Techn. Universiẗat, Diss., 2000--Berlin.

Techn. Universiẗat, Diss., 2002--Darmstadt.

Universiẗat, Diss., 2001--Jena.

Techn. Hochsch., Diss., 2002--Aachen.

Techn. University, Diss., 2004--Darmstadt.

University, Diss., 2003--Regensburg. / Erscheinungsjahr an der Haupttitelstelle: 2003.

University, Diss., 2004--Kiel.

Introduction Recently in our laboratory we needed a reliable and relatively simple source of aqueous solutions of [11C]CO2. We examined various methods of trapping [11C]CO2 gas both in solution and on ion exchange resins, followed by elution into aqueous phase. We favor simple methods that have high trapping and elution efficiencies and produce a highly concentrated solution. Furthermore, we desired methods that would minimize the use of hazardous reagents and materials with respect to both handling and disposal. We also considered the formulation of the final solution in terms of chemical compatibility with contacted materials, working with the assumption that dilute bicarbonate or carbonate solutions will have little reactivity with many materials. In a phantom, compatibility with materials (i.e. plastics, glues, metals, etc.) is important (1-4), while in (bio)geochemical studies – where transport of carbon is important – the chemical form of the radiolabelled molecule is important, but compatibility must be determined on a case-by-case basis (5-7). Small medical cyclotrons can easily produce carbon-11 as gaseous [11C]CO2, and various methods are utilized to incorporate carbon-11 into solution, often with unfavorable resource requirements, costs, or chemical properties. Commonly [11C]CO2 gas is bubbled through a strong base, forming the carbonate anion; but neutralizing a strong base (as to avoid special handling or disposal requirements) requires a large volume of diluent or buffer; or a very precise addition of acid – which if done improperly – may lead to an acidic pH and subsequent loss of [11C]CO2 from solution (8,9). Alternatively, [11C]CO2 (or [11C]CH4) can be converted to [11C]CH3I at high-yield, but requires specialized, expensive radio-synthesis equipment (10-12). [11C]CH3I can then be trapped in DMSO (albeit providing a volatile and hazardous solution) or used as a synthon en route to water soluble compounds such as [11C]choline (13). Finally, leftover radiolabelled radiopharmaceuticals from a carbon-11 imaging experiment could be used, but chemical compatibility (i.e. lipophilicity) of the radiolabelled compound may be of concern. Carbon dioxide gas will dissolve with a solubility of 1.5 g/L at STP (9) and slowly react with water to generate carbonic acid (H2CO3), a weak acid. Passing [11C]CO2 through a base-activated ion exchange cartridge, the [11C]CO2 reacts with hydroxide ions to form [11C]carbonate which is bound to the resin due to its higher selectivity for carbonate than hydroxide (14). Elution with excess bicarbonate displaces [11C]carbonate and neutralizes any remaining hydroxide, providing a 11C aqueous solution that is mildly basic, chemically non-hazardous, and very concentrated. Material and Methods [11C]CO2 gas trapping efficiency was evaluated for solutions and base-activated ion exchange resins. The gas was delivered either rapidly in a high-flow bolus directly from the cyclotron target or slowly in a low-flow helium stream during heating of a carbosieves column. Elution efficiency of ion exchange cartridges were evaluated for both fraction of trapped activity eluted and volume of solution needed for elution. [11C]CO2 was produced via the 14N(p,α)11C reaction on a CTI RDS111 – 11 MeV cyclotron at the Lawrence Berkeley National Laboratory’s Bio-medical Isotope Facility. The 7 mL target is pressurized to 315 psi with 1% O2/N2 gas, equating to 150 mL gas at STP. For direct-from-target trapping experiments, the target was decompressed and routed to the cartridge via 50 feet of 0.020” I.D. tubing until the target falls to atmospheric pressure (~55 seconds) providing an inhomogeneous flow – a short rapid burst of flow followed by a longer low-flow bleed. For helium-eluted experiments, the [11C]CO2 was unloaded from the cyclotron target and trapped on a room-temperature carbosieves column (15). Target gases were subsequently flushed from the column for 30 seconds with helium at 50 mL/min. After heating the column to 125 °C without gas flow, [11C]CO2 was eluted off the column in helium at 15 mL/min. [11C]CO2/He was bubbled through 9 aqueous and 2 organic solutions to test for trapping efficiency in a slow, steady helium stream at 15 mL/min (sodium hydroxide (0.96M, 0.096M, 0.0096M), sodium bicarbonate (1.14M, 0.57M, 0.057M), sodium carbonate (2.0M, 1.0M, 0.10M), ethanol, and DMSO (2mL ea.). An Ascarite-filled cartridge was attached to trap any untrapped [11C]CO2. Measures of radioactivity were made using a Capintec CRC-15R dose calibrator. Trapping efficiency for solutions is calculated as the fraction of radioactivity captured in solution relative to the sum of the solution and the Ascarite trap. Three different commercially available, ion ex-change cartridges were evaluated for trapping and elution efficiencies. FIGURE 1 shows a photo-graphic comparison of the physical size and shapes of the cartridges as well as a X-ray computed tomography (CT) cross sectional view of the internal ion exchange resin volume and dead volume of the cartridges. All cartridges were activated with 1 mL of 1 N aqueous NaOH followed by passing 10 mL deionized water then 10 mL of air through the cartridge. In both direct-from-target (n = 4) and helium-stream experiments (n = 3 or 4), cartridges were connected to [11C]CO2 delivery lines via Luer connections. The gas exiting the cartridge passed through an empty 3 mL crimp-top vial as a liquid trap en route to an Ascarite trap on the vent needle as described above. Trapping efficiency for cartridges is calculated as the fraction of radioactivity captured on the cartridge relative to the sum of the cartridge, the empty vial, and the Ascarite trap. Cartridges were eluted with 0.5 mL of saturated sodium bicarbonate solution (1.14 M @ 20°C) followed by 9.5 mL water and 10 mL air. Elution efficiency is calculated as the fraction of radioactivity eluted in 10 mL relative to the sum of the spent cartridge following elution and the 10 mL eluate (Equation 5). The pH of the eluate was measured using 0-14 pH test strips. Results and Conclusion The trapping of [11C]CO2 in all solutions was less than 70% of the total radioactivity with the exception of the 0.96 M and 0.096 M NaOH. With a higher concentration of base driving equilibrium towards carbonate stability, it could be expected that the most basic solution had the best trapping efficiency, but this attribute also means it is least desirable solution to work with from a hazardous material or chemical compatibility perspective. When [11C]CO2 was delivered in a helium stream, all three cartridges performed at near 100% efficiency, as shown in FIGURE 4. With higher flow, direct-from-target delivery, the cartridges trapped [11C]CO2 with a wider range of efficiencies: ICOH (99 ± 1 %), ORTG (90 ± 2 %), and QMA (79 ± 4 %). Elution resulted in > 99 % release of carbon-11 activity for both QMA and ORTG cartridges, but only 39 ± 3 % release from the ICOH cartridge. Elution efficiency of the trapped radioactivity (Equation 5) was independent of the method of [11C]CO2 delivery. Across all cartridges and delivery methods, the eluate was at about pH = 10. We recommend that the ORTG cartridge be used for trapping of [11C]CO2 gas with elution by > 300 µL of saturated bicarbonate solution. This recommendation is based on the better trapping for ORTG cartridges compared to the QMA cartridges in the direct-from-target [11C]CO2 delivery method and the smaller volume needed for elution of all trapped carbon. This method excels based on its simplicity, adaptability to automation, low-cost ($5/cartridge), and observations that a single ORTG cartridge suffers no loss of performance after multiple uses. A potential disadvantage to this method is that it involves using a carbon-containing eluent, which means that this method cannot be used for imaging experiments that require high specific activity. However, considering the eluate is a mildly basic aqueous solution, we expect that it will be compatible with a wide variety of materials and experimental applications.

The performance of a home-built tunable diode laser (TDL) spectrometer has been optimized regarding multi-line detection of carbon dioxide in natural gases. In the regime of the (30<SUP>0</SUP>1)<SUB>III</SUB> ← (000) band of <SUP>12</SUP>CO<SUB>2</SUB> around 1.6 μm, the dominating isotope species <SUP>12</SUP>CO<SUB>2</SUB>, <SUP>13</SUP>CO<SUB>2</SUB>, and <SUP>12</SUP>C<SUP>18</SUP>O<SUP>16</SUP>O were detected simultaneously. In contrast to most established techniques, selective measurements are performed without any sample preparation. This is possible since the CO<SUB>2</SUB> detection is free of interference from water, ubiquitous in natural gases. Detection limits in the range of a few ppmv were obtained for each species utilizing wavelength modulation (WM) spectroscopy with balanced detection in a long-path absorption cell set-up. Linear calibration plots cover a dynamic range of four orders of magnitude, allowing for quantitative CO<SUB>2</SUB> detection in various samples, like soil and breath gas. High isotopic resolution enables the excellent selectivity, sensitivity, and stability of the chosen analytical concept. The obtained isotopic resolution of typically ± 1.0 ‰ and ± 1.5 ‰ (for 3 vol. % and 0.7 vol. % of CO<SUB>2</SUB>, respectively) offers a promising analytical tool for isotope-ratio determination of carbon dioxide in soil gas. Preliminary experiments on soil respiration for the first time combine the on-line quantification of the overall carbon dioxide content with an optode sensor and isotopic determination (TDL system) of natural gas species.

The landfilling of biodegradable waste is proven to contribute to environmental degradation. Much wood and lumber is discharged as waste from the cleared fields. These woody wastes are subsequently disposed of by burning. However, it would be preferable to dispose of them without combustion to avoid the release of carbon dioxide, one of the critical greenhouse gases. Instead of burning these woody wastes, we should recycle them as future resources. One solution to this problem is to make compost from the waste. Compost use in agriculture is increasing as both an alternative to landfilling for the management of biodegradable waste, as well as means of increasing or preserving soil organic matter. This research aimed to contribute to the identification of a system for managing the production and utilization of wood waste (Quercus rubra and Pinus sylvestris) compost for sustainable agriculture, with particular regards to carbon dioxide produced from both compost and combustion of wood. Compost of wood was implemented in two consecutive trials. The first was carried out in greenhouse experiment in 4 liter pot of Quercus rubra and Pinus sylvestris (QR and PS) moisted by compost and tap water and infected by tiger worm (Eisenia fetida, EF) and European night crawlers (Dendrobaena veneta, DV) at different mixed ratios with lake mud (LM). The second was conducted in greenhouse experiment in 40 liter pot of the successful wood and worm from the first compost trial (QR and EF respectively). The tested wood (QR) was mixed separately by lake mud and horse manure and irrigated by compost and tap water. The final product, successful wood compost (QR) produced from the first trial (4 liter pot) was utilized in different mixed ratios with coal mine tailings (tertiary sand) in greenhouse pot trial to study his effects on improving soil physical and chemical properties and some plant growth parameters of RSM 7.2.1 grass. The wood compost produced from the second compost experiment (40 liter pot) and other artificial component named Arkadolith® were used as soil amelioration in field experiments of different selected sites with extremely unsuitable characteristics (tertiary and quaternary sand in Lusatia lignite region, Germany). The soil in each site was sowed by RSM 7.2.1 and autochthonous grasses. Also, some vermicompost samples were selected to study its thermal stability which compared with a soil sample (Niedermoorgleys) by using thermogravimetric analysis technique. Further investigation was achieved to evaluate the effect of charcoal as a source of carbon on vermicompost stability. Moreover some selected vermicompost samples were used to examine its microstructure under scanning electron microscope which compared also with the same soil used in thermal analysis. The obtained results under all studied experiments can be arranged as follow: First compost trial, Cumulative amount of carbon dioxide produced during composting period was lower than that evolved by combustion of wood. The results showed composting of wood can reduce the emitted CO2 up to 50 % when compared with the amount of CO2 produced from combustion of wood. The effect of different studied factors on different studied parameters show that, QR wood compost have more responsive to decomposition processes and humification rate in comparison with PS wood compost. Under different infection worms, Eisenia fetida (EF) was better than Dendrobaena veneta (DV) in biodegradation rate. Compost water has had a better impact of tap water in all studied decomposition parameters. For example, The compost content of OM and total OC was decreased with the increase of the decomposition period in the treatments of compost water and EF worm, where this decrease was higher at mixed ratio of 1:3 (wood: mud, w/w). The total content of N in the final products takes reversible trend regarding to OM and C content. The high content of N was found in QR wood compost moisted by compost water and infected by EF worm. The content of both macro-and micro-nutrients was clearly positive affected by the studied factors. The content of these nutrients in QR wood compost was higher than that found in the compost of PS wood. Second compost trial, The observed data show that, the amount of CO2 produced by composting was lower than that evolved by combustion of wood. Composting of wood reduced CO2 emission up to 40 % of the combustion wood CO2. Cumulative amount of CO2 produced from wood compost treated by horse manure was higher than that fount in the other treated by LM. The compost of wood treated by horse manure has had a high decomposition rate in comparison with that treated by lake mud. The treatments left without worms during all composting period and moisted by compost water have a responsive effects but it was lower than that infected by worms. Total and available contents of N, P, K, Mg, Zn, and Cu in the compost treated by HM were higher than that found in compost treated by LM. The other nutrients (Ca, Fe, Cu, and Mn) take reversible trend, which it was higher in LM than HM treatments. Thermal and microstructure analysis, The selected vermicompost samples from both first and second compost experiments showed, up to 200° C temperature the mass loss was due to free water and bound water (It was in vermicompost samples higher than soil sample). Mass loss from 200 to 550° C is due to easily oxidizable organic forms and it was higher in vermicompost than soil. In this stage the soil OM seems to be more stable than vermicompost which can be explained by a more intensive bond between the organic and inorganic components. At higher temperatures (T> 550° C) no significant detectable was appeared of soil organic matter. In contrast, the vermicompost treatments showed a high proportion of stable groups, especially aromatic compounds. These statements seem to be importance particularly for the practical application of the wood compost in terms of their long-term effect in the soil. The application of charcoal, showed no additional stabilizing effect of vermicompost. Also, the data show that, vermicompost structure characterized with high homogeneity and ratio of surface area to volume compared to those in soil structure. First plant trials (greenhouse), Different compost mixed ratios had positive impact on different extreme soil physiochemical properties. At the end of experiment (42 days) compost increased soil water holding capacity, decreased soil bulk and particle density and increased total porosity. The used wood compost modified soil buffering capacity and soil acidity. The availability of soil macro and micro nutrients were increased after adding wood compost. The wood compost had a positive effect in some growth parameters like fresh and dry matter yield of the selected grass. High dry matter yield and nutrients uptake was achieved with higher rates of compost application (25.0% > 12.5% > 3.0% > 0.0 %, w/w). Second plant trials (field experiment), Regarding to the effect of wood compost (QR) and Arkadolith® component on tertiary and quaternary sand, at the end of grown season (6 month) most soil and plant characteristics of tertiary sand were improved and it was better than that in quaternary sand. This trend reveals to, physical and chemical properties of tertiary sand was better than that in quaternary sand, like organic matter content, CEC, WHC, TOC, available nutrients. In the both sites, the effects of different type of soil conditioners arranged as follow: the treatments treated with wood compost is the better followed by the other treated with both wood compost and Arkadolith. Wood compost increased soil pH, CEC, soil buffering capacity, OM content, and soil WHC in comparison with Arkadolith which make a small improvement of these properties in both sites. Finally, Different growth parameters (height, covering, fresh and dry matter yield) of the used grasses were clearly positive affected by wood compost, with the highest production inherent to the treatments treated by the high amount of wood compost. / Entsprechend der Zielstellung wurden zunächst verschiedene Varianten der Kompostierung von Holzsubstanz getestet, um eine optimale Technologie, die auch für Entwicklungsländer realisierbar ist, herauszufinden. Hierzu sind in Pflanztöpfe Holzspäne (Woodchips) von zwei verschieden Holzarten (Laub- und Nadelholz) gefüllt und mit verschiedenen natürlichen Stickstoffquellen gemischt worden. Diese Ansätze wurden regelmäßig mit Kompostwasser appliziert. Nach vier Wochen sind zwei verschiedene Wurmarten (Dendrobaena veneta und Eisenia fetida) hinzugegeben worden. Die Feuchthaltung erfolgte ab diesem Zeitpunkt durch Frischwasser. Die qualitativ beste Versuchsvariante ist im nächsten Schritt mit weiteren natürlichen Stickstoffquellen, die in Entwicklungsländern zur Verfügung gestellt werden könnten, getestet worden. Von allen Kompostvarianten sind im Labor eine Vielzahl von bodenphysikalischen (z.B. Dichte, Wasserhaltekapazität) und bodenchemischen Zustandsgrößen (z.B. Elektrische Leitfähigkeit, Totalgehalte biophiler Elemente, Bodenreaktion, organische Substanzgehalte, Kationenaustauschkapazität) bestimmt worden. Die Wiederum qualitativ beste Mischung ist in einer weiteren Versuchsreihe in verschiedenen Mengenverhältnissen mit tertiärerem Abraumsand des Braunkohlebergbaus gemischt worden. In diese Versuchsmischungen wurde die Grasmischung RSM 7.2.1 eingesät und regelmäßig bewässert sowie die Wuchshöhe gemessen. Nach 42 Tagen wurden das Gras geerntet und die biometrischen Parameter, die Nährstoffgehalte (pflanzenverfügbare Fraktionen), die Bodenreaktion, die effektive bzw. potentielle Kationenaustauschkapazität sowie die Pufferkapazitäten der Mischsubstrate bestimmt. Die nächsten Versuchsvarianten sind als Feldversuche in der Niederlausitz durchgeführt worden. Für ihre Realisierung wurde als weiterer Zuschlagsstoff Arkadolith® zugemischt. Die Plotflächen sind sowohl auf Abraumsanden des Tertiärs als auch Quartärs angelegt worden. In jeweils eine Subvariante ist RSM 7.2.1, in die andere eine autochthone Grasmischung eingesät worden. Diese Experimente wurden nach 6 Monaten beendet, die Bestimmung aller Parameter erfolgte in gleicher Weise wie bei den Gewächshausversuchen. Auf Basis aller Versuchsreihen konnten die besten Kompostqualitäten und ihre optimalen Herstellungsvarianten ermittelt werden. Eine weitere Aufgabe war es zu untersuchen, wie im Vergleich zur Verbrennung von Holzmasse die CO2-Emission in die Atmosphäre durch Holzkompostierung verringert werden kann. Hierzu wurde während der verschiedenen Kompostierungsvarianten die CO2-Freisetzung gemessen. Im Vergleich dazu ist jeweils die gleiche Masse an Holzsubstanz verbrannt worden. Die Ergebnisse zeigten, dass im Vergleich zu der thermischen Verwertung von Holsubstanz die CO2-Emission bis zu 50 % verringert werden kann. Dem Boden kann darüber hinaus energiereiche organische Substanz zugeführt werden, die eine Entwicklung der Bodenorganismen ermöglicht. Ein weiteres Experiment zielte darauf ab, die Stabilität der Holzkomposte zu bestimmen. Darüber hinaus sollte untersucht werden, ob durch die Zufuhr von pyrogenem Kohlenstoff eine Vergrößerung der Stabilität zu erreichen ist. Diese Untersuchungen wurden mit Hilfe der Thermogravimetrie vorgenommen. Alle wichtigen Kompostierungsvarianten sind sowohl mit verschiedenen Zusatzmengen als auch ohne Zusatz von pyrogenem Kohlenstoff vermessen worden. Als Vergleichssubstanz diente der Oberboden eines Niedermoorgleys, der naturgemäß einen relativ hohen Anteil an organischer Substanz aufweist. Die Ergebnisse zeigten, dass im Bereich niedriger Temperaturen die Wasserbindung im Naturboden fester ist. In der Fraktion der oxidierbaren organischen Substanz, im mittleren Temperaturbereich gemessen, ist die natürliche Bodensubstanz ebenfalls stabiler, was auf eine intensivere Bindung zwischen den organischen und anorganischen Bestandteilen, also auf stabilere organisch-mineralische Komplexe, schlussfolgern lässt. Im Bereich höherer Temperaturen (T> 550° C) waren im Naturboden keine nennenswerten organischen Bestandteile mehr nachweisbar. Hingegen wiesen die Kompostvarianten einen hohen Anteil stabiler Fraktionen, vor allem aromatische Verbindungen, auf. Diese Aussagen erscheinen vor allem für die praktische Anwendung der Holzkomposte in Hinblick auf ihre Langzeitwirkung bedeutsam. Der Zusatz von pyrogenem Kohlenstoff zeigte keine zusätzliche Stabilisierungswirkung.