasing chlorine trends and to overestimate the fluorine increase in the Northern Hemisphere. At most sites, the models simulate a stronger decrease of ClONO2 than of HCl. In the FTIR measurements, this difference between the trends of HCl and ClONO2 depends strongly on latitude, especially in the Northern Hemisphere.

Description: High molecular weight (300–650 Da) naturally charged negative ions have previously been observed at a boreal forest site in Hyytiälä, Finland. The long-term measurements conducted in this work showed that these ions are observed practically every night between spring and autumn in Hyytiälä. The ambient mass spectral patterns could be reproduced in striking detail during additional measurements of α-pinene (C10H16) oxidation at low-OH conditions in the Jülich Plant Atmosphere Chamber (JPAC). The ions were identified as clusters of the nitrate ion (NO3−) and α-pinene oxidation products reaching oxygen to carbon ratios of 0.7–1.3, while retaining most of the initial ten carbon atoms. Attributing the ions to clusters instead of single molecules was based on additional observations of the same extremely oxidized organics in clusters with HSO4− (Hyytiälä) and C3F5O2− (JPAC). The most abundant products in the ion spectra were identified as C10H14O7, C10H14O9, C10H16O9, and C10H14O11. The mechanism responsible for forming these molecules is still not clear, but the initial reaction is most likely ozone attack at the double bond, as the ions are mainly observed under dark conditions. β-pinene also formed highly oxidized products under the same conditions, but less efficiently, and mainly C9 compounds which were not observed in Hyytiälä, where β-pinene on average is 4–5 times less abundant than α-pinene. Further, to explain the high O/C together with the relatively high H/C, we propose that geminal diols and/or hydroperoxide groups may be important. We estimate that the night-time concentration of the sum of the neutral extremely oxidized products is on the order of 0.1–1 ppt (~106–107 molec cm−3). This is in a similar range as the amount of gaseous H2SO4 in Hyytiälä during day-time. As these highly oxidized organics are roughly 3 times heavier, likely with extremely low vapor pressures, their role in the initial steps of new aerosol particle formation and growth may be important and needs to be explored in more detail in the future.

Description: The mesospheric hydroxyl radical (OH) is mainly produced by the water vapor (H2O) photolysis and could be considered as a proxy for the influence of the solar irradiance variability on the mesosphere. We analyze the tropical mean response of the mesospheric OH and H2O data as observed by the Aura Microwave Limb Sounder (MLS) to 27-day solar variability. The analysis is performed for two time periods corresponding to the different phases of the 11-yr cycle: from December 2004 to December 2005 (the period of "high activity" with a pronounced 27-day solar cycle) and from August 2008 to August 2009 ("solar minimum" period with a vague 27-day solar cycle). We demonstrate, for the first time, that in the mesosphere the daily time series of OH concentrations correlate well with the solar irradiance (correlation coefficients up to 0.79) at zero time-lag. At the same time H2O anticorrelates (correlation coefficients up to −0.74) with the solar irradiance at non-zero time-lag. We found that the response of OH and H2O to the 27-day variability of the solar irradiance is strong for the period of the high solar activity and negligible for the solar minimum conditions. It allows us to suggest that the 27-day cycle in the solar irradiance and in OH and H2O are physically connected.

Description: Observations of aerosol chemical composition in Cabauw, the Netherlands, are presented for two intensive measurement periods in May 2008 and March 2009. Sub-micron aerosol chemical composition was measured by an Aerodyne Aerosol Mass Spectrometer (AMS) and is compared to observations from aerosol size distribution measurements as well as composition measurements with a Monitor for AeRosol and GAses (MARGA) based instrument and a Thermal-Desorption Proton-Transfer-Reaction Mass-Spectrometer (TD-PTR-MS). An overview of the data is presented and the data quality is discussed. In May 2008 enhanced pollution was observed with organics contributing 40% to the PM1 mass. In contrast the observed average mass loading was lower in March 2009 and a dominance of ammonium nitrate (42%) was observed. The semi-volatile nature of ammonium nitrate is evident in the diurnal cycles with maximum concentrations observed in the morning hours in May 2008 and little diurnal variation observed in March 2009. Size dependent composition data from AMS measurements are presented and show a dominance of organics in the size range below 200 nm. A higher O:C ratio of the organics is observed for May 2008 than for March 2009. Together with the time series of individual tracer ions this shows the dominance of OOA over HOA in May 2008.

Description: The study investigates the sources of fine organic aerosol (OA) in the boreal forest, based on measurements including both filter sampling (PM1) and online methods and carried out during a one-month campaign held in Hyytiälä, Finland, in spring 2007. Two aerosol mass spectrometers (Q-AMS, ToF-AMS) were employed to measure on-line concentrations of major non-refractory aerosol species, while the water extracts of the filter samples were analyzed by nuclear magnetic resonance (NMR) spectroscopy for organic functional group characterization of the polar organic fraction of the aerosol. AMS and NMR spectra were processed separately by non-negative factorization algorithms, in order to apportion the main components underlying the submicrometer organic aerosol composition and depict them in terms of both mass fragmentation patterns and functional group compositions. The NMR results supported the AMS speciation of oxidized organic aerosol (OOA) into two main fractions, which could be generally labelled as more and less oxidized organics. The more oxidized component was characterized by a mass spectrum dominated by the m/z 44 peak, and in parallel by a NMR spectrum showing aromatic and aliphatic backbones highly substituted with oxygenated functional groups (carbonyls/carboxyls and hydroxyls). Such component, contributing on average 50% of the OA mass throughout the observing period, was associated with pollution outbreaks from the Central Europe. The less oxidized component was enhanced in concomitance with air masses originating from the North-to-West sector, in agreement with previous investigations conducted at this site. NMR factor analysis was able to separate two distinct components under the less oxidized fraction of OA. One of these NMR-factors was associated with the formation of terrestrial biogenic secondary organic aerosol (BSOA), based on the comparison with spectral profiles obtained from laboratory experiments of terpenes photo-oxidation. The second NMR factor associated with western air masses was linked to biogenic marine sources, and was enriched in low-molecular weight aliphatic amines. Such findings provide evidence of at least two independent sources originating biogenic organic aerosols in Hyytiälä by oxidation and condensation mechanisms: reactive terpenes emitted by the boreal forest and compounds of marine origin, with the latter relatively more important when predominantly polar air masses reach the site. This study is an example of how spectroscopic techniques, such as proton NMR, can add functional group specificity for certain chemical features (like aromatics) of OA with respect to AMS. They can therefore be profitably exploited to complement aerosol mass spectrometric measurements in organic source apportionment studies.

Description: Ice and snow in the environment are important because they not only act as a host to rich chemistry but also provide a matrix for physical exchanges of contaminants within the ecosystem. This review discusses how the structure of snow influences both chemical reactivity and physical processes, which thereby makes snow a unique medium for study. The focus is placed on impacts of the presence of liquid and surface disorder using many experimental studies, simulations, and field observations from the molecular to the micro-scale.

Description: From 12 to 14 August 2010, heavy rainstorms occurred in the Sichuan province in SW China in areas which were affected by the 2008 Wenchuan Earthquake, inducing catastrophic debris flows. This disaster is named as "the 8.13 debris flows". The results of the research presented in this paper show that the 8.13 debris flows are characterized by a simultaneous occurrence, rapid-onsets, destructive impacts, and disaster chain effects. They are located along the seismic fault, because the source materials mainly originate from loose deposits of landslides which were triggered by the Wenchuan Earthquake. The presence of large amounts of these loose materials on the slopes and the development of high intensity rainfall events are the main causes for the formation of these debris flows. The study of the 8.13 debris flows can provide a benchmark for the analysis of the long-term evolution of these debris flows in order to make proper engineering decisions. A flexible drainage system is proposed in this paper as a preventive measure to mitigate the increasing activity of these debris flows in the earthquake-affected area.

Description: The occurrence of debris flows has been recorded for more than a century in the European Alps, accounting for the risk to settlements and other human infrastructure that have led to death, building damage and traffic disruptions. One of the difficulties in the quantitative hazard assessment of debris flows is estimating the run-out behavior, which includes the run-out distance and the related hazard intensities like the height and velocity of a debris flow. In addition, as observed in the French Alps, the process of entrainment of material during the run-out can be 10–50 times in volume with respect to the initially mobilized mass triggered at the source area. The entrainment process is evidently an important factor that can further determine the magnitude and intensity of debris flows. Research on numerical modeling of debris flow entrainment is still ongoing and involves some difficulties. This is partly due to our lack of knowledge of the actual process of the uptake and incorporation of material and due the effect of entrainment on the final behavior of a debris flow. Therefore, it is important to model the effects of this key erosional process on the formation of run-outs and related intensities. In this study we analyzed a debris flow with high entrainment rates that occurred in 2003 at the Faucon catchment in the Barcelonnette Basin (Southern French Alps). The historic event was back-analyzed using the Voellmy rheology and an entrainment model imbedded in the RAMMS 2-D numerical modeling software. A sensitivity analysis of the rheological and entrainment parameters was carried out and the effects of modeling with entrainment on the debris flow run-out, height and velocity were assessed.

Description: Hydrological processes control the behaviour of many unstable slopes, and their importance for landslide activity is generally accepted. The presence of fissures influences the storage capacity of a soil and affects the infiltration processes of rainfall. The effectiveness of the fissure network depends upon fissure size, their spatial distribution, and connectivity. Moreover, fissure connectivity is a dynamic characteristic, depending on the degree of saturation of the medium. This research aims to investigate the influence of the fissure network on hydrological responses of a landslide. Special attention is given to spatial and temporal variations in fissure connectivity, which makes fissures act both as preferential flow paths for deep infiltration (disconnected fissures) and as lateral groundwater drains (connected fissures). To this end, the hydrological processes that control the exchange of water between the fissure network and the matrix have been included in a spatially distributed hydrological and slope stability model. The ensuing feedbacks in landslide hydrology were explored by running the model with one year of meteorological forcing. The effect of dynamic fissure connectivity was evaluated by comparing simulations with static fissure patterns to simulations in which these patterns change as a function of soil saturation. The results highlight that fissure connectivity and fissure permeability control the water distribution within landslides. Making the fissure connectivity function of soil moisture results in composite behaviour spanning the above end members and introduces stronger seasonality of the hydrological responses.