Dating paleochannel iron ore by (U-Th)/He analysis of supergene goethite, Hamersley province, Australia

(U-Th)/He dating of late-stage authigenic goethite, combined with corrections for diffusive loss of He-4 by the He-4/He-3 methodology, reveals strong correlation between a sample's age and its depth in ferruginized channel sediments from the Yandicoogina deposit, Western Australia. Corrected ages, ranging from ca. 18 Ma near the surface to ca. 5 Ma at the bottom of the profile, indicate that ferruginization of the aggraded channels becomes progressively younger with depth. This trend is consistent with goethite precipitation at the groundwater-atmosphere interface during water table drawdown driven by the aridification of Western Australia during the Neogene. The results demonstrate that the (U-Th)/He system is ideal for dating goethite if diffusive loss corrections are applied. The approach is suitable for dating weathering reactions on Earth and should also be suitable for dating Fe oxyhydroxides in the Martian regolith.

Spectroscopic analysis of terrestrial analogues for the interpretation of surface composition of rocky bodies in the solar system. Effects of mineral mixing and particle size. Applications to moon, mars and implications for mercury.

Among the Solar System’s bodies, Moon, Mercury and Mars are at present, or have been in the recent years, object of space missions aimed, among other topics, also at improving our knowledge about surface composition. Between the techniques to detect planet’s mineralogical composition, both from remote and close range platforms, visible and near-infrared reflectance (VNIR) spectroscopy is a powerful tool, because crystal field absorption bands are related to particular transitional metals in well-defined crystal structures, e.g., Fe2+ in M1 and M2 sites of olivine or pyroxene (Burns, 1993). Thanks to the improvements in the spectrometers onboard the recent missions, a more detailed interpretation of the planetary surfaces can now be delineated. However, quantitative interpretation of planetary surface mineralogy could not always be a simple task. In fact, several factors such as the mineral chemistry, the presence of different minerals that absorb in a narrow spectral range, the regolith with a variable particle size range, the space weathering, the atmosphere composition etc., act in unpredictable ways on the reflectance spectra on a planetary surface (Serventi et al., 2014). One method for the interpretation of reflectance spectra of unknown materials involves the study of a number of spectra acquired in the laboratory under different conditions, such as different mineral abundances or different particle sizes, in order to derive empirical trends. This is the methodology that has been followed in this PhD thesis: the single factors previously listed have been analyzed, creating, in the laboratory, a set of terrestrial analogues with well-defined composition and size. The aim of this work is to provide new tools and criteria to improve the knowledge of the composition of planetary surfaces. In particular, mixtures composed with different content and chemistry of plagioclase and mafic minerals have been spectroscopically analyzed at different particle sizes and with different mineral relative percentages. The reflectance spectra of each mixture have been analyzed both qualitatively (using the software ORIGIN®) and quantitatively applying the Modified Gaussian Model (MGM, Sunshine et al., 1990) algorithm. In particular, the spectral parameter variations of each absorption band have been evaluated versus the volumetric FeO% content in the PL phase and versus the PL modal abundance. This delineated calibration curves of composition vs. spectral parameters and allow implementation of spectral libraries. Furthermore, the trends derived from terrestrial analogues here analyzed and from analogues in the literature have been applied for the interpretation of hyperspectral images of both plagioclase-rich (Moon) and plagioclase-poor (Mars) bodies.

Stabilisation of isocyanate cross linked polybutadiene binder

Isocyanate cross-linked hydroxy terminated polybutadiene is used as a binder for solid rocket propellant. Rocket motors containing this propellant require a storage life of at least 20 years. During storage it has been found that the important rubbery properties of the binder can be lost due to oxidative cross-linking of the polybutadiene chains. This could cause catastrophic failure when the rocket motor is required. At present the bis-hindered phenol Calco 2246 is used as a thermal oxidative stabiliser, but it's performance is only adequate. This has led to the search for a more efficient stabiliser system. To hasten the evaluation of new antioxidant systems the use of dynamic thermal analysis was investigated. Results showed that a tentative relationship existed between predictions by thermal analysis and the long term oven ageing for simple single antioxidant systems. But for more complex systems containing either autosynergistic or mixed antioxidants no relationship was observed suggesting that results for such an "accelerated" technique cannot be used for the purpose of extrapolation for long term performance. This was attributed to the short time and more aggressive condition used (hjgher temperature and oxygen rich atmosphere in thermal analysis) altering the mechanism of action of the antioxidants and not allowing time for co-operative effect of the combined antioxidant system to form. One potential problem for the binder system is the use of an diisocyanate as a cross-linking agent. This reacts with the hydroxyl hydrogen on the polymer as well as other active hydrogens such as those contained in a number of antioxidants, affecting both cross-linking and antioxidant effectiveness. Studies in this work showed that only antioxidants containing amine moieties have a significant affect on binder preparation, with the phenolic antioxidants not reacting. This is due to the greater nucleophilicity of the amines. Investigation of a range of antioxidant systems, including potentially homo, hetero and autosynergistic systems, has highlighted a number of systems which show considerably greater effectiveness than the currently used antioxidant Calco 2246. The only single antioxidant which showed improvement was the partially unhindered phenol y-Tocopherol. Of the mixed systems combinations of the sulphur containing antioxidants e.g. DLTP with higher levels of chain-breaking antioxidants, especially Calco 2246, were the most promising. Also the homosynergistic mix of an aromatic amine and a phenol was seen to be very effective but the results were inconsistent. This inconsistency could be explained by the method of sample preparation used. It was shown that the efficiency of a number of antioxidant.s could be dramatically improved by the use of ultrasound during the mixing stage of preparation. The reason for this increase in performance is unclear but in the case of the homosynergistic amine/phenol mix both more efficient mixing and/or the production of a novel mechanism of action are suggested

Analysis of rubber vulcanisates

A study has been made, using High Pressure Liquid Chromatography, of the migration of TMQ (a quinoline type) and 6PPD (a paraphenylenediamine type) antidegradants from a tyre sidewall compound into adjacent casing and liner compounds containing no antidegradant. Migration takes place at a rapid rate, even during the vulcanisation of the composite. After 4000 hours ageing in nitrogen at 100oC, there is a higher level of antidegradants in the casing than in the sidewall. An equilibrium distribution is not obtained. After 114 days at 50oC in 95% relative humidity, the level of solvent extractable 6PPD fell to zero, but subsequent ageing for 2 years in 50 pphm ozone showed no evidence of sidewall cracking. It is suggested that the antidegradant is still active but linked to the polymer chain. An analytical method, for the type and amount of sulphenamide accelerators in vulcanised rubber compounds, has been developed. During the vulcanisation process, the accelerators decay, liberating specific amines which have been solvent extracted, derivatised with 1-chloro-2,4-dinitrobenzene and the yellow coloured zwitter ion analysed using High Pressure Liquid Chromatography. The decay of the accelerator and sulphur during the vulcanisation process, has been studied. It has been demonstrated that the sulphur crosslinking with a styrenebutadiene polymer is a first order reaction, after an initial period during which the accelerator content falls to zero. Variations in sulphur to accelerator ratios gave consistent rate constants for the crosslinking, except for a sulphur level of less than 1% by weight and a ratiio of accelerator to sulphur of 1:1.3. The retention time of the reaction product between sulphur and accelerator from an HPLC column changes with cure time, showing that the precurser to crosslinking is an ever changing material. One of these reaction products has been analysed.

Influence of reaction atmosphere (H2O, N2, H2, CO2, CO) on fluidized-bed fast pyrolysis of biomass using detailed tar vapor chemistry in computational fluid dynamics

Secondary pyrolysis in fluidized bed fast pyrolysis of biomass is the focus of this work. A novel computational fluid dynamics (CFD) model coupled with a comprehensive chemistry scheme (134 species and 4169 reactions, in CHEMKIN format) has been developed to investigate this complex phenomenon. Previous results from a transient three-dimensional model of primary pyrolysis were used for the source terms of primary products in this model. A parametric study of reaction atmospheres (H2O, N2, H2, CO2, CO) has been performed. For the N2 and H2O atmosphere, results of the model compared favorably to experimentally obtained yields after the temperature was adjusted to a value higher than that used in experiments. One notable deviation versus experiments is pyrolytic water yield and yield of higher hydrocarbons. The model suggests a not overly strong impact of the reaction atmosphere. However, both chemical and physical effects were observed. Most notably, effects could be seen on the yield of various compounds, temperature profile throughout the reactor system, residence time, radical concentration, and turbulent intensity. At the investigated temperature (873 K), turbulent intensity appeared to have the strongest influence on liquid yield. With the aid of acceleration techniques, most importantly dimension reduction, chemistry agglomeration, and in-situ tabulation, a converged solution could be obtained within a reasonable time (∼30 h). As such, a new potentially useful method has been suggested for numerical analysis of fast pyrolysis.

Cost-benefit analysis of climate change – A methodological overview of recent studies

Global warming16 has already begun. Climate change has become a self-propelling and self-reinforcing process as a result of the externality associated with greenhouse- gas (GHG) emissions. Although it is an externality related to humankind, according to a number of unique features we should distinguish it from other externalities. Climate change is a global phenomenon in its causes and consequences. The long-term and persistent impacts of climate change will likely continue over centuries without further anthropogenic mechanism. The preindustrial (equilibrium) level of GHG concentration in the atmosphere cannot be restored since it is irreversible, but if we do not stabilise the actual level of atmospheric concentration, the situation will become much worse than it is now. Assessing the impacts of climate change requires careful considerations because of the pervasive uncertainties and risks associated with it.

A comparative analysis of school satisfaction and dropout risk of middle school students attending programs for students with emotional handicaps, severe emotional disturbance and general education students attending center schools and satellite schools

This study evaluated school satisfaction as an indicator of dropout risk of students with Emotional Handicaps (EH) and students with Severe Emotional Disturbance (SED). The students attended two different kinds of middle schools in a largely urban school district in South Florida. One hundred eight students in grade 8 (ages 13-16) participated in this study. Participants were administered the National Dropout Prevention Assessment (NDPA). Forty participants with EH and SED attended a special center school. Thirty-one participants with EH and SED attended satellite programs in a regular middle school. Thirty-seven general education participants attended the same regular middle school. Overall school satisfaction scores were generated, as well as three primary factors (school, environment and personal) and 16 subscales (school atmosphere, future income, difficulty level of classwork, teacher relationships, peer relationships, intrinsic interest in classwork, school hours, classwork stress, general attitude towards school, family influence, perceived opportunity for career, future goals, travel distance, leisure time, self-appraisal of performance, and self-esteem).^ Comparison of students with EH and SED revealed that both groups of students were rated at "low risk" of becoming dropouts on the Environmental factor and the Difficulty of Schoolwork subscale. Students with EH were rated at "caution risk" risk on the Travel Distance subscale. Students with SED were rated at "high risk" on this subscale.^ There were no significant differences in school satisfaction and dropout risk between different program delivery models. There were also no significant differences for category of students (EH, SED) by school type (center school, satellite program). All students were rated at "low risk" of dropping out of school.^ There were significant differences between general education students and students with EH and SED attending satellite programs. Students with EH and SED were rated at "caution risk" for dropping out on the Travel Distance and the Leisure Time subscales. Discussion of results, implications for practice and recommendations for further research are included. ^

Hierarchical structures in Northern Hemispheric extratropical winter ocean-atmosphere interactions

Acknowledgements MW and RVD have been supported by the German Federal Ministry for Education and Research via the BMBF Young Investigators Group CoSy-CC2 (grant 18 Marc Wiedermann et al. no. 01LN1306A). JFD thanks the Stordalen Foundation and BMBF (project GLUES) for financial support. JK acknowledges the IRTG 1740 funded by DFG and FAPESP. Coupled climate network analysis has been performed using the Python package pyunicorn (Donges et al, 2015a) that is available at https://github.com/pik-copan/pyunicorn.

Hierarchical structures in Northern Hemispheric extratropical winter ocean-atmosphere interactions

Acknowledgements MW and RVD have been supported by the German Federal Ministry for Education and Research via the BMBF Young Investigators Group CoSy-CC2 (grant 18 Marc Wiedermann et al. no. 01LN1306A). JFD thanks the Stordalen Foundation and BMBF (project GLUES) for financial support. JK acknowledges the IRTG 1740 funded by DFG and FAPESP. Coupled climate network analysis has been performed using the Python package pyunicorn (Donges et al, 2015a) that is available at https://github.com/pik-copan/pyunicorn.

Options to advance co-ordination and analysis of climate data in Europe

Systematic, high-quality observations of the atmosphere, oceans and terrestrial environments are required to improve understanding of climate characteristics and the consequences of climate change. The overall aim of this report is to carry out a comparative assessment of approaches taken to addressing the state of European observations systems and related data analysis by some leading actors in the field. This research reports on approaches to climate observations and analyses in Ireland, Switzerland, Germany, The Netherlands and Austria and explores options for a more coordinated approach to national responses to climate observations in Europe. The key aspects addressed are: an assessment of approaches to develop GCOS and provision of analysis of GCOS data; an evaluation of how these countries are reporting development of GCOS; highlighting best practice in advancing GCOS implementation including analysis of Essential Climate Variables (ECVs); a comparative summary of the differences and synergies in terms of the reporting of climate observations; an overview of relevant European initiatives and recommendations on how identified gaps might be addressed in the short to medium term.

Bridging the Scale Gap from Leaf to Canopy in Biosphere-Atmosphere Gas and Particle Exchanges

Terrestrial ecosystems, occupying more than 25% of the Earth's surface, can serve as

`biological valves' in regulating the anthropogenic emissions of atmospheric aerosol

particles and greenhouse gases (GHGs) as responses to their surrounding environments.

While the signicance of quantifying the exchange rates of GHGs and atmospheric

aerosol particles between the terrestrial biosphere and the atmosphere is

hardly questioned in many scientic elds, the progress in improving model predictability,

data interpretation or the combination of the two remains impeded by

the lack of precise framework elucidating their dynamic transport processes over a

wide range of spatiotemporal scales. The diculty in developing prognostic modeling

tools to quantify the source or sink strength of these atmospheric substances

can be further magnied by the fact that the climate system is also sensitive to the

feedback from terrestrial ecosystems forming the so-called `feedback cycle'. Hence,

the emergent need is to reduce uncertainties when assessing this complex and dynamic

feedback cycle that is necessary to support the decisions of mitigation and

adaptation policies associated with human activities (e.g., anthropogenic emission

controls and land use managements) under current and future climate regimes.

With the goal to improve the predictions for the biosphere-atmosphere exchange

of biologically active gases and atmospheric aerosol particles, the main focus of this

dissertation is on revising and up-scaling the biotic and abiotic transport processes

from leaf to canopy scales. The validity of previous modeling studies in determining

iv

the exchange rate of gases and particles is evaluated with detailed descriptions of their

limitations. Mechanistic-based modeling approaches along with empirical studies

across dierent scales are employed to rene the mathematical descriptions of surface

conductance responsible for gas and particle exchanges as commonly adopted by all

operational models. Specically, how variation in horizontal leaf area density within

the vegetated medium, leaf size and leaf microroughness impact the aerodynamic attributes

and thereby the ultrane particle collection eciency at the leaf/branch scale

is explored using wind tunnel experiments with interpretations by a porous media

model and a scaling analysis. A multi-layered and size-resolved second-order closure

model combined with particle

uxes and concentration measurements within and

above a forest is used to explore the particle transport processes within the canopy

sub-layer and the partitioning of particle deposition onto canopy medium and forest

oor. For gases, a modeling framework accounting for the leaf-level boundary layer

eects on the stomatal pathway for gas exchange is proposed and combined with sap

ux measurements in a wind tunnel to assess how leaf-level transpiration varies with

increasing wind speed. How exogenous environmental conditions and endogenous

soil-root-stem-leaf hydraulic and eco-physiological properties impact the above- and

below-ground water dynamics in the soil-plant system and shape plant responses

to droughts is assessed by a porous media model that accommodates the transient

water

ow within the plant vascular system and is coupled with the aforementioned

leaf-level gas exchange model and soil-root interaction model. It should be noted

that tackling all aspects of potential issues causing uncertainties in forecasting the

feedback cycle between terrestrial ecosystem and the climate is unrealistic in a single

dissertation but further research questions and opportunities based on the foundation

derived from this dissertation are also brie

y discussed.

Enhanced Volatile Organic Compounds emissions and organic aerosol mass increase the oligomer content of atmospheric aerosols

Secondary organic aerosol (SOA) accounts for a dominant fraction of the submicron atmospheric particle mass, but knowledge of the formation, composition and climate effects of SOA is incomplete and limits our understanding of overall aerosol effects in the atmosphere. Organic oligomers were discovered as dominant components in SOA over a decade ago in laboratory experiments and have since been proposed to play a dominant role in many aerosol processes. However, it remains unclear whether oligomers are relevant under ambient atmospheric conditions because they are often not clearly observed in field samples. Here we resolve this long-standing discrepancy by showing that elevated SOA mass is one of the key drivers of oligomer formation in the ambient atmosphere and laboratory experiments. We show for the first time that a specific organic compound class in aerosols, oligomers, is strongly correlated with cloud condensation nuclei (CCN) activities of SOA particles. These findings might have important implications for future climate scenarios where increased temperatures cause higher biogenic volatile organic compound (VOC) emissions, which in turn lead to higher SOA mass formation and significant changes in SOA composition. Such processes would need to be considered in climate models for a realistic representation of future aerosol-climate-biosphere feedbacks.

Molecular composition of organic aerosols in central Amazonia: an ultra-high-resolution mass spectrometry study

The Amazon Basin plays key role in atmospheric chemistry, biodiversity and climate change. In this study we applied nanoelectrospray (nanoESI) ultra-high-resolution mass spectrometry (UHRMS) for the analysis of the organic fraction of PM2.5 aerosol samples collected during dry and wet seasons at a site in central Amazonia receiving background air masses, biomass burning and urban pollution. Comprehensive mass spectral data evaluation methods (e.g. Kendrick mass defect, Van Krevelen diagrams, carbon oxidation state and aromaticity equivalent) were used to identify compound classes and mass distributions of the detected species. Nitrogen- and/or sulfur-containing organic species contributed up to 60 % of the total identified number of formulae. A large number of molecular formulae in organic aerosol (OA) were attributed to later-generation nitrogen- and sulfur-containing oxidation products, suggesting that OA composition is affected by biomass burning and other, potentially anthropogenic, sources. Isoprene-derived organosulfate (IEPOX-OS) was found to be the most dominant ion in most of the analysed samples and strongly followed the concentration trends of the gas-phase anthropogenic tracers confirming its mixed anthropogenic–biogenic origin. The presence of oxidised aromatic and nitro-aromatic compounds in the samples suggested a strong influence from biomass burning especially during the dry period. Aerosol samples from the dry period and under enhanced biomass burning conditions contained a large number of molecules with high carbon oxidation state and an increased number of aromatic compounds compared to that from the wet period. The results of this work demonstrate that the studied site is influenced not only by biogenic emissions from the forest but also by biomass burning and potentially other anthropogenic emissions from the neighbouring urban environments.

EUSAAR size distribution analysis database

Two years of harmonized aerosol number size distribution data from 24 European field monitoring sites have been analysed. The results give a comprehensive overview of the European near surface aerosol particle number concentrations and number size distributions between 30 and 500 nm of dry particle diameter. Spatial and temporal distribution of aerosols in the particle sizes most important for climate applications are presented. We also analyse the annual, weekly and diurnal cycles of the aerosol number concentrations, provide log-normal fitting parameters for median number size distributions, and give guidance notes for data users. Emphasis is placed on the usability of results within the aerosol modelling community. We also show that the aerosol number concentrations of Aitken and accumulation mode particles (with 100 nm dry diameter as a cut-off between modes) are related, although there is significant variation in the ratios of the modal number concentrations. Different aerosol and station types are distinguished from this data and this methodology has potential for further categorization of stations aerosol number size distribution types. The European submicron aerosol was divided into characteristic types: Central European aerosol, characterized by single mode median size distributions, unimodal number concentration histograms and low variability in CCN-sized aerosol number concentrations; Nordic aerosol with low number concentrations, although showing pronounced seasonal variation of especially Aitken mode particles; Mountain sites (altitude over 1000 m a.s.l.) with a strong seasonal cycle in aerosol number concentrations, high variability, and very low median number concentrations. Southern and Western European regions had fewer stations, which decreases the regional coverage of these results. Aerosol number concentrations over the Britain and Ireland had very high variance and there are indications of mixed air masses from several source regions; the Mediterranean aerosol exhibit high seasonality, and a strong accumulation mode in the summer. The greatest concentrations were observed at the Ispra station in Northern Italy with high accumulation mode number concentrations in the winter. The aerosol number concentrations at the Arctic station Zeppelin in Ny-Ålesund in Svalbard have also a strong seasonal cycle, with greater concentrations of accumulation mode particles in winter, and dominating summer Aitken mode indicating more recently formed particles. Observed particles did not show any statistically significant regional work-week or weekday related variation in number concentrations studied. Analysis products are made for open-access to the research community, available in a freely accessible internet site. The results give to the modelling community a reliable, easy-to-use and freely available comparison dataset of aerosol size distributions.

Long-term chemical characterization of aerosols at CVAO from 2007 to 2011

The first long-term aerosol sampling and chemical characterization results from measurements at the Cape Verde Atmospheric Observatory (CVAO) on the island of São Vicente are presented and are discussed with respect to air mass origin and seasonal trends. In total 671 samples were collected using a high-volume PM10 sampler on quartz fiber filters from January 2007 to December 2011. The samples were analyzed for their aerosol chemical composition, including their ionic and organic constituents. Back trajectory analyses showed that the aerosol at CVAO was strongly influenced by emissions from Europe and Africa, with the latter often responsible for high mineral dust loading. Sea salt and mineral dust dominated the aerosol mass and made up in total about 80% of the aerosol mass. The 5-year PM10 mean was 47.1 ± 55.5 µg/m**2, while the mineral dust and sea salt means were 27.9 ± 48.7 and 11.1 ± 5.5 µg/m**2, respectively. Non-sea-salt (nss) sulfate made up 62% of the total sulfate and originated from both long-range transport from Africa or Europe and marine sources. Strong seasonal variation was observed for the aerosol components. While nitrate showed no clear seasonal variation with an annual mean of 1.1 ± 0.6 µg/m**3, the aerosol mass, OC (organic carbon) and EC (elemental carbon), showed strong winter maxima due to strong influence of African air mass inflow. Additionally during summer, elevated concentrations of OM were observed originating from marine emissions. A summer maximum was observed for non-sea-salt sulfate and was connected to periods when air mass inflow was predominantly of marine origin, indicating that marine biogenic emissions were a significant source. Ammonium showed a distinct maximum in spring and coincided with ocean surface water chlorophyll a concentrations. Good correlations were also observed between nss-sulfate and oxalate during the summer and winter seasons, indicating a likely photochemical in-cloud processing of the marine and anthropogenic precursors of these species. High temporal variability was observed in both chloride and bromide depletion, differing significantly within the seasons, air mass history and Saharan dust concentration. Chloride (bromide) depletion varied from 8.8 ± 8.5% (62 ± 42%) in Saharan-dust-dominated air mass to 30 ± 12% (87 ± 11%) in polluted Europe air masses. During summer, bromide depletion often reached 100% in marine as well as in polluted continental samples. In addition to the influence of the aerosol acidic components, photochemistry was one of the main drivers of halogenide depletion during the summer; while during dust events, displacement reaction with nitric acid was found to be the dominant mechanism. Positive matrix factorization (PMF) analysis identified three major aerosol sources: sea salt, aged sea salt and long-range transport. The ionic budget was dominated by the first two of these factors, while the long-range transport factor could only account for about 14% of the total observed ionic mass.