Insights into Pathways of Nitrous Oxide Generation from Novel Isotopologue Measurements

The accumulation of nitrous oxide (N2O) in the atmosphere is a significant manifestation of human perturbations of the nitrogen cycle. This thesis reports the development and first applications of a novel isotopic technique for characterizing nitrous oxide sources. Chapter 1 describes the development of methods to use the newly available technology of high- resolution dual-inlet multi-collector mass spectrometry to measure six isotopic parameters in nitrous oxide. It reports the standardization and initial biological application of these methods. Chapter 2 presents a model for the generation of isotope effects in an important N2O generating enzyme, the bacterial nitric oxide reductase; this model and published isotopic constraints are used to provide insights into the mechanism of that enzyme. Chapter 3 describes the six-dimensional isotopic characterization of nitrous oxide from bacterial denitrifiers, while Chapter 4 describes nitrous oxide generated by ammonia oxidizing bacteria.</p

Measurement of nitrous oxide isotopologues and isotopomers by the MAT 253 Ultra

The global budget of nitrous oxide is dominated by terrestrial and marine biological sources and atmospheric sinks. Details of the budget remain unclear, including the cause of increasing atmospheric N_2O concentrations. Marine sources of N_2O include denitrification and nitrification. Our understanding of the major microbial players in the nitrogen cycle has changed in recent years (for example, the nitrifying Archaea), and the overall contributions of these organisms to N_2O production and their isotopic signatures are poorly constrained [1]

Measurement of rare isotopologues of nitrous oxide by high-resolution multi-collector mass spectrometry

Rationale: Bulk and position-specific stable isotope characterization of nitrous oxide represents one of the most powerful tools for identifying its environmental sources and sinks. Constraining ^(14)N^(15)N^(18)O and ^(15)N^(14)N^(18)O will add two new dimensions to our ability to uniquely fingerprint N_2O sources. Methods: We describe a technique to measure six singly and doubly substituted isotopic variants of N2O, constraining the values of δ^(15)N, δ^(18)O, ∆^(17)O, ^(15)N site preference, and the clumped isotopomers ^(14)N^(15)N^(18)O and ^(15)N^(14)N^(18)O. The technique uses a Thermo MAT 253 Ultra, a high-resolution multi-collector gas source isotope ratio mass spectrometer. It requires 8–10 hours per sample and ~10 micromoles or more of pure N_2O. Results: We demonstrate the precision and accuracy of these measurements by analyzing N_2O brought to equilibrium in its position-specific and clumped isotopic composition by heating in the presence of a catalyst. Finally, an illustrative analysis of biogenic N_2O from a denitrifying bacterium suggests that its clumped isotopic composition is controlled by kinetic isotope effects in N_2O production. Conclusions: We developed a method for measuring six isotopic variants of N_2O and tested it with analyses of biogenic N_2O. The added isotopic constraints provided by these measurements will enhance our ability to apportion N_2O sources

Physics of intense, high energy radiation effects.

This document summarizes the work done in our three-year LDRD project titled 'Physics of Intense, High Energy Radiation Effects.' This LDRD is focused on electrical effects of ionizing radiation at high dose-rates. One major thrust throughout the project has been the radiation-induced conductivity (RIC) produced by the ionizing radiation. Another important consideration has been the electrical effect of dose-enhanced radiation. This transient effect can produce an electromagnetic pulse (EMP). The unifying theme of the project has been the dielectric function. This quantity contains much of the physics covered in this project. For example, the work on transient electrical effects in radiation-induced conductivity (RIC) has been a key focus for the work on the EMP effects. This physics in contained in the dielectric function, which can also be expressed as a conductivity. The transient defects created during a radiation event are also contained, in principle. The energy loss lead the hot electrons and holes is given by the stopping power of ionizing radiation. This information is given by the inverse dielectric function. Finally, the short time atomistic phenomena caused by ionizing radiation can also be considered to be contained within the dielectric function. During the LDRD, meetings about the work were held every week. These discussions involved theorists, experimentalists and engineers. These discussions branched out into the work done in other projects. For example, the work on EMP effects had influence on another project focused on such phenomena in gases. Furthermore, the physics of radiation detectors and radiation dosimeters was often discussed, and these discussions had impact on related projects. Some LDRD-related documents are now stored on a sharepoint site (https://sharepoint.sandia.gov/sites/LDRD-REMS/default.aspx). In the remainder of this document the work is described in catergories but there is much overlap between the atomistic calculations, the continuum calculations and the experiments

Measurement of rare isotopologues of nitrous oxide by high-resolution multi-collector mass spectrometry

Rationale: Bulk and position-specific stable isotope characterization of nitrous oxide represents one of the most powerful tools for identifying its environmental sources and sinks. Constraining ^(14)N^(15)N^(18)O and ^(15)N^(14)N^(18)O will add two new dimensions to our ability to uniquely fingerprint N_2O sources. Methods: We describe a technique to measure six singly and doubly substituted isotopic variants of N2O, constraining the values of δ^(15)N, δ^(18)O, ∆^(17)O, ^(15)N site preference, and the clumped isotopomers ^(14)N^(15)N^(18)O and ^(15)N^(14)N^(18)O. The technique uses a Thermo MAT 253 Ultra, a high-resolution multi-collector gas source isotope ratio mass spectrometer. It requires 8–10 hours per sample and ~10 micromoles or more of pure N_2O. Results: We demonstrate the precision and accuracy of these measurements by analyzing N_2O brought to equilibrium in its position-specific and clumped isotopic composition by heating in the presence of a catalyst. Finally, an illustrative analysis of biogenic N_2O from a denitrifying bacterium suggests that its clumped isotopic composition is controlled by kinetic isotope effects in N_2O production. Conclusions: We developed a method for measuring six isotopic variants of N_2O and tested it with analyses of biogenic N_2O. The added isotopic constraints provided by these measurements will enhance our ability to apportion N_2O sources

The MAT-253 Ultra — a novel high-resolution, multi-collector gas source mass spectrometer

We present the design, performance and representative applications of the MAT 253 Ultra – the first prototype of a new class of high-resolution gas source isotope ratio mass spectrometers

Multi-proxy dentition analyses reveal niche partitioning between sympatric herbivorous dinosaurs

Dentitions of the sympatric herbivorous dinosaurs Hungarosaurus (Ankylosauria, Nodosauridae) and Mochlodon (Ornithopoda, Rhabdodontidae) (Santonian, Hungary) were analysed to investigate their dietary ecology, using several complementary methods—orientation patch count, tooth replacement rate, macrowear, tooth wear rate, traditional microwear, and dental microwear texture analysis (DMTA). Tooth formation time is similar in Hungarosaurus and Mochlodon , and traditional and DMTA microwear features suggest low-browsing habits for both taxa, consistent with their inferred stances and body sizes. However, Mochlodon possesses a novel adaptation for increasing dental durability: the dentine on the working side of the crown is double the thickness of that on the balancing side. Moreover, crown morphology, enamel thickness, macrowear orientation, and wear rate differ greatly between the two taxa. Consequently, these sympatric herbivores probably exploited plants of different toughness, implying dietary selectivity and niche partitioning. Hungarosaurus is inferred to have eaten softer vegetation, whereas Mochlodon likely fed on tougher material. Compared to the much heavier, quadrupedal Hungarosaurus , the bipedal Mochlodon wore down more than twice as much of its crown volume during the functional life of the tooth. This heavy tooth wear might correlate with more intensive food processing and, in turn, could reflect differences in the metabolic requirements of these animals

A New Approach in Determining the Decadal Common Trends in the Groundwater Table of the Watershed of Lake “Neusiedlersee”

Shallow groundwater is one of the primary sources of fresh water, providing river base-flow and root-zone soil water between precipitation events. However, with urbanization and the increase in demand for water for irrigation, shallow groundwater bodies are being endangered. In the present study, 101 hydrographs of shallow groundwater monitoring wells from the watershed of the westernmost brackish lake in Europe were examined for the years 1997–2012 using a combination of dynamic factor and cluster analyses. The aims were (i) the determination of the main driving factors of the water table, (ii) the determination of the spatial distribution and importance of these factors, and (iii) the estimation of shallow groundwater levels using the obtained model. Results indicate that the dynamic factor models were capable of accurately estimating the hydrographs (avg. mean squared error = 0.29 for standardized water levels), meaning that the two driving factors identified (evapotranspiration and precipitation) describe most of the variances of the fluctuations in water level. Both meteorological parameters correlated with an obtained dynamic factor (r = −0.41 for evapotranspiration &amp; r = 0.76 for precipitation). The strength of these effects displayed a spatial pattern, as did the factor loadings. On this basis, the monitoring wells could be objectively distinguished into two groups using hierarchical cluster analysis and verified by linear discriminant analysis in 98% of the cases. This grouping in turn was determined to be primarily related to the elevation and the geology of the area. It can be concluded that the application of the data analysis toolset suggested herein permits a more efficient, objective, and reproducible delineation of the primary driving factors of the shallow groundwater table in the area. Additionally, it represents an effective toolset for the forecasting of water table variations, a quality which, in the view of the likelihood of further climate change to come, is a distinctive advantage. The knowledge of these factors is crucial to a better understanding of the hydrogeological processes that characterize the water table and, thus, to developing a proper water resource management strategy for the area

Widefield two laser interferometry

A novel system has been developed that can capture the wide- field interference pattern generated by interfering two independent and incoherent laser sources. The interferograms are captured using a custom CMOS modulated light camera (MLC) which is capable of demodulating light in the megahertz region. Two stabilised HeNe lasers were constructed in order to keep the optical frequency difference (beat frequency) between the beams within the operational range of the camera. This system is based on previously reported work of an ultrastable heterodyne interferometer [Opt. Express 20, 17722 (2012)]. The system used an electronic feedback system to mix down the heterodyne signal captured at each pixel on the camera to cancel out the effects of time varying piston phase changes observed across the array. In this paper, a similar technique is used to track and negate the effects of beat frequency variations across the two laser pattern. This technique makes it possible to capture the full field interferogram caused by interfering two independent lasers even though the beat frequency is effectively random. As a demonstration of the system’s widefield interferogram capture capability, an image of a phase shifting object is taken using a very simple two laser interferometer

LDRD project 151362 : low energy electron-photon transport.

At sufficiently high energies, the wavelengths of electrons and photons are short enough to only interact with one atom at time, leading to the popular %E2%80%9Cindependent-atom approximation%E2%80%9D. We attempted to incorporate atomic structure in the generation of cross sections (which embody the modeled physics) to improve transport at lower energies. We document our successes and failures. This was a three-year LDRD project. The core team consisted of a radiation-transport expert, a solid-state physicist, and two DFT experts