Entwicklung von neuen Radiomarkierungsverfahren und deren Anwendung zur Synthese von Radiotracern für die Positronen-Emissions-Tomographie

In den letzten 30 Jahren hat sich die Positronen Emissions Tomographie (PET) zu einem der wichtigsten Instrumente in der klinischen Diagnostik entwickelt. Neben den ständigen technischen Verbesserungen verdankt die PET ihren klinischen Stellenwert vor allem dem ihr inhärenten Potenzial, physiologische und biochemische Prozesse auf molekularer Ebene und in Echtzeit darzustellen. Aufgrund der wachsenden Zahl neuer und krankheitsspezifischer Radiotracer nimmt sie auch auf dem Gebiet der Wirkstoffentwicklung sowie beim Monitoring von pharmakologischen Interventionen eine immer wichtigere Rolle ein. Grundlegend hierfür ist einerseits das intelligente Design innovativer und selektiver molekularer Sonden mit der Fähigkeit zur Visualisierung molekularer Targets, die in physiologischen und pathophysiologischen Prozessen involviert sind und andererseits die Entwicklung der dafür notwendigen fortschrittlichen Markierungsstrategien. Letzteres ist zentraler Bestandteil der radiochemischen Grundlagenforschung und Hauptgegenstand dieser kumulativen Promotionsarbeit, in dessen Rahmen ein neues „minimalistisches“ Protokoll zur Radiofluorierung ausgearbeitet wurde. Die Entwicklung der sog. „minimalistische“ Methode ermöglicht eine vereinfachte und zeitsparende Herstellung von unterschiedlichsten 18F-markierten Verbindungen, da sie weder der azeotropen Trocknung noch des Zusatzes einer Base oder anderer Additive bedarf. Das neue Radiomarkierungsverfahren umfasst eine direkte Elution von 18F- mittels alkoholischer Lösung der Ammonium-, Diaryliodonium- oder Triarylsulfoniumsalz Vorläufern. Nach Entfernung des Alkohols wird das resultierende [18F]Fluoridsalz in einem geeigneten Lösungsmittel erhitzt. Die hohe Effizienz der auf der „minimalistischen“ Methode basierenden Synthese bietet somit auch einen schnellen Zugang zu 18F-markierten Fluorbenzaldehyden ([18F]FBAs) in großen Aktivitätsmengen, was einen entscheidenden Vorteil für die Entwicklung neuer Markierungsmethoden mit Hilfe dieses Radiomarkierungsbausteins darstellt. Darauf aufbauend wurde, ausgehend von [18F]FBA, auf der Basis der Seyferth-Gilbert Homologisierung, ein innovatives Verfahren zur Synthese von bisher unbekannten 18F-markierten Fluorarylacetylenen entwickelt. Hierdurch konnten über Cycloadditions- und Kreuzkupplungsreaktionen unterschiedliche radiomarkierte Modellverbindungen sowie PET-Tracer hergestellt und somit die Vielseitigkeit der neuen radiomarkierten Synthone aufgezeigt werden. Die durch die „minimalistische“ Methode gesteigerte Effizienz der Synthese von [18F]FBA ermöglicht es ebenfalls, den bereits in der Literatur bekannten Markierungsbaustein C-(4-[18F]Fluorphenyl)-N-phenylnitron [18F]FPPN in ausreichenden Mengen zu produzieren und für die zielgerichtete Synthese diverser radiofluorierter -Lactame über die Kinugasa-Reaktion einzusetzen. Mit dem Erhalt der radiofluorierten β-Lactam-Peptid und -Protein-Konjugate in hohen radiochemischen Ausbeuten unter sehr milden Bedingungen, konnte die Eignung der Kinugasa-Reaktion als neues und leistungsstarkes Radiofluorierungsverfahren eindrucksvoll demonstriert werden. 

Monitoring Mercury Deposition: A Key Tool to Understanding the Link Between Emissions and Effects

Illinois State Water Survey/National Atmospheric Deposition Program

Measuring nitrous oxide emissions from conventional and controlled release fertilisers in south-east Queensland pineapple production

Nitrous oxide (N2O) is a potent greenhouse gas with a global warming potential 298 times higher than carbon dioxide. Soils are a natural source of N2O, contributing 65% of global emissions. This paper is the first in Australia to measure and compare N2O emissions from pre-plant controlled release (CR) and conventional granular (CV) fertilisers in pineapple production using static PVC chambers to capture N2O emissions. Farm 1 cumulative emissions from the CR fertiliser were 3.22 kg ha-1 compared to 6.09 kg ha-1 produced by the CV. At farm 2 the CV blend emitted 2.36 kg ha-1 in comparison to the CR blend of 2.92 kg ha-1. Daily N2O flux rates showed a relationship of direct response to rainfall and soil moisture availability. High emissions were observed for wheel tracks where increased N2O emissions may be linked to soil compaction and waterlogging that creates anaerobic conditions after rain events. Emission measurements over three months highlighted the inconsistencies found in other studies relative to reducing emissions through controlled release nitrogen. More investigations are required to verify the benefits associated with controlled release fertiliser use in pineapples, placement and seasonal timing to address N2O emissions in pineapples.

Review of greenhouse gas emissions from the storage and land application of farm dairy effluent

The amounts of farm dairy effluent stored in ponds and irrigated to land have steadily increased with the steady growth of New Zealand's dairy industry. About 80% of dairy farms now operate with effluent storage ponds allowing deferred irrigation. These storage and irrigation practices cause emissions of greenhouse gases (GHG) and ammonia. The current knowledge of the processes causing these emissions and the amounts emitted is reviewed here. Methane emissions from ponds are the largest contributor to the total GHG emissions from effluent in managed manure systems in New Zealand. Nitrous oxide emissions from anaerobic ponds are negligible, while ammonia emissions vary widely between different studies, probably because they depend strongly on pH and manure composition. The second-largest contribution to GHG emissions from farm dairy effluent comes from nitrous oxide emissions from land application. Ammonia emissions from land application of effluent in New Zealand were found to be less than those reported elsewhere from the application of slurries. Recent studies have suggested that New Zealand's current GHG inventory method to estimate methane emissions from effluent ponds should be revised. The increasing importance of emissions from ponds, while being a challenge for the inventory, also provides an opportunity to achieve mitigation of emissions due to the confined location of where these emissions occur. © 2015 © 2015 The Royal Society of New Zealand.

Effects of incomplete combustion on atmospheric chemistry: Black carbon climate forcing and global carbon monoxide emissions

This thesis is actually the composition of two separate studies aimed at further understanding the role of incomplete combustion products on atmospheric chemistry. The first explores the sensitivity of black carbon (BC) forcing to aerosol vertical location since BC has an increased forcing per unit mass when it is located above reflective clouds. We used a column radiative transfer model to produce globally-averaged values of normalized direct radiative forcing (NDRF) for BC over and under different types of clouds. We developed a simple column-weighting scheme based on the mass fractions of BC that are over and under clouds in measured vertical profiles. The resulting NDRF is in good agreement with global 3-D model estimates, supporting the column-weighted model as a tool for exploring uncertainties due to diversity in vertical distribution. BC above low clouds accounts for about 20% of the global burden but 50% of the forcing. We estimate maximum-minimum spread in NDRF due to modeled profiles as about 40% and uncertainty as about 25%. Models overestimate BC in the upper troposphere compared with measurements; modeled NDRF might need to be reduced by about 15%. Redistributing BC within the lowest 4 km of the atmosphere affects modeled NDRF by only about 5% and cannot account for very high forcing estimates. The second study estimated global year 2000 carbon monoxide (CO) emissions using a traditional bottom-up inventory. We applied literature-derived emission factors to a variety of fuel and technology combinations. Combining these with regional fuel use and production data we produced CO emissions estimates that were separable by sector, fuel type, technology, and region. We estimated year 2000 stationary source emissions of 685.9 Tg/yr and 885 Tg/yr if we included adopted mobile sources from EDGAR v3.2FT2000. Open/biomass burning contributed most significantly to global CO burden, while the residential sector, primarily in Asia and Africa, were the largest contributors with respect to contained combustion sources. Industry production in Asia, including brick, cement, iron and steel-making, also contributed significantly to CO emissions. Our estimates of biofuel emissions are lower than most previously published bottom-up estimates while our other fuel emissions are generally in good agreement. Our values are also universally lower than recently estimated CO emissions from models using top-down methods.

Quantifying nitrous oxide emissions from sugarcane cropping systems : Optimum sampling time and frequency

Nitrous oxide (N2O) emissions from soil are often measured using the manual static chamber method. Manual gas sampling is labour intensive, so a minimal sampling frequency that maintains the accuracy of measurements would be desirable. However, the high temporal (diurnal, daily and seasonal) variabilities of N2O emissions can compromise the accuracy of measurements if not addressed adequately when formulating a sampling schedule. Assessments of sampling strategies to date have focussed on relatively low emission systems with high episodicity, where a small number of the highest emission peaks can be critically important in the measurement of whole season cumulative emissions. Using year-long, automated sub-daily N2O measurements from three fertilised sugarcane fields, we undertook an evaluation of the optimum gas sampling strategies in high emission systems with relatively long emission episodes. The results indicated that sampling in the morning between 09:00–12:00, when soil temperature was generally close to the daily average, best approximated the daily mean N2O emission within 4–7% of the ‘actual’ daily emissions measured by automated sampling. Weekly sampling with biweekly sampling for one week after >20 mm of rainfall was the recommended sampling regime. It resulted in no extreme (>20%) deviations from the ‘actuals’, had a high probability of estimating the annual cumulative emissions within 10% precision, with practicable sampling numbers in comparison to other sampling regimes. This provides robust and useful guidance for manual gas sampling in sugarcane cropping systems, although further adjustments by the operators in terms of expected measurement accuracy and resource availability are encouraged. By implementing these sampling strategies together, labour inputs and errors in measured cumulative N2O emissions can be minimised. Further research is needed to quantify the spatial variability of N2O emissions within sugarcane cropping and to develop techniques for effectively addressing both spatial and temporal variabilities simultaneously.

Climate Clever Beef: options to improve business performance and reduce greenhouse gas emissions in northern Australia

The Rangeland Journal – Climate Clever Beef special issue examines options for the beef industry in northern Australia to contribute to the reduction in global greenhouse gas (GHG) emissions and to engage in the carbon economy. Relative to its gross value (A$5 billion), the northern beef industry is responsible for a sizable proportion of national reportable GHG emissions (8–10%) through enteric methane, savanna burning, vegetation clearing and land degradation. The industry occupies large areas of land and has the potential to impact the carbon cycle by sequestering carbon or reducing carbon loss. Furthermore, much of the industry is currently not achieving its productivity potential, which suggests that there are opportunities to improve the emissions intensity of beef production. Improving the industry’s GHG emissions performance is important for its environmental reputation and may benefit individual businesses through improved production efficiency and revenue from the carbon economy. The Climate Clever Beef initiative collaborated with beef businesses in six regions across northern Australia to better understand the links between GHG emissions and carbon stocks, land condition, herd productivity and profitability. The current performance of businesses was measured and alternate management options were identified and evaluated. Opportunities to participate in the carbon economy through the Australian Government’s Emissions Reduction Fund (ERF) were also assessed. The initiative achieved significant producer engagement and collaboration resulting in practice change by 78 people from 35 businesses, managing more than 1 272 000 ha and 132 000 cattle. Carbon farming opportunities were identified that could improve both business performance and emissions intensity. However, these opportunities were not without significant risks, trade-offs and limitations particularly in relation to business scale, and uncertainty in carbon price and the response of soil and vegetation carbon sequestration to management. This paper discusses opportunities for reducing emissions, improving emission intensity and carbon sequestration, and outlines the approach taken to achieve beef business engagement and practice change. The paper concludes with some considerations for policy makers.

The effect of earlier mating and improving fertility on greenhouse gas emissions intensity of beef production in northern Australian herds

Approximately 5% of Australian national greenhouse gas (GHG) emissions are derived from the northern beef industry. Improving the reproductive performance of cows has been identified as a key target for increasing profitability, and this higher efficiency is also likely to reduce the GHG emissions intensity of beef production. The effects of strategies to increase the fertility of breeding herds and earlier joining of heifers as yearlings were studied on two properties at Longreach and Boulia in western Queensland. The beef production, GHG emissions, emissions intensity and profitability were investigated and compared with typical management in the two regions. Overall weaning rates achieved on the two properties were 79% and 74% compared with typical herd weaning rates of 58% in both regions. Herds with high reproductive performance had GHG emissions intensities (t CO2-e t–1 liveweight sold) 28% and 22% lower than the typical herds at Longreach and Boulia, with most of the benefit from higher weaning rates. Farm gross margin analysis showed that it was more profitable, by $62 000 at Longreach and $38 000 at Boulia, to utilise higher reproductive performance to increase the amount of liveweight sold with the same number of adult equivalents compared with reducing the number of adult equivalents to maintain the same level of liveweight sold and claiming a carbon credit for lower farm emissions. These gains achieved at two case study properties which had different rainfall, country types, and property sizes suggest similar improvements can be made on-farm across the Mitchell Grass Downs bioregion of northern Australia.

Influence of climate variability and stocking strategies on greenhouse gas emissions (GHGE), production and profit of a northern Queensland beef cattle herd

Previous studies of greenhouse gas emissions (GHGE) from beef production systems in northern Australia have been based on models of ‘steady-state’ herd structures that do not take into account the considerable inter-annual variation in liveweight gain, reproduction and mortality rates that occurs due to seasonal conditions. Nor do they consider the implications of flexible stocking strategies designed to adapt these production systems to the highly variable climate. The aim of the present study was to quantify the variation in total GHGE (t CO2e) and GHGE intensity (t CO2e/t liveweight sold) for the beef industry in northern Australia when variability in these factors was considered. A combined GRASP–Enterprise modelling platform was used to simulate a breeding–finishing beef cattle property in the Burdekin River region of northern Queensland, using historical climate data from 1982–2011. GHGE was calculated using the method of Australian National Greenhouse Gas Inventory. Five different stocking-rate strategies were simulated with fixed stocking strategies at moderate and high rates, and three flexible stocking strategies where the stocking rate was adjusted annually by up to 5%, 10% or 20%, according to pasture available at the end of the growing season. Variation in total annual GHGE was lowest in the ‘fixed moderate’ (~9.5 ha/adult equivalent (AE)) stocking strategy, ranging from 3799 to 4471 t CO2e, and highest in the ‘fixed high’ strategy (~5.9 ha/AE), which ranged from 3771 to 7636 t CO2e. The ‘fixed moderate’ strategy had the least variation in GHGE intensity (15.7–19.4 t CO2e/t liveweight sold), while the ‘flexible 20’ strategy (up to 20% annual change in AE) had the largest range (10.5–40.8 t CO2e/t liveweight sold). Across the five stocking strategies, the ‘fixed moderate’ stocking-rate strategy had the highest simulated perennial grass percentage and pasture growth, highest average rate of liveweight gain (121 kg/steer), highest average branding percentage (74%) and lowest average breeding-cow mortality rate (3.9%), resulting in the lowest average GHGE intensity (16.9 t CO2e/t liveweight sold). The ‘fixed high’ stocking rate strategy (~5.9 ha/AE) performed the poorest in each of these measures, while the three flexible stocking strategies were intermediate. The ‘fixed moderate’ stocking strategy also yielded the highest average gross margin per AE carried and per hectare. These results highlight the importance of considering the influence of climate variability on stocking-rate management strategies and herd performance when estimating GHGE. The results also support a body of previous work that has recommended the adoption of moderate stocking strategies to enhance the profitability and ecological stability of beef production systems in northern Australia.

Down scaling to regional assessment of greenhouse gas emissions to enable consistency in accounting for emissions reduction projects and national inventory accounts for northern beef production in Australia

This paper explores the effect of using regional data for livestock attributes on estimation of greenhouse gas (GHG) emissions for the northern beef industry in Australia, compared with using state/territory-wide values, as currently used in Australia’s national GHG inventory report. Regional GHG emissions associated with beef production are reported for 21 defined agricultural statistical regions within state/territory jurisdictions. A management scenario for reduced emissions that could qualify as an Emissions Reduction Fund (ERF) project was used to illustrate the effect of regional level model parameters on estimated abatement levels. Using regional parameters, instead of state level parameters, for liveweight (LW), LW gain and proportion of cows lactating and an expanded number of livestock classes, gives a 5.2% reduction in estimated emissions (range +12% to –34% across regions). Estimated GHG emissions intensity (emissions per kilogram of LW sold) varied across the regions by up to 2.5-fold, ranging from 10.5 kg CO2-e kg–1 LW sold for Darling Downs, Queensland, through to 25.8 kg CO2-e kg–1 LW sold for the Pindan and North Kimberley, Western Australia. This range was driven by differences in production efficiency, reproduction rate, growth rate and survival. This suggests that some regions in northern Australia are likely to have substantial opportunities for GHG abatement and higher livestock income. However, this must be coupled with the availability of management activities that can be implemented to improve production efficiency; wet season phosphorus (P) supplementation being one such practice. An ERF case study comparison showed that P supplementation of a typical-sized herd produced an estimated reduction of 622 t CO2-e year–1, or 7%, compared with a non-P supplemented herd. However, the different model parameters used by the National Inventory Report and ERF project means that there was an anomaly between the herd emissions for project cattle excised from the national accounts (13 479 t CO2-e year–1) and the baseline herd emissions estimated for the ERF project (8 896 t CO2-e year–1) before P supplementation was implemented. Regionalising livestock model parameters in both ERF projects and the national accounts offers the attraction of being able to more easily and accurately reflect emissions savings from this type of emissions reduction project in Australia’s national GHG accounts.

Feeding low protein diets to meat chickens: Effects on emissions of toxic and odorous metabolites

Low protein diet and odour emissions in meat chickens

Resource use and greenhouse gas emissions from grain-finishing beef cattle in seven Australian feedlots: a life cycle assessment

Grain finishing of cattle has become increasingly common in Australia over the past 30 years. However, interest in the associated environmental impacts and resource use is increasing and requires detailed analysis. In this study we conducted a life cycle assessment (LCA) to investigate impacts of the grain-finishing stage for cattle in seven feedlots in eastern Australia, with a particular focus on the feedlot stage, including the impacts from producing the ration, feedlot operations, transport, and livestock emissions while cattle are in the feedlot (gate-to-gate). The functional unit was 1 kg of liveweight gain (LWG) for the feedlot stage and results are included for the full supply chain (cradle-to-gate), reported per kilogram of liveweight (LW) at the point of slaughter. Three classes of cattle produced for different markets were studied: short-fed domestic market (55–80 days on feed), mid-fed export (108–164 days on feed) and long-fed export (>300 days on feed). In the feedlot stage, mean fresh water consumption was found to vary from 171.9 to 672.6 L/kg LWG and mean stress-weighted water use ranged from 100.9 to 193.2 water stress index eq. L/kg LWG. Irrigation contributed 57–91% of total fresh water consumption with differences mainly related to the availability of irrigation water near the feedlot and the use of irrigated feed inputs in rations. Mean fossil energy demand ranged from 16.5 to 34.2 MJ lower heating values/kg LWG and arable land occupation from 18.7 to 40.5 m2/kg LWG in the feedlot stage. Mean greenhouse gas (GHG) emissions in the feedlot stage ranged from 4.6 to 9.5 kg CO2-e/kg LWG (excluding land use and direct land-use change emissions). Emissions were dominated by enteric methane and contributions from the production, transport and milling of feed inputs. Linear regression analysis showed that the feed conversion ratio was able to explain >86% of the variation in GHG intensity and energy demand. The feedlot stage contributed between 26% and 44% of total slaughter weight for the classes of cattle fed, whereas the contribution of this phase to resource use varied from 4% to 96% showing impacts from the finishing phase varied considerably, compared with the breeding and backgrounding. GHG emissions and total land occupation per kilogram of LWG during the grain finishing phase were lower than emissions from breeding and backgrounding, resulting in lower life-time emissions for grain-finished cattle compared with grass finishing.

Rapid continuous chemical analysis of meat chicken shed emissions by SIFT–MS

Assessing and addressing odour impacts from poultry production is extremely difficult and subjective because the odorants involved and their dynamics over time and space are poorly understood. This knowledge gap is due, in part, to the lack of suitable analytical tools for measuring and monitoring odorants in the field. The emergence of Selected Ion Flow Tube – Mass Spectrometry (SIFT–MS) and similar instruments is changing that. These tools can rapidly quantify targeted odorants in ambient air in real time, even at very low concentrations. Such data is essential for developing better odour abatement strategies, assessment methods and odour dispersion models. This project trialled a SIFT–MS to determine its suitability for assessing the odorants in meat chicken shed emissions over time and space. This report details evaluations in New Zealand and Australia to determine the potential of SIFT–MS as a tool for the chicken meat industry, including odour measurement (as a proxy for dynamic olfactometry). The report is specifically targeted at those funding and conducting poultry odour research. It will be of interest to those involved with environmental odour monitoring and assessment in general. The high upfront cost of SIFT–MS will lead to potential users wanting compelling evidence that SIFT–MS will meet their needs before they invest in one.

NITROUS OXIDE EMISSIONS IN COVER CROP-BASED CORN PRODUCTION SYSTEMS

Nitrous oxide (N2O) is a potent greenhouse gas; the majority of N2O emissions are the result of agricultural management, particularly the application of N fertilizers to soils. The relationship of N2O emissions to varying sources of N (manures, mineral fertilizers, and cover crops) has not been well-evaluated. Here we discussed a novel methodology for estimating precipitation-induced pulses of N2O using flux measurements; results indicated that short-term intensive time-series sampling methods can adequately describe the magnitude of these pulses. We also evaluated the annual N2O emissions from corn-cover crop (Zea mays; cereal rye [Secale cereale], hairy vetch [Vicia villosa], or biculture) production systems when fertilized with multiple rates of subsurface banded poultry litter, as compared with tillage incorporation or mineral fertilizer. N2O emissions increased exponentially with total N rate; tillage decreased emissions following cover crops with legume components, while the effect of mineral fertilizer was mixed across cover crops.

Chronic Polyaromatic Hydrocarbon (PAH) Contamination Is a Marginal Driver for Community Diversity and Prokaryotic Predicted Functioning in Coastal Sediments

Benthic microorganisms are key players in the recycling of organic matter and recalcitrant compounds such as polyaromatic hydrocarbons (PAHs) in coastal sediments. Despite their ecological importance, the response of microbial communities to chronic PAH pollution, one of the major threats to coastal ecosystems, has received very little attention. In one of the largest surveys performed so far on coastal sediments, the diversity and composition of microbial communities inhabiting both chronically contaminated and non-contaminated coastal sediments were investigated using high-throughput sequencing on the 18S and 16S rRNA genes. Prokaryotic alpha-diversity showed significant association with salinity, temperature, and organic carbon content. The effect of particle size distribution was strong on eukaryotic diversity. Similarly to alpha-diversity, beta-diversity patterns were strongly influenced by the environmental filter, while PAHs had no influence on the prokaryotic community structure and a weak impact on the eukaryotic community structure at the continental scale. However, at the regional scale, PAHs became the main driver shaping the structure of bacterial and eukaryotic communities. These patterns were not found for PICRUSt predicted prokaryotic functions, thus indicating some degree of functional redundancy. Eukaryotes presented a greater potential for their use as PAH contamination biomarkers, owing to their stronger response at both regional and continental scales.