Synthesis and characterisation of novel nitrogen and fluorine containing spirobifluorene derivatives for electronic applications and crystal engineering

Among organic materials, spirobifluorene derivatives represent a very attractive class of materials for electronic devices. These compounds have high melting points, glass transitions temperatures and morphological stability, which makes these materials suitable for organic electronic applications. In addition, some of spirobifluorenes can form porous supramolecular associations with significant volumes available for the inclusion of guests. These molecular associations based on the spirobifluorenes are noteworthy because they are purely molecular analogues of zeolites and other microporous solids, with potential applications in separation, catalysis, sensing and other areas.

Application of biogas slurries from energy crops to arable soils and their impact on carbon and nitrogen dynamics

The use of renewable primary products as co-substrate or single substrate for biogas production has increased consistently over the last few years. Maize silage is the preferential energy crop used for fermentation due to its high methane (CH4) yield per hectare. Equally, the by-product, namely biogas slurry (BS), is used with increasing frequency as organic fertilizer to return nutrients to the soil and to maintain or increase the organic matter stocks and soil fertility. Studies concerning the application of energy crop-derived BS on the carbon (C) and nitrogen (N) mineralization dynamics are scarce. Thus, this thesis focused on the following objectives: I) The determination of the effects caused by rainfall patterns on the C and N dynamics from two contrasting organic fertilizers, namely BS from maize silage and composted cattle manure (CM), by monitoring emissions of nitrous oxide (N2O), carbon dioxide (CO2) and CH4 as well as leaching losses of C and N. II) The investigation of the impact of differences in soil moisture content after the application of BS and temperature on gaseous emissions (CO2, N2O and CH4) and leaching of C and N compounds. III) A comparison of BS properties obtained from biogas plants with different substrate inputs and operating parameters and their effect on C and N dynamics after application to differently textured soils with varying application rates and water contents. For the objectives I) and II) two experiments (experiment I and II) using undisturbed soil cores of a Haplic Luvisol were carried out. Objective III) was studied on a third experiment (experiment III) with disturbed soil samples. During experiment I three rainfall patterns were implemented including constant irrigation, continuous irrigation with periodic heavy rainfall events, and partial drying with rewetting periods. Biogas slurry and CM were applied at a rate of 100 kg N ha-1. During experiment II constant irrigation and an irrigation pattern with partial drying with rewetting periods were carried out at 13.5°C and 23.5°C. The application of BS took place either directly before a rewetting period or one week after the rewetting period stopped. Experiment III included two soils of different texture which were mixed with ten BS’s originating from ten different biogas plants. Treatments included low, medium and high BS-N application rates and water contents ranging from 50% to 100% of water holding capacity (WHC). Experiment I and II showed that after the application of BS cumulative N2O emissions were 4 times (162 mg N2O-N m-2) higher compared to the application of CM caused by a higher content of mineral N (Nmin) in the form of ammonium (NH4+) in the BS. The cumulative emissions of CO2, however, were on the same level for both fertilizers indicating similar amounts of readily available C after composting and fermentation of organic material. Leaching losses occurred predominantly in the mineral form of nitrate (NO3-) and were higher in BS amended soils (9 mg NO3--N m-2) compared to CM amended soils (5 mg NO3--N m-2). The rainfall pattern in experiment I and II merely affected the temporal production of C and N emissions resulting in reduced CO2 and enhanced N2O emissions during stronger irrigation events, but showed no effect on the cumulative emissions. Overall, a significant increase of CH4 consumption under inconstant irrigation was found. The time of fertilization had no effect on the overall C and N dynamics. Increasing temperature from 13.5°C to 23.5°C enhanced the CO2 and N2O emissions by a factor of 1.7 and 3.7, respectively. Due to the increased microbial activity with increasing temperature soil respiration was enhanced. This led to decreasing oxygen (O2) contents which in turn promoted denitrification in soil due to the extension of anaerobic microsites. Leaching losses of NO3- were also significantly affected by increasing temperature whereas the consumption of CH4 was not affected. The third experiment showed that the input materials of biogas plants affected the properties of the resulting BS. In particular the contents of DM and NH4+ were determined by the amount of added plant biomass and excrement-based biomass, respectively. Correlations between BS properties and CO2 or N2O emissions were not detected. Solely the ammonia (NH3) emissions showed a positive correlation with NH4+ content in BS as well as a negative correlation with the total C (Ct) content. The BS-N application rates affected the relative CO2 emissions (% of C supplied with BS) when applied to silty soil as well as the relative N2O emissions (% of N supplied with BS) when applied to sandy soil. The impacts on the C and N dynamics induced by BS application were exceeded by the differences induced by soil texture. Presumably, due to the higher clay content in silty soils, organic matter was stabilized by organo-mineral interactions and NH4+ was adsorbed at the cation exchange sites. Different water contents induced highest CO2 emissions and therefore optimal conditions for microbial activity at 75% of WHC in both soils. Cumulative nitrification was also highest at 75% and 50% of WHC whereas the relative N2O emissions increased with water content and showed higher N2O losses in sandy soils. In summary it can be stated that the findings of the present thesis confirmed the high fertilizer value of BS’s, caused by high concentrations of NH4+ and labile organic compounds such as readily available carbon. These attributes of BS’s are to a great extent independent of the input materials of biogas plants. However, considerably gaseous and leaching losses of N may occur especially at high moisture contents. The emissions of N2O after field application corresponded with those of animal slurries.

Nitrogen requirements of cassava in selected soils of Thailand

Cassava (Manihot esculenta) is one of the most important export crops in Thailand, yet the nitrogen requirement is unknown and not considered by growers and producers. Cassava requirements for N were determined in field experiments during a period of four years and four sites on the Satuk (Suk), Don Chedi (Dc), Pak Chong (Pc),and Ban Beung (BBg) soil series in Lopburi, Supanburi, Nakhon Ratchasima, and Chonburi sites, respectively. The fertilizer treatment structure comprised 0, 62.5, 125, 187.5, 250 and 312.5 kg N ha^(-1) as urea. At each site cassava was harvested at nine months and yield parameters and the minimum datasets were taken. The fertilizer rate which resulted in maximum yield ranged from 187.5 kg N ha^(-1) in Supanburi and Chonburi (fresh weight yield of 47,500 and 30,000 kg ha^(-1) respectively) to 250 kg N ha^(-1) in Lopburi and Nakhon Ratchasima (fresh weight yield of 64,100 and 46,700 kg ha^(-1) respectively). Yield appeared to decrease at the higher, 312 kg ha^(-1), at Supanburi and Lopburi, and 250 kg ha^(-1) (Chonburi) fertilizer N rates. Net revenue was 70.4 and 72.9 % higher than where no N was appliedLopburi and Nakhon Ratchasima sites. Net revenue at the Supanburi and Chonburi sites were 53.8 and 211.0 % higher than that where no N was applied. This study suggests that at all sites improved cassava production and net revenue could be obtained with the judicious application of higher quantities of N. The results provide needed guidance to nitrogen fertilization of the important industrial crop cassava in Thailand.

Nitrogen and carbon dynamics in grassland soils and plants after application of digestate

A better understanding of effects after digestate application on plant community, soil microbial community as well as nutrient and carbon dynamics is crucial for a sustainable grassland management and the prevention of species and functional diversity loss. The specific research objectives of the thesis were: (i) to investigate effects after digestate application on grass species and soil microbial community, especially focussing on nitrogen dynamic in the plant-soil system and to examine the suitability of the digestate from the “integrated generation of solid fuel and biogas from biomass” (IFBB) system as fertilizer (Chapter 3). (ii) to investigate the relationship between plant community and functionality of soil microbial community of extensively managed meadows, taking into account temporal variations during the vegetation period and abiotic soil conditions (Chapter 4). (iii) to investigate the suitability of IFBB-concept implementation as grassland conservation measure for meadows and possible associated effects of IFBB digestate application on plant and soil microbial community as well as soil microbial substrate utilization and catabolic evenness (Chapter 5). Taken together the results indicate that the digestate generated during the IFBB process stands out from digestates of conventional whole crop digestion on the basis of higher nitrogen use efficiency and that it is useful for increasing harvestable biomass and the nitrogen content of the biomass, especially of L. perenne, which is a common species of intensively used grasslands. Further, a medium application rate of IFBB digestate (50% of nitrogen removed with harvested biomass, corresponding to 30 50 kg N ha-1 a-1) may be a possibility for conservation management of different meadows without changing the functional above- and belowground characteristic of the grasslands, thereby offering an ecologically worthwhile alternative to mulching. Overall, the soil microbial biomass and catabolic performance under planted soil was marginally affected by digestate application but rather by soil properties and partly by grassland species and legume occurrence. The investigated extensively managed meadows revealed a high soil catabolic evenness, which was resilient to medium IFBB application rate after a three-year period of application.

Anàlisi comparativa dels processos emergents sharon i anammox per al tractament d’aigües amb una alta càrrega de nitrogen

Estudi de tractaments innovadors en aigües residuals amb elevada concentració de nitrogen mitjançant la tecnologia ANAMMOX (Anaerobic Ammonium Oxidation) i SHARON i posterior anàlisi teòrica de la gestió dels fangs residuals d’una EDAR

Anammox contra el nitrogen

Les elevades concentracions de nitrogen en forma d’amoni que contenen determinats efluents industrials generats per l’activitat humana són un problema que actualment porta associat un alt consum energètic, la qual cosa n’encareix el procés de depuració. Un equip de la Universitat de Girona, amb el suport de l’empresa CESPA, és a punt de provar a escala real una solució per resoldre aquest problema. Al darrere hi ha sis anys a linvestigació, que va començar des del no-res i que ha estat un èxit gràcies als coneixements i la intuïció dels investigadors gironins, que van creure que serien capaços de trobar i fer créixer el microorganisme anammox

A system to reduce the effect of CCDs saturation

Colour image segmentation based on the hue component presents some problems due to the physical process of image formation. One of that problems is colour clipping, which appear when at least one of the sensor components is saturated. We have designed a system, that works for a trained set of colours, to recover the chromatic information of those pixels on which colour has been clipped. The chromatic correction method is based on the fact that hue and saturation are invariant to the uniform scaling of the three RGB components. The proposed method has been validated by means of a specific colour image processing board that has allowed its execution in real time. We show experimental results of the application of our method

Correlación entre saturación venosa, ruptura de anastomosis y formación de fístulas en pacientes con trauma abdominal en el Hospital Occidente de Kennedy

El manejo del trauma abdominal supone el reto de realizar una anastomosis o sutura intestinal en pacientes comprometidos hemodinámicamente. La decisión de cirugía de control de daños ante la presencia de acidosis, hipotermia y coagulopatía es evidente, sin embargo la situación no siempre es tan clara. En individuos con trauma se desarrollan cambios moleculares e inflamatorios por inadecuado balance entre aporte y demanda de oxígeno, que afectan el proceso de reparación de los tejidos con el riesgo de aparición de fístulas. Una forma rápida y práctica de detectar esta hipoperfusión es midiendo la saturación venosa de oxígeno (SVO2) y el Lactato Sérico. OBJETIVOS: Establecer correlación entre los valores de SVO2 transoperatorio y la aparición de fístulas intestinales en pacientes intervenidos por trauma abdominal. MATERIALES Y METODOS: Estudio de cohorte prospectivo que analiza diferentes variables en relación con la aparición de fistulas en pacientes con trauma abdominal que requieren suturas en el tracto gastrointestinal, haciendo énfasis en los niveles de SVO2. RESULTADOS: Los pacientes con falla anastomótica, presentaron un promedio de SVO2 más baja (60.0% ± 2.94%), versus los no fistulizados (69.89% ± 7.21%) (p =0.010). Todos los pacientes de la cohorte expuesta (SVO2<65%), presentaron dehiscencia de la anastomosis (RR =39.8, IC95%: 2.35,659.91, p<0.001, Test exacto de Fisher). El valor predictivo positivo de la saturación (<65%) fue de 57.14% (IC 95%: 13.34%, 100%) y el valor predictivo negativo fue de 100% (IC 95%:81.75%, 100%). La sensibilidad fue de 100% (IC 95%:87.50%, 100%) y especificidad de 91.89% (IC 95%: 81.75%, 100%). En el análisis bivariante determinó que el índice de trauma abdominal, el nivel de hemoglobina y el requerimiento de transfusión de glóbulos rojos, son factores de riesgo directamente relacionados con la falla de la anastomosis en pacientes con trauma abdominal CONCLUSIONES: - Hay una fuerte relación entre la falla en la reparación intestinal y SVO2 < 65%. - El pronóstico de una anastomosis intestinal está directamente relacionada con el estado hemodinámico y la perfusión tisular al momento de la intervención quirúrgica. - El nivel de SVO2 puede apoyar al cirujano en la decisión de realizar o no una reparación en víscera hueca al momento de intervención quirúrgica en un paciente con trauma abdominal.

Control and optimization of an SBR for nitrogen removal: from model calibration to plant operation

En aquesta tesis s'ha desenvolupat un sistema de control capaç d'optimitzar el funcionament dels Reactors Discontinus Seqüencials dins el camp de l'eliminació de matèria orgànica i nitrogen de les aigües residuals. El sistema de control permet ajustar en línia la durada de les etapes de reacció a partir de mesures directes o indirectes de sondes. En una primera etapa de la tesis s'ha estudiat la calibració de models matemàtics que permeten realitzar fàcilment provatures de diferents estratègies de control. A partir de l'anàlisis de dades històriques s'han plantejat diferents opcions per controlar l'SBR i les més convenients s'han provat mitjançant simulació. Després d'assegurar l'èxit de l'estratègia de control mitjançant simulacions s'ha implementat en una planta semi-industrial. Finalment es planteja l'estructura d'uns sistema supervisor encarregat de controlar el funcionament de l'SBR no només a nivell de fases sinó també a nivell cicle.

Bald eagle (Haliaeetus leucocephalus) population increases in Placentia Bay, Newfoundland: evidence for habitat saturation?

Across North America, Bald Eagle (Haliaeetus leucocephalus) populations appear to be recovering following bans of DDT. A limited number of studies from across North America have recorded a surplus of nonbreeding adult Bald Eagles in dense populations when optimal habitat and food become limited. Placentia Bay, Newfoundland is one of these. The area has one of the highest densities of Bald Eagles in eastern North America, and has recently experienced an increase in the proportion of nonbreeding adults within the population. We tested whether the observed Bald Eagle population trends in Placentia Bay, Newfoundland during the breeding seasons 1990-2009 are due to habitat saturation. We found no significant differences in habitat or food resource characteristics between occupied territories and pseudo-absence data or between nest sites with high vs. low nest activity/occupancy rates. Therefore there is no evidence for habitat saturation for Bald Eagles in Placentia Bay and alternative hypotheses for the high proportion of nonbreeding adults should be considered. The Newfoundland population provides an interesting case for examination because it did not historically appear to be affected by pollution. An understanding of Bald Eagle population dynamics in a relatively pristine area with a high density can be informative for restoration and conservation of Bald Eagle populations elsewhere.

Impact of perturbations of nitrogen oxide emissions from global aviation