Diffusivity and enzymatic activity control the exchange of carbonyl sulfide (COS) between soils and the atmosphere

Carbonylsulfid (COS) ist eines der stabilsten reduzierten schwefelhaltigen Spurengase in der Atmosphäre. In der gut durchmischten Troposphäre bewegt sich seine Konzentration um 500 ppt. COS spielt eine wichtige Rolle in der Produktion von stratosphärischem Aerosol und im Ozon Zyklus. Dieses Spurengas hat eine Vielfalt an natürlichen und anthropogenen Quellen, denen gleichstarke Senken, darunter die dominanten wie Vegetation und Boden, gegenüber stehen. Die Stärke der Senken ist trotz langjähriger Forschungen immer noch Gegenstand der Diskussionen. Daher ist es wichtig die kontrollierenden Parameter zu charakterisieren. Alle Austauschmessungen vor 1990 vermuteten Böden als Quelle von COS, was aber durch Castro and Galloway (1991) klar widerlegt wurde. Heute werden Böden in Ergänzung zur Vegetation grundsätzlich als Senke betrachtet. Vor diesem Hintergrund wurden Bodenproben auf den Austausch von Carbonylsulfid mit der Atmosphäre unter verschiedenen Umgebungsbedingungen untersucht. Drei Ackerböden aus Deutschland, China und Finnland und zwei Waldböden aus Sibirien und Surinam konnten parametrisiert werden in Relation zur atmosphärischen Umgebungskonzentration, Temperatur und Bodenfeuchte (WC). Neben Umgebungskonzentration und Bodenfeuchte, scheinen Bodenstruktur und enzymatische Aktivität die Richtung und Größe des Austauschflusses zu kontrollieren. Die übereinstimmenden Optima für boreale Böden in Relation zum wassergefüllten Porenvolumen des Bodens (WFPS) und die Linearität zwischen Depositionsgeschwindigkeit (Vd) und Bulk density lassen auf eine Dominanz der Abhängigkeit der COS-Aufnahme von der durch WFPS bestimmten Diffusionsfähigkeit schließen. WFPS ist abhängig von WC, Bodenstruktur und Bodenporosität. In Ergänzung zu diesen eher physikalischen Parametern konnte die Carboanhydrase (CA) als kontrollierendes Enzym in Böden identifiziert werden. Erste Versuche zur direkten Bestimmung der CA in den untersuchten Böden erlaubten eine erste, aber noch sehr ungenaue Abschätzung der Enzymaktivität.

Chemistry of aerosol particles and fog droplets during fall-winter season in the Po Valley

Air quality represents a key issue in the so-called pollution “hot spots”: environments in which anthropogenic sources are concentrated and dispersion of pollutants is limited. One of these environments, the Po Valley, normally experiences exceedances of PM10 and PM2.5 concentration limits, especially in winter when the ventilation of the lower layers of the atmosphere is reduced. This thesis provides a highlight of the chemical properties of particulate matter and fog droplets in the Po Valley during the cold season, when fog occurrence is very frequent. Fog-particles interactions were investigated with the aim to determine their impact on the regional air quality. Size-segregated aerosol samples were collected in Bologna, urban site, and San Pietro Capofiume (SPC), rural site, during two campaigns (November 2011; February 2013) in the frame of Supersito project. The comparison between particles size-distribution and chemical composition in both sites showed the relevant contribution of the regional background and secondary processes in determining the Po Valley aerosol concentration. Occurrence of fog in November 2011 campaign in SPC allowed to investigate the role of fog formation and fog chemistry in the formation, processing and deposition of PM10. Nucleation scavenging was investigated with relation to the size and the chemical composition of particles. We found that PM1 concentration is reduced up to 60% because of fog scavenging. Furthermore, aqueous-phase secondary aerosol formation mechanisms were investigated through time-resolved measurements. In SPC fog samples have been systematically collected and analysed since the nineties; a 20 years long database has been assembled. This thesis reports for the first time the results of this long time series of measurements, showing a decrease of sulphate and nitrate concentration and an increase of pH that reached values close to neutrality. A detailed discussion about the occurred changes in fog water composition over two decades is presented.

Exchange of nitrogen dioxide (NO 2) between plants and the atmosphere under laboratory and field conditions

Nitrogen is an essential nutrient. It is for human, animal and plants a constituent element of proteins and nucleic acids. Although the majority of the Earth’s atmosphere consists of elemental nitrogen (N2, 78 %) only a few microorganisms can use it directly. To be useful for higher plants and animals elemental nitrogen must be converted to a reactive oxidized form. This conversion happens within the nitrogen cycle by free-living microorganisms, symbiotic living Rhizobium bacteria or by lightning. Humans are able to synthesize reactive nitrogen through the Haber-Bosch process since the beginning of the 20th century. As a result food security of the world population could be improved noticeably. On the other side the increased nitrogen input results in acidification and eutrophication of ecosystems and in loss of biodiversity. Negative health effects arose for humans such as fine particulate matter and summer smog. Furthermore, reactive nitrogen plays a decisive role at atmospheric chemistry and global cycles of pollutants and nutritive substances.rnNitrogen monoxide (NO) and nitrogen dioxide (NO2) belong to the reactive trace gases and are grouped under the generic term NOx. They are important components of atmospheric oxidative processes and influence the lifetime of various less reactive greenhouse gases. NO and NO2 are generated amongst others at combustion process by oxidation of atmospheric nitrogen as well as by biological processes within soil. In atmosphere NO is converted very quickly into NO2. NO2 is than oxidized to nitrate (NO3-) and to nitric acid (HNO3), which bounds to aerosol particles. The bounded nitrate is finally washed out from atmosphere by dry and wet deposition. Catalytic reactions of NOx are an important part of atmospheric chemistry forming or decomposing tropospheric ozone (O3). In atmosphere NO, NO2 and O3 are in photosta¬tionary equilibrium, therefore it is referred as NO-NO2-O3 triad. At regions with elevated NO concentrations reactions with air pollutions can form NO2, altering equilibrium of ozone formation.rnThe essential nutrient nitrogen is taken up by plants mainly by dissolved NO3- entering the roots. Atmospheric nitrogen is oxidized to NO3- within soil via bacteria by nitrogen fixation or ammonium formation and nitrification. Additionally atmospheric NO2 uptake occurs directly by stomata. Inside the apoplast NO2 is disproportionated to nitrate and nitrite (NO2-), which can enter the plant metabolic processes. The enzymes nitrate and nitrite reductase convert nitrate and nitrite to ammonium (NH4+). NO2 gas exchange is controlled by pressure gradients inside the leaves, the stomatal aperture and leaf resistances. Plant stomatal regulation is affected by climate factors like light intensity, temperature and water vapor pressure deficit. rnThis thesis wants to contribute to the comprehension of the effects of vegetation in the atmospheric NO2 cycle and to discuss the NO2 compensation point concentration (mcomp,NO2). Therefore, NO2 exchange between the atmosphere and spruce (Picea abies) on leaf level was detected by a dynamic plant chamber system under labo¬ratory and field conditions. Measurements took place during the EGER project (June-July 2008). Additionally NO2 data collected during the ECHO project (July 2003) on oak (Quercus robur) were analyzed. The used measuring system allowed simultaneously determina¬tion of NO, NO2, O3, CO2 and H2O exchange rates. Calculations of NO, NO2 and O3 fluxes based on generally small differences (∆mi) measured between inlet and outlet of the chamber. Consequently a high accuracy and specificity of the analyzer is necessary. To achieve these requirements a highly specific NO/NO2 analyzer was used and the whole measurement system was optimized to an enduring measurement precision.rnData analysis resulted in a significant mcomp,NO2 only if statistical significance of ∆mi was detected. Consequently, significance of ∆mi was used as a data quality criterion. Photo-chemical reactions of the NO-NO2-O3 triad in the dynamic plant chamber’s volume must be considered for the determination of NO, NO2, O3 exchange rates, other¬wise deposition velocity (vdep,NO2) and mcomp,NO2 will be overestimated. No significant mcomp,NO2 for spruce could be determined under laboratory conditions, but under field conditions mcomp,NO2 could be identified between 0.17 and 0.65 ppb and vdep,NO2 between 0.07 and 0.42 mm s-1. Analyzing field data of oak, no NO2 compensation point concentration could be determined, vdep,NO2 ranged between 0.6 and 2.71 mm s-1. There is increasing indication that forests are mainly a sink for NO2 and potential NO2 emissions are low. Only when assuming high NO soil emissions, more NO2 can be formed by reaction with O3 than plants are able to take up. Under these circumstance forests can be a source for NO2.

Aircraft-based in-situ aerosol mass spectrometry: Chemical characterization and source identification of submicron particulate matter in the free and upper troposphere and lower stratosphere

The composition of the atmosphere is frequently perturbed by the emission of gaseous and particulate matter from natural as well as anthropogenic sources. While the impact of trace gases on the radiative forcing of the climate is relatively well understood the role of aerosol is far more uncertain. Therefore, the study of the vertical distribution of particulate matter in the atmosphere and its chemical composition contribute valuable information to bridge this gap of knowledge. The chemical composition of aerosol reveals information on properties such as radiative behavior and hygroscopicity and therefore cloud condensation or ice nucleus potential. rnThis thesis focuses on aerosol pollution plumes observed in 2008 during the POLARCAT (Polar Study using Aircraft, Remote Sensing, Surface Measurements and Models, of Climate, Chemistry, Aerosols, and Transport) campaign over Greenland in June/July and CONCERT (Contrail and Cirrus Experiment) campaign over Central and Western Europe in October/November. Measurements were performed with an Aerodyne compact time-of-flight aerosol mass spectrometer (AMS) capable of online size-resolved chemical characterization of non-refractory submicron particles. In addition, the origins of pollution plumes were determined by means of modeling tools. The characterized pollution episodes originated from a large variety of sources and were encountered at distinct altitudes. They included pure natural emissions from two volcanic eruptions in 2008. By the time of detection over Western Europe between 10 and 12 km altitude the plume was about 3 months old and composed to 71 % of particulate sulfate and 21 % of carbonaceous compounds. Also, biomass burning (BB) plumes were observed over Greenland between 4 and 7 km altitude (free troposphere) originating from Canada and East Siberia. The long-range transport took roughly one and two weeks, respectively. The aerosol was composed of 78 % organic matter and 22 % particulate sulfate. Some Canadian and all Siberian BB plumes were mixed with anthropogenic emissions from fossil fuel combustion (FF) in North America and East Asia. It was found that the contribution of particulate sulfate increased with growing influences from anthropogenic activity and Asia reaching up to 37 % after more than two weeks of transport time. The most exclusively anthropogenic emission source probed in the upper troposphere was engine exhaust from commercial aircraft liners over Germany. However, in-situ characterization of this aerosol type during aircraft chasing was not possible. All long-range transport aerosol was found to have an O:C ratio close to or greater than 1 implying that low-volatility oxygenated organic aerosol was present in each case despite the variety of origins and the large range in age from 3 to 100 days. This leads to the conclusion that organic particulate matter reaches a final and uniform state of oxygenation after at least 3 days in the free troposphere. rnExcept for aircraft exhaust all emission sources mentioned above are surface-bound and thus rely on different types of vertical transport mechanisms, such as direct high altitude injection in the case of a volcanic eruption, or severe BB, or uplift by convection, to reach higher altitudes where particles can travel long distances before removal mainly caused by cloud scavenging. A lifetime for North American mixed BB and FF aerosol of 7 to 11 days was derived. This in consequence means that emission from surface point sources, e.g. volcanoes, or regions, e.g. East Asia, do not only have a relevant impact on the immediate surroundings but rather on a hemispheric scale including such climate sensitive zones as the tropopause or the Arctic.

Retrieval simulations of the vertical profiles of water vapour and other chemical species in the Martian atmosphere using PACS

Water vapour, despite being a minor constituent in the Martian atmosphere with its precipitable amount of less than 70 pr. μm, attracts considerable attention in the scientific community because of its potential importance for past life on Mars. The partial pressure of water vapour is highly variable because of its seasonal condensation onto the polar caps and exchange with a subsurface reservoir. It is also known to drive photochemical processes: photolysis of water produces H, OH, HO2 and some other odd hydrogen compounds, which in turn destroy ozone. Consequently, the abundance of water vapour is anti-correlated with ozone abundance. The Herschel Space Observatory provides for the first time the possibility to retrieve vertical water profiles in the Martian atmosphere. Herschel will contribute to this topic with its guaranteed-time key project called "Water and related chemistry in the solar system". Observations of Mars by Heterodyne Instrument for the Far Infrared (HIFI) and Photodetector Array Camera and Spectrometer (PACS) onboard Herschel are planned in the frame of the programme. HIFI with its high spectral resolution enables accurate observations of vertically resolved H2O and temperature profiles in the Martian atmosphere. Unlike HIFI, PACS is not capable of resolving the line-shape of molecular lines. However, our present study of PACS observations for the Martian atmosphere shows that the vertical sensitivity of the PACS observations can be improved by using multiple-line observations with different line opacities. We have investigated the possibility of retrieving vertical profiles of temperature and molecular abundances of minor species including H2O in the Martian atmosphere using PACS. In this paper, we report that PACS is able to provide water vapour vertical profiles for the Martian atmosphere and we present the expected spectra for future PACS observations. We also show that the spectral resolution does not allow the retrieval of several studied minor species, such as H2O2, HCl, NO, SO2, etc.

Measurements of Humidity in the Atmosphere and Validation Experiments MOHAVE-2009; overview of campaign operations and results

The Measurements of Humidity in the Atmosphere and Validation Experiment (MOHAVE) 2009 campaign took place on 11–27 October 2009 at the JPL Table Mountain Facility in California (TMF). The main objectives of the campaign were to (1) validate the water vapor measurements of several instruments, including, three Raman lidars, two microwave radiometers, two Fourier-Transform spectrometers, and two GPS receivers (column water), (2) cover water vapor measurements from the ground to the mesopause without gaps, and (3) study upper tropospheric humidity variability at timescales varying from a few minutes to several days. A total of 58 radiosondes and 20 Frost-Point hygrometer sondes were launched. Two types of radiosondes were used during the campaign. Non negligible differences in the readings between the two radiosonde types used (Vaisala RS92 and InterMet iMet-1) made a small, but measurable impact on the derivation of water vapor mixing ratio by the Frost-Point hygrometers. As observed in previous campaigns, the RS92 humidity measurements remained within 5% of the Frost-point in the lower and mid-troposphere, but were too dry in the upper troposphere. Over 270 h of water vapor measurements from three Raman lidars (JPL and GSFC) were compared to RS92, CFH, and NOAA-FPH. The JPL lidar profiles reached 20 km when integrated all night, and 15 km when integrated for 1 h. Excellent agreement between this lidar and the frost-point hygrometers was found throughout the measurement range, with only a 3% (0.3 ppmv) mean wet bias for the lidar in the upper troposphere and lower stratosphere (UTLS). The other two lidars provided satisfactory results in the lower and mid-troposphere (2–5% wet bias over the range 3–10 km), but suffered from contamination by fluorescence (wet bias ranging from 5 to 50% between 10 km and 15 km), preventing their use as an independent measurement in the UTLS. The comparison between all available stratospheric sounders allowed to identify only the largest biases, in particular a 10% dry bias of the Water Vapor Millimeter-wave Spectrometer compared to the Aura-Microwave Limb Sounder. No other large, or at least statistically significant, biases could be observed. Total Precipitable Water (TPW) measurements from six different co-located instruments were available. Several retrieval groups provided their own TPW retrievals, resulting in the comparison of 10 different datasets. Agreement within 7% (0.7 mm) was found between all datasets. Such good agreement illustrates the maturity of these measurements and raises confidence levels for their use as an alternate or complementary source of calibration for the Raman lidars. Tropospheric and stratospheric ozone and temperature measurements were also available during the campaign. The water vapor and ozone lidar measurements, together with the advected potential vorticity results from the high-resolution transport model MIMOSA, allowed the identification and study of a deep stratospheric intrusion over TMF. These observations demonstrated the lidar strong potential for future long-term monitoring of water vapor in the UTLS.

A prospective study of the impact of air pollution on respiratory symptoms and infections in infants

Rationale: There is increasing evidence that short-term exposure to air pollution has a detrimental effect on respiratory health, but data from healthy populations, particularly infants, are scarce. Objectives: To assess the association of air pollution with frequency and severity of respiratory symptoms and infections measured weekly in healthy infants. Methods: In a prospective birth cohort of 366 infants of unselected mothers, respiratory health was assessed weekly by telephone interviews during the first year of life (19,106 total observations). Daily mean levels of particulate matter (PM10), nitrogen dioxide (NO2), and ozone (O3) were obtained from local monitoring stations. We determined the association of the preceding week's pollutant levels with symptom scores and respiratory tract infections using a generalized additive mixed model with an autoregressive component. In addition, we assessed whether neonatal lung function influences this association and whether duration of infectious episodes differed between weeks with normal PM10 and weeks with elevated levels. Measurements and Main Results: We found a significant association between air pollution and respiratory symptoms, particularly in the week after respiratory tract infections (risk ratio, 1.13 [1.02-1.24] per 10 μg/m(3) PM10 levels) and in infants with premorbid lung function. During times of elevated PM10 (>33.3 μg/m(3)), duration of respiratory tract infections increased by 20% (95% confidence interval, 2-42%). Conclusions: Exposure to even moderate levels of air pollution was associated with increased respiratory symptoms in healthy infants. Particularly in infants with premorbid lung function and inflammation, air pollution contributed to longer duration of infectious episodes with a potentially large socioeconomic impact.