La réactivité totale OH est la perte totale du radical hydroxyle (le principal oxydant de l'atmosphère) avec les gaz réactifs dans l'air ambiant. Elle représente la mesure de la quantité totale des réactifs dans un environnement donné.Nous présentons ici un travail expérimental se concentrant sur les améliorations techniques d'une méthode appelée "Comparative Reactivity Method" pour mesurer la réactivité OH su le terrain ainsi que sur des résultats obtenus sur deux sites ciblés dans le bassin méditerranéen.La réactivité OH mesurée était élevée dans les deux sites. Sur le site récepteur en Corse (France) au cours de l'été 2013, nous avons observé que la réactivité OH était en moyenne de 5,5 s-1 (avec un maximum de 17 s-1). Ces mesures ont été comparées avec les observations de composés en phase gazeuse réalisées pendant la campagne. Il a été noté que pendant une période de la campagne, seulement 50% de la réactvité était expliqué par les mesures complémentaires.Lors de mesures dans une forêt de chênes pubescents, émetteurs isoprène, dans le sud de la France, nous avons observé que la réactivité OH maximale était très élevée (69 s-1), en accord avec la réactivité calculée à partir des mesures des gaz réactifs.Ce travail de thèse met en évidence que: (i) le bassin méditerranéen est un fort émetteur de gaz réactifs, (ii) la réactivité mesurée dans ces deux sites de la Méditerranée a été fortement impactée par les émissions biogéniques, (iii) il reste encore beaucoup de composés inconnus associés aux émissions biogéniques primaires et secondaires. A l'avenir, plusieurs approches pourraient etre utilisées pour identifier ces composés inconnus: en couplant la mesure de la réactivité OH avec des mesures de plantes dans des enceintes fermées (composés primaires), études en chambre de vieillissement (composés primaires et secondaires), ainsi que des approches de modélisation. / The total OH reactivity is the total loss rate of the hydroxyl radical with the reactive gases in ambient air. It represents the measure of the total loading of reactants in a given environment.Here we present an experimental work focusing on the technical improvements of the Comparative Reactivity Method to measure the OH reactivity on the field and field measurements of OH reactivity at two targeted sites in the Mediterranean basin.The measured OH reactivity was high at both sites. At a receptor site in Corsica (France) during summer 2013, we observed that the OH reactivity was maximum 17 s-1, on average 5.5 s-1 and during one week only 50% was explained by the complementary measurements in the gas phase.At a forest of downy oak trees, high isoprene emitters, in the south of France, we observed that the OH reactivity was maximum 69 s-1, in agreement with the reactivity calculated from the measurements of reactive gases only during daytime.This thesis work highlights that: (i) the Mediterranean basin is a strong emitter of reactive gases, (ii) the reactivity measured in these two sites in the Mediterranean was strongly impacted by the biogenic emissions, (iii) there are still many unknowns associated to measures of biogenic volatiles primary emitted and secondary produced. Such unknowns might be reduced in the future by coupling the measurement of the OH reactivity with plants enclosures and chambers studies as well as modelling approaches.

The goal of this research is to understand the impacts of the 2010 Deepwater Horizon oil spill and the 1970-1980 IXTOC-I oil spill and other anthropogenic activity (e.g. dam construction) on surface water primary productivity by measuring sedimentary biogenic silica. It is known that sedimentary biogenic silica is distinct from mineral – bound silica, therefore it has been used as a proxy record for surface water primary productivity (e.g. diatom blooms). The Deepwater Horizon oil spill resulted in a widespread Marine Oil Snow Sedimentation and Flocculent Accumulation (MOSSFA) event. The IXTOC-I oil spill was one of the largest oil spills in history and it is likely that the MOSSFA event occurred as a direct result. MOSSFA is characterized by increased deposition of surface derived components and dramatic changes in post-depositional chemical (redox) and biological (benthic meio- and macro-fauna) conditions. Sedimentary biogenic silica provides an independent record of the surface derived portion of MOSSFA inputs. Occurrences of MOSSFA after IXTOC-I and Deepwater Horizon were compared by collecting sediment cores from the northern Gulf of Mexico (Deepwater Horizon) and the southern Gulf of Mexico (IXTOC-I). An age model for each core was developed using short-lived radioisotopes (i.e. 210Pbxs). Sedimentary biogenic silica was significantly elevated in sedimentary intervals affected by the Deepwater Horizon spill. This suggests that a significant portion of the surface biological materials entrained during the MOSSFA event were sourced by diatom production. However, only one core (of three from the oil spill influenced area utilized in this study) from shallower depth had elevated levels of sedimentary biogenic silica in the sedimentary interval associated with IXTOC-I. Also, the down-core profiles of sedimentary biogenic silica from the other cores collected in the southern Gulf of Mexico are consistent with the history of dam construction (1949 to 1989) on the Grijalva and Papaloapan river systems. These two river systems are the dominant freshwater and nutrient sources for primary production in the Bay of Campeche region in the southern Gulf of Mexico and therefore the dominant control on diatom productivity and sedimentary biogenic silica distribution. Consequently, distribution of annual fresh water outflow and nutrient supply has transitioned from seasonal (before 1940’s) to stable (after 1980’s). Overall, sedimentary biogenic silica provides an independent record of surface derived MOSSFA inputs and serves as a proxy for other anthropogenic influences related to surface primary productivity variability.

The reduction of greenhouse gases in the atmosphere and the transformation from a fossil-based to a bio-based economy are declared social, political and entrepreneurial goals. The efficient material and energetic use of biogenic residues, by-products and wastes offers numerous means of working towards these goals. However, it is still unclear what raw materials can be understood under these collective terms, what quantities exist across sectors and what additional contribution can be expected from their improved use. In the context of this thesis, an internationally applicable method has been developed which can be used to continuously balance and evaluate the technical biomass potential and current use. The basis for this is a modular monitoring system that is used to develop a multi-stage biomass categorisation, a regularly updatable network of biomass-specific calculation elements and a procedure for the continuous improvement of data quality. The monitoring system was tested for a consistent reference year using Germany as an example. In addition, the temporal and spatial dynamics of the biomass availability were analysed for the case study of cereal straw using a geoinformation system. With the help of 1,113 calculation elements, the supply and use of 77 biomasses from five sectors were balanced. On this basis, the technical biomass potential for the year 2015 amounts to 86–140 million tonnes of dry matter. Between 65 % and 84 % are already tied up in a material or energetic use. There is a clear focus on only a few raw materials; 20 % of the resources make up more than 80 % of the supply. By further tapping the mobilisable potential of 14–48 million tonnes of dry matter, an annual primary energy contribution of at least 6 % and up to 15 % could be achieved in future, for example. The detailed analysis for the case study also shows that, despite significant fluctuations over time, large parts of the potential are concentrated in only a few regions. The overall broad ranges of results indicate that the data quality is uncertain and, in particular in the areas of soil and water quality, biodiversity and eutrophication of ecosystems, there is a need for research on how the complex interactions can be integrated into future calculations of biomass potentials, using which data sets. The consequent provision of the monitoring results and calculation methodology in an online data repository (http://webapp.dbfz.de) provides the opportunity to reflect on the existing approaches in an open debate and to continue developing them in line with the respective needs. Using the findings generated by the monitoring system, the focus can be placed on the most important raw materials and regions for the implementation of political and entrepreneurial strategies and for filling gaps in the data. On this basis, the next steps for an optimal and sustainable contribution to a bio-based circular economy can be prioritised and discussed with regional stakeholders and shareholders. / Die Reduktion von Treibhausgasen in der Atmosphäre und die Transformation von einer fossilbasierten zu einer bio-basierten Wirtschaftsweise sind erklärte gesellschaftliche, politische und unternehmerische Ziele. Die effiziente stoffliche und energetische Nutzung von biogenen Reststoffen, Nebenprodukten und Abfällen bietet zahlreiche Möglichkeiten, diesen Zielen näher zu kommen. Unklar ist bisher jedoch, welche Rohstoffe unter diesen Sammelbegriffen verstanden werden können, welche Mengen sektorenübergreifend existieren und welcher zusätzlichentzliche Beitrag aus einer optimierten Nutzung erwartet werden kann. Im Rahmen dieser Arbeit wurde daher eine international anwendbare Methode entwickelt, mit der das technische Biomassepotenzial und die aktuelle Nutzung fortlaufend bilanziert und bewertet werden kann. Die Grundlage bildet hierfür ein modulares Monitoringsystem, mit dem u. a. eine mehrstufige Biomassekategorisierung, ein regelmäßig aktualisierbares Netzwerk aus biomassespezifischen Berechnungselementen sowie ein Vorgehen zur kontinuierlichen Verbesserung der Datenqualität entwickelt wurde. Das Monitoringsystem wurde am Beispiel von Deutschland und für ein konsistentes Bezugsjahr erprobt. Für das Fallbeispiel Getreidestroh wurde darüber hinaus die zeitliche und räumliche Dynamik der Rohstoffverfügbarkeit mit einem Geo-Informationssystem analysiert. Mit Hilfe von 1.113 Berechnungselementen wurden das Aufkommen und die Nutzung für 77 Biomassen aus fünf Sektoren bilanziert. Auf dieser Grundlage ergibt sich für das Jahr 2015 ein technisches Biomassepotenzial in Höhe von 86–140 Millionen Tonnen Trockenmasse. Zwischen 65 % und 84 % waren bereits in einer stofflichen oder energetischen Nutzung gebunden. Ein deutlicher Schwerpunkt liegt auf nur wenigen Rohstoffen; 20 % der Rohstoffe repräsentieren über 80 % des Potenzials. Durch die weitere Erschließung der noch mobilisierbaren Potenziale in Höhe von 14–48 Millionen Tonnen Trockenmasse könnte zukünftig z. B. ein jährlicher Primärenergiebeitrag von mindestens 6 % und bis zu 15 % realisiert werden. Die Detailanalyse für das Fallbeispiel zeigt darüber hinaus, dass trotz erheblicher zeitlicher Schwankungen große Teile des Potenzials in nur wenigen Regionen konzentriert sind. Die insgesamt hohen Ergebnisbandbreiten deuten jedoch auf eine unsichere Datenqualität hin und insbesondere bei den Themen Boden- und Wasserqualität, Biodiversität und Eutrophierung von Ökosystemen besteht Forschungsbedarf, wie und mit welchen Datensätzen die komplexen Wirkungsgefüge zukünftig in die Potenzialberechnungen integriert werden können. Durch die konsequente Offenlegung der Monitoringergebnisse und der Berechnungsmethodik in einem Online-Datenrepositorium (http://webapp.dbfz.de) besteht die Möglichkeit, die bisherigen Ansätze in einem offenen Diskurs zu reflektieren und bedarfsgerecht weiterzuentwickeln. Mit Hilfe der Erkenntnisse aus dem Monitoringsystem kann der Fokus für die Umsetzung von Politik- und Unternehmensstrategien und das Schließen von Datenlücken auf die wichtigsten Rohstoffe und Regionen gelenkt werden. Zusammen mit den regionalen Stake- und Shareholdern können auf dieser Grundlage die nächsten Schritte für einen optimalen und nachhaltigen Beitrag zu einer bio-basierten Kreislaufwirtschaft priorisiert und weiterführend diskutiert werden.

To explore a recently established association between histaminergic and dopaminergic neuronal phenotypic systems in brain, we determined the effect of the respective histaminergic H3 receptor agonist and antagonist/inverse agonist, imetit and thioperamide, on L-DOPA - derived tissue and extracellular dopamine (DA) and metabolite levels in the striatum of 6-hydroxydopamine (6-OHDA) - lesioned rats (i.e., parkinsonian rats). We also examined the influence of histamine H3 ligands on L-DOPA evoked behavioral responses (locomotor activity, number of rearings, stereotyped behavior and motor coordination). Using HPLC/ED and in vivo microdialysis technique, imetit (5 mg/kg, i.p.) but not thioperamide (5 mg/kg, i.p.) was shown to attenuate an L-DOPA-evoked (15 mg/ kg, i.p.; carbidopa, 30 min pretreatment) increase in extracellular DA in the neostriatum of 6-OHDA-lesioned rats. However, both imetit and thioperamide increased microdialysate levels of DOPAC and HVA, probably by enhancing intraneuronal DA utilization. As indicated by neurochemical analysis of the striatum imetit produced a decrease in tissue DA content. These findings support the hypothesis that central H3 histaminergic receptors have a modulatory role in the storage, metabolism and release of DA derived from exogenous L-DOPA challenge. Furthermore, evidence from behavioral studies indicate that histamine H3 receptor block markedly improved motor coordination. Conversely, histamine H3 receptor stimulation, being without effect on motor coordination, enhanced vertical activity in rats. From the above we conclude that histamine H3 agonism may augment motor dyskinesia in Parkinson's disease (PD) patients and presumably worsen L-DOPA therapy. Consequently, the histaminergic system represents a viable target for modulating the effectiveness of L-DOPA therapy in Parkinson's disease.

On the morning of the first day of pregnancy, Wistar rats were administered a single IP injection of either zinc sulfate (10.0 mg/kg) or saline. For the remainder of pregnancy, half the rats in each group then consumed filtered tap water while the other half consumed filtered tap water with 50 ppm of cadmium (CdCl2). At eight weeks after birth, the behavioral profile of male offspring was assessed in the following way: Apomorphine (non-selective dopamine receptor agonist), (+)-7-hydroxy-2-(di-n-propylamino) tetralin (7-OH-DPAT) (D3 agonist) and (+/-)-1-phenyl-2,3,4,5-tetrahydro-(1H)-3-benzazepine-7,8-diol (SKF 38393) (D1 agonist) were used to evaluate stereotyped behavior, yawning activity and oral movements - indices for these respective agonists. In addition, two dopamine receptor antagonists, haloperidol (D2 antagonist) and 7-chloro-8-hydroxy-3-methyl-1-phenyl-2,3,4,5-tetrahydro-(1H)-3-benzapine (SCH 23390) (D1 antagonist) were used to evaluate cataleptogenic activity. Additional behavioral parameters studied were locomotor activity, irritability and reaction to a painful stimulus. Dopamine and its metabolites 3,4-dihydroxyphenylacetic acid (DOPAC), homovanillic acid (HVA) and 3-methoxytyramine (3-MT) were quantified in the striatum, hippocampus and in the frontal cortex of the brain by means of HPLC/ED technique. In addition, cadmium levels were analyzed in the brain, liver, kidney and bone of newborn rats. Our results indicate that prenatal exposure of pregnant rats to cadmium produced alterations in the reactivity of central dopamine receptors and modulated the level of dopamine and its metabolites in the offsprings' brains. A single injection of zinc, preceding cadmium consumption, attenuated some of the effects of cadmium on the offsprings' dopaminergic system. Zinc also reduced cadmium deposition in the brain, kidney and bone, but enhanced its accumulation in liver. In summary, zinc may exert some neuroprotective effects against cadmium neurotoxicity.

No description available.

Quantifying individual differences in behavior and the extent that behavior is influenced by circadian control is of paramount importance in behavioral ecology. In addition, the proximate mechanisms underlying behavior are also critical in order to obtain a more complete picture of how behavior evolves. Biogenic amines (BAs) are simple nitrogenous compounds derived from amino acids and have been consistently and extensively linked to behavior. For this study, we analyzed temporal patterns of BAs in relation to the antipredator (boldness) and aggressive behavior in female Agelenopsis pennsylvanica, a funnel-web spider. Using HPLC-ED, we compared behavioral responses to temporal patterns of octopamine and serotonin, two BAs known to influence behavior in invertebrates. Our results suggest that, while there was a clear diel cycling pattern of both aggression and boldness, BAs do not follow this same pattern, suggesting that oscillations in absolute levels of BAs are not the underpinnings of behavioral oscillations.

Biogenic volatile organic compounds (VOCs) react with Cl and OH radicals and the resulting radicals combine with oxygen to form peroxy radicals RO2. Organic peroxy radicals can then react with NO to form NO2, a precursor of tropospheric ozone. The work presented here explored the initial reaction between Cl and thujone, a VOC emitted by Great Basin sagebrush. The rate constant for the reaction of thujone + Cl at 296 K was measured with the method of relative rates with FTIR for detection of reactants. LEDs were used to photolyze Cl2 to generate Cl in the reaction cell. Thujone was also photolyzed by the LEDs and therefore the relative rates model was revised to account for this photolysis. With toluene as the reference compound, the rate constant for thujone + Cl at 296 K is 2.62 ± 1.90 × 10-12 molecules-1 s-1, giving an atmospheric lifetime of 0.5--2.6 minutes for thujone. Cline et al. showed that the rate of the self-reaction of HO2CH2CH2O2 (β-HEP) increases in the presence of water vapor. This enhancement has a strong temperature dependence with a greater enhancement observed at colder temperatures. The observed rate enhancement has been attributed to the formation of a β-HEP--H2O complex. In this work, the equilibrium constant for the formation of the β-HEP--H2O complex was calculated by ab initio calculations. Given the energy available at room temperature, the complex will populate three local minimum geometries and β-HEP will populate two local minimum geometries. The partition function for each of these geometries was calculated and used to calculate the equilibrium constant for complex formation as a function of temperature. Based on these computational results, the observed temperature dependence for the rate enhancement can be attributed to the strong temperature dependence for the rate constant of the reaction of β-HEP--H2O + β-HEP rather than the temperature dependence of complex formation.

Previous biostratigraphic studies in the Indian Ocean, equatorial Pacific, Atlantic Ocean and the Caribbean Sea document the temporal disappearance of Reticulofenestra pseudoumbilicus in the late Miocene (Tortonian age). This interval has been subsequently defined as the R. pseudoumbilicus paracme. While the cause of the event remains unknown, the geographical extent and global synchronicity of the interval represent an open subject for research. Answers to these questions could help establish the biostratigraphic reliability of the interval and its use for global correlation. In this study, 49 deep-sea drilling sites spread across all major ocean basins were compiled into a biostratigraphic database and studied to evaluate the global extent and timing of the R. pseudoumbilicus paracme. To ensure accurate comparison of the studied sites, the timing of the event was estimated at all sites using the age estimates generated through Undatable MatLab software, which made use of established nannofossil bioevents as age-depth tie points for the analysis. Ages of all nannofossil bioevents were updated to the latest geological time scale. This systematic analysis reveals a prominent distribution of the paracme in the tropical and subtropical regions. The timing of the event in the tropical region appears to be synchronous, with the base around 8.8 Ma and the top of the event around 7.2 Ma. Sites in the equatorial Pacific, central Atlantic and the Indian Oceans record a similar duration of the event. The paracme had a shorter duration towards the southern higher latitudes. Although timings in southern high latitudes are diachronous compared to the tropics, the duration is consistent between sites (Sites 1088 and 1264) in the southern South Atlantic, thereby establishing a new time frame for the event in the region. This study narrows down on ODP Site 806 for a critical evaluation of the nannofossil assemblages, accumulation rates and Reticulofenestra size variation in the late Miocene, including the paracme. Thirty-four samples were collected and analysed for absolute abundance and nannofossil accumulation rates (NAR). Absolute abundance and NAR reveal three distinct stages, herein described as generally low, high, and “crashed” export production of nannofossils. The period of high NAR is characteristic of the late Miocene biogenic bloom interval (ca. 9–4.4 Ma). Importantly, the R. pseudoumbilicus paracme does not only coincide with the start of the biogenic bloom but it was also associated with remarkable changes in Reticulofenestra assemblages. Just before the base of the paracme, all except the smallest (&lt;3 µm in coccolith size) Reticulofenestra groups experienced a sharp decline in abundance. Subsequently, the relative abundance of the Reticulofenestra morphospecies indicates the dominance of bloom-forming small and medium Reticulofenestra during the late Miocene biogenic bloom interval. The end of the biogenic bloom interval is concurrent with a decrease in the contribution of small Reticulofenestra. The exact biotic and abiotic processes that led to these major shifts in plankton composition are yet to be discovered, but the findings presented herein show that the mechanisms behind the temporary disappearance of R. pseudoumbilicus in the tropics most likely involved the interplay between a broad range of ecological changes and evolutionary processes affecting the Reticulofenestra assemblages. / <p>The work for this thesis was financially supported by the Erasmus Mundus Joint Master Degree PANGEAprogramme.</p>

A thermo-chemical treatment method was used to produce biogenic amorphous silica from South African sugarcane and maize residues. Different fractions of South African sugarcane (leaves, pith, and fiber) were processed for silica production. The biomass samples were leached with either 7 wt% citric acid or 7 wt% sulfuric acid at 353 K for 2 h prior to being rinsed, dried and combusted using a four-step program ranging from room temperature to 873 K in a furnace. The characterization of the pre-treated biomass samples was conducted using thermogravimetric analysis (TG/DTA), X-ray fluorescence analysis (XRF) and elemental analysis (CHN), while the final products were characterized by XRF, X-ray diffraction (XRD), elemental analysis, nitrogen physisorption and scanning electron microscopy (SEM). Citric acid pre-treatment proved to be an attractive alternative to mineral acids. Amorphous biogenic silica was produced from sugarcane leaves in good quality (0.1 wt% residual carbon and up to 99.3 wt% silica content). The produced biogenic silica also had great textural properties such as a surface area of up to 323 m2 g−1, average pore diameter of 5.0 nm, and a pore volume of 0.41 cm3 g−1.