Design and Applications of a Decade-Spanning Terahertz Frequency Comb Spectrometer: Doppler-limited Rotational Spectroscopy of Methanol and Methanol-OD

This thesis details the design and applications of a terahertz (THz) frequency comb spectrometer. The spectrometer employs two offset locked Ti:Sapphire femtosecond oscillators with repetition rates of approximately 80 MHz, offset locked at 100 Hz to continuously sample a time delay of 12.5 ns at a maximum time delay resolution of 15.6 fs. These oscillators emit continuous pulse trains, allowing the generation of a THz pulse train by the master, or pump, oscillator and the sampling of this THz pulse train by the slave, or probe, oscillator via the electro-optic effect. Collecting a train of 16 consecutive THz pulses and taking the Fourier transform of this pulse train produces a decade-spanning frequency comb, from 0.25 to 2.5 THz, with a comb tooth width of 5 MHz and a comb tooth spacing of ~80 MHz. This frequency comb is suitable for Doppler-limited rotational spectroscopy of small molecules. Here, the data from 68 individual scans at slightly different pump oscillator repetition rates were combined, producing an interleaved THz frequency comb spectrum, with a maximum interval between comb teeth of 1.4 MHz, enabling THz frequency comb spectroscopy.

The accuracy of the THz frequency comb spectrometer was tested, achieving a root mean square error of 92 kHz measuring selected absorption center frequencies of water vapor at 10 mTorr, and a root mean square error of 150 kHz in measurements of a K-stack of acetonitrile. This accuracy is sufficient for fitting of measured transitions to a model Hamiltonian to generate a predicted spectrum for molecules of interest in the fields of astronomy and physical chemistry. As such, the rotational spectra of methanol and methanol-OD were acquired by the spectrometer. Absorptions from 1.3 THz to 2.0 THz were compared to JPL catalog data for methanol and the spectrometer achieved an RMS error of 402 kHz, improving to 303 kHz when excluding low signal-to-noise absorptions. This level of accuracy compares favorably with the ~100 kHz accuracy achieved by JPL frequency multiplier submillimeter spectrometers. Additionally, the relative intensity performance of the THz frequency comb spectrometer is linear across the entire decade-spanning bandwidth, making it the preferred instrument for recovering lineshapes and taking absolute intensity measurements in the THz region. The data acquired by the Terahertz Frequency Comb Spectrometer for methanol-OD is of comparable accuracy to the methanol data and may be used to refine the fit parameters for the predicted spectrum of methanol-OD.

Échanges d’énergie et d’eau des écosystèmes nordiques dans un contexte de changement climatique

Le réchauffement climatique affecte fortement les régions nordiques du Canada où le dégel du pergélisol discontinu à sa limite sud est accompagné du mouvement de la limite des arbres vers le nord en zone de pergélisol continu. Ces altérations faites aux paysages de la Taïga des Plaines sont le point de départ de plusieurs rétroactions puisque les changements apportés aux caractéristiques de la surface (au niveau de l’albédo, l’humidité du sol et la rugosité de la surface) vont à leur tour entraîner des modifications biophysiques et éventuellement influencer l’augmentation ou la diminution subséquente des températures et de l’humidité de l’air. Seulement, il y a un nombre important de facteurs d’influence qu’il est difficile de projeter toutes les boucles rétroactives qui surviendront avec les présents changements climatiques en régions nordiques. Dans le but de caractériser les échanges d’eau et d’énergie entre la surface et l’atmosphère de trois sites des Territoires du Nord-Ouest subissant les conséquences de l’augmentation des températures de l’air, la méthode micro-météorologique de covariance des turbulences fut utilisée en 2013 aux sites de Scotty Creek (forêt boréale et tourbière nordique en zone de pergélisol sporadique-discontinu), de Havikpak Creek (forêt boréale nordique en zone de pergélisol continu) et de Trail Valley Creek (toundra arctique en zone de pergélisol continu). En identifiant les procédés biotiques et abiotiques (ex. intensité lumineuse, disponibilité en eau, etc.) d’évapotranspiration aux trois sites, les contrôles par l’eau et l’énergie furent caractérisés et permirent ainsi de projeter une augmentation de la limitation en eau, mais surtout en énergie du site de Trail Valley Creek. La répartition de l’énergie projetée est semblable à celle de Havikpak Creek, avec une augmentation de la proportion du flux de chaleur sensible au détriment de celui latent suite aux modifications des caractéristiques de la surface (albédo, rugosité et humidité du sol). L’augmentation relative du flux d’énergie sensible laisse présager une boucle rétroactive positive de l’augmentation des températures de l’air à ce site. Ensuite, en comparant des données modelées de la hauteur de la couche limite planétaire et des données provenant de profils atmosphériques d’Environnement Canada entre les trois sites, les changements de hauteur de cette couche atmosphérique furent aussi projetés. Trail Valley Creek pourrait connaître une hausse de la hauteur de sa couche limite planétaire avec le temps alors que Scotty Creek connaîtrait une diminution de celle-ci. Ces changements au niveau des couches atmosphériques liés à la répartition des flux d’énergie dans les écosystèmes se répercuteraient alors sur le climat régional de façon difficile à déterminer pour l’instant. Les changements apportés désignent une boucle rétroactive positive des températures de l’air à Trail Valley Creek et l’inverse à Scotty Creek. Les deux axes d’analyse arrivent donc aux mêmes conclusions et soulignent aussi l’importance de l’influence mutuelle entre le climat et les caractéristiques spécifiques des écosystèmes à la surface.

Free Troposphere Ozone and Carbon Monoxide over the North Atlantic for 2001-2011

Carbon Monoxide (CO) and Ozone (O3) are considered to be one of the most important atmospheric pollutants in the troposphere with both having significant effects on human health. Both are included in the U.S. E.P.A list of criteria pollutants. CO is primarily emitted in the source region whereas O3 can be formed near the source, during transport of the pollution plumes containing O3 precursors or in a receptor region as the plumes subside. The long chemical lifetimes of both CO and O3 enable them to be transported over long distances. This transport is important on continental scales as well, commonly referred to as inter-continental transport and affects the concentrations of both CO and O3 in downwind receptor regions, thereby having significant implications for their air quality standards. Over the period 2001-2011, there have been decreases in the anthropogenic emissions of CO and NOx in North America and Europe whereas the emissions over Asia have increased. How these emission trends have affected concentrations at remote sites located downwind of these continents is an important question. The PICO-NARE observatory located on the Pico Mountain in Azores, Portugal is frequently impacted by North American pollution outflow (both anthropogenic and biomass burning) and is a unique site to investigate long range transport from North America. This study uses in-situ observations of CO and O3 for the period 2001-2011 at PICO-NARE coupled with output from the full chemistry (with normal and fixed anthropogenic emissions) and tagged CO simulations in GEOS-Chem, a global 3-D chemical transport model of atmospheric composition driven by meteorological input from the Goddard Earth Observing System (GEOS) of the NASA Global Modeling and Assimilation Office, to determine and interpret the trends in CO and O3 concentrations over the past decade. These trends would be useful in ascertaining the impacts emission reductions in the United States have had over Pico and in general over the North Atlantic. A regression model with sinusoidal functions and a linear trend term was fit to the in-situ observations and the GEOS-Chem output for CO and O3 at Pico respectively. The regression model yielded decreasing trends for CO and O3 with the observations (-0.314 ppbv/year & -0.208 ppbv/year respectively) and the full chemistry simulation with normal emissions (-0.343 ppbv/year & -0.526 ppbv/year respectively). Based on analysis of the results from the full chemistry simulation with fixed anthropogenic emissions and the tagged CO simulation it was concluded that the decreasing trends in CO were a consequence of the anthropogenic emission changes in regions such as USA and Asia. The emission reductions in USA are countered by Asian increases but the former have a greater impact resulting in decreasing trends for CO at PICO-NARE. For O3 however, it is the increase in water vapor content (which increases O3 destruction) along the pathways of transport from North America to PICO-NARE as well as around the site that has resulted in decreasing trends over this period. This decrease is offset by increase in O3 concentrations due to anthropogenic influence which could be due to increasing Asian emissions of O3 precursors as these emissions have decreased over the US. However, the anthropogenic influence does not change the final direction of the trend. It can thus be concluded that CO and O3 concentrations at PICO-NARE have decreased over 2001-2011.

Development of measurement and modeling techniques to quantify atmospheric deposition of persistent, bioaccumulative and toxic chemicals in the Great Lakes

Measurement and modeling techniques were developed to improve over-water gaseous air-water exchange measurements for persistent bioaccumulative and toxic chemicals (PBTs). Analytical methods were applied to atmospheric measurements of hexachlorobenzene (HCB), polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs). Additionally, the sampling and analytical methods are well suited to study semivolatile organic compounds (SOCs) in air with applications related to secondary organic aerosol formation, urban, and indoor air quality. A novel gas-phase cleanup method is described for use with thermal desorption methods for analysis of atmospheric SOCs using multicapillary denuders. The cleanup selectively removed hydrogen-bonding chemicals from samples, including much of the background matrix of oxidized organic compounds in ambient air, and thereby improved precision and method detection limits for nonpolar analytes. A model is presented that predicts gas collection efficiency and particle collection artifact for SOCs in multicapillary denuders using polydimethylsiloxane (PDMS) sorbent. An approach is presented to estimate the equilibrium PDMS-gas partition coefficient (Kpdms) from an Abraham solvation parameter model for any SOC. A high flow rate (300 L min-1) multicapillary denuder was designed for measurement of trace atmospheric SOCs. Overall method precision and detection limits were determined using field duplicates and compared to the conventional high-volume sampler method. The high-flow denuder is an alternative to high-volume or passive samplers when separation of gas and particle-associated SOCs upstream of a filter and short sample collection time are advantageous. A Lagrangian internal boundary layer transport exchange (IBLTE) Model is described. The model predicts the near-surface variation in several quantities with fetch in coastal, offshore flow: 1) modification in potential temperature and gas mixing ratio, 2) surface fluxes of sensible heat, water vapor, and trace gases using the NOAA COARE Bulk Algorithm and Gas Transfer Model, 3) vertical gradients in potential temperature and mixing ratio. The model was applied to interpret micrometeorological measurements of air-water exchange flux of HCB and several PCB congeners in Lake Superior. The IBLTE Model can be applied to any scalar, including water vapor, carbon dioxide, dimethyl sulfide, and other scalar quantities of interest with respect to hydrology, climate, and ecosystem science.

Échanges d’énergie et d’eau des écosystèmes nordiques dans un contexte de changement climatique

Le réchauffement climatique affecte fortement les régions nordiques du Canada où le dégel du pergélisol discontinu à sa limite sud est accompagné du mouvement de la limite des arbres vers le nord en zone de pergélisol continu. Ces altérations faites aux paysages de la Taïga des Plaines sont le point de départ de plusieurs rétroactions puisque les changements apportés aux caractéristiques de la surface (au niveau de l’albédo, l’humidité du sol et la rugosité de la surface) vont à leur tour entraîner des modifications biophysiques et éventuellement influencer l’augmentation ou la diminution subséquente des températures et de l’humidité de l’air. Seulement, il y a un nombre important de facteurs d’influence qu’il est difficile de projeter toutes les boucles rétroactives qui surviendront avec les présents changements climatiques en régions nordiques. Dans le but de caractériser les échanges d’eau et d’énergie entre la surface et l’atmosphère de trois sites des Territoires du Nord-Ouest subissant les conséquences de l’augmentation des températures de l’air, la méthode micro-météorologique de covariance des turbulences fut utilisée en 2013 aux sites de Scotty Creek (forêt boréale et tourbière nordique en zone de pergélisol sporadique-discontinu), de Havikpak Creek (forêt boréale nordique en zone de pergélisol continu) et de Trail Valley Creek (toundra arctique en zone de pergélisol continu). En identifiant les procédés biotiques et abiotiques (ex. intensité lumineuse, disponibilité en eau, etc.) d’évapotranspiration aux trois sites, les contrôles par l’eau et l’énergie furent caractérisés et permirent ainsi de projeter une augmentation de la limitation en eau, mais surtout en énergie du site de Trail Valley Creek. La répartition de l’énergie projetée est semblable à celle de Havikpak Creek, avec une augmentation de la proportion du flux de chaleur sensible au détriment de celui latent suite aux modifications des caractéristiques de la surface (albédo, rugosité et humidité du sol). L’augmentation relative du flux d’énergie sensible laisse présager une boucle rétroactive positive de l’augmentation des températures de l’air à ce site. Ensuite, en comparant des données modelées de la hauteur de la couche limite planétaire et des données provenant de profils atmosphériques d’Environnement Canada entre les trois sites, les changements de hauteur de cette couche atmosphérique furent aussi projetés. Trail Valley Creek pourrait connaître une hausse de la hauteur de sa couche limite planétaire avec le temps alors que Scotty Creek connaîtrait une diminution de celle-ci. Ces changements au niveau des couches atmosphériques liés à la répartition des flux d’énergie dans les écosystèmes se répercuteraient alors sur le climat régional de façon difficile à déterminer pour l’instant. Les changements apportés désignent une boucle rétroactive positive des températures de l’air à Trail Valley Creek et l’inverse à Scotty Creek. Les deux axes d’analyse arrivent donc aux mêmes conclusions et soulignent aussi l’importance de l’influence mutuelle entre le climat et les caractéristiques spécifiques des écosystèmes à la surface.

Linking thermal imaging to physiological indicators in Carica papaya L. under different watering regimes

Water deficit is the most limiting factor for yield and fruit-quality parameters in papaya crop (Carica papaya L.), deficit-irrigation (DI) strategies offering a feasible alternative to manage limiting water resources. When DI is applied, it is crucial to assess the physiological status of the crop in order to maintain the plant within a threshold value of water stress so as no to affect yield or fruit-quality parameters. The aim of this work was to evaluate the feasibility of thermal imaging in young papaya plants to assess the physiological status of this crop when it is subjected to different DI regimes, studying the relationships between the changes in leaf temperature (Tleaf) and in the major physiological parameters (i.e., stomatal conductance to water vapor, gs; transpiration, E; and net photosynthesis, An). The trial was conducted in a greenhouse from March to April of 2012. Plants were grown in pots and subjected to four irrigation treatments: (1) a full irrigation treatment (control), maintained at field capacity; (2) a partial root-zone drying treatment, irrigated with 50% of the total water applied to control to only one side of roots, alternating the sides every 7 days; (3) a regulated deficit irrigation (50% of the control, applied to both sides of plant); (4) and a non-irrigated treatment, in which irrigation was withheld from both sides of the split root for 14 days, followed by full irrigation until the end of the study. Significant relationships were found between Tleaf and major physiological variables such as gs, E and An. Additionally, significant relationships were found between the difference of leaf-to-air temperature (ΔTleaf–air) and gas-exchange measurements, which were used to establish the optimum range of ΔTleaf–air as a preliminary step to the crop-water monitoring and irrigation scheduling in papaya, using thermal imaging as the main source of information. According to the results, we conclude that thermal imaging is a promising technique to monitor the physiological status of papaya during drought conditions.

Linking thermal imaging to physiological indicators in Carica papaya L. under different watering regimes

Water deficit is the most limiting factor for yield and fruit-quality parameters in papaya crop (Carica papaya L.), deficit-irrigation (DI) strategies offering a feasible alternative to manage limiting water resources. When DI is applied, it is crucial to assess the physiological status of the crop in order to maintain the plant within a threshold value of water stress so as no to affect yield or fruit-quality parameters. The aim of this work was to evaluate the feasibility of thermal imaging in young papaya plants to assess the physiological status of this crop when it is subjected to different DI regimes, studying the relationships between the changes in leaf temperature (Tleaf) and in the major physiological parameters (i.e., stomatal conductance to water vapor, gs; transpiration, E; and net photosynthesis, An). The trial was conducted in a greenhouse from March to April of 2012. Plants were grown in pots and subjected to four irrigation treatments: (1) a full irrigation treatment (control), maintained at field capacity; (2) a partial root-zone drying treatment, irrigated with 50% of the total water applied to control to only one side of roots, alternating the sides every 7 days; (3) a regulated deficit irrigation (50% of the control, applied to both sides of plant); (4) and a non-irrigated treatment, in which irrigation was withheld from both sides of the split root for 14 days, followed by full irrigation until the end of the study. Significant relationships were found between Tleaf and major physiological variables such as gs, E and An. Additionally, significant relationships were found between the difference of leaf-to-air temperature (ΔTleaf–air) and gas-exchange measurements, which were used to establish the optimum range of ΔTleaf–air as a preliminary step to the crop-water monitoring and irrigation scheduling in papaya, using thermal imaging as the main source of information. According to the results, we conclude that thermal imaging is a promising technique to monitor the physiological status of papaya during drought conditions.

Scalar turbulent behavior in the roughness sublayer of an Amazonian forest.

An important current problem in micrometeorology is the characterization of turbulence in the roughness sublayer (RSL), where most of the measurements above tall forests are made. There, scalar turbulent fluctuations display significant departures from the predictions of Monin?Obukhov similarity theory (MOST). In this work, we analyze turbulence data of virtual temperature, carbon dioxide, and water vapor in the RSL above an Amazonian forest (with a canopy height of 40 m), measured at 39.4 and 81.6 m above the ground under unstable conditions. We found that dimensionless statistics related to the rate of dissipation of turbulence kinetic energy (TKE) and the scalar variance display significant departures from MOST as expected, whereas the vertical velocity variance follows MOST much more closely. Much better agreement between the dimensionless statistics with the Obukhov similarity variable, however, was found for the subset of measurements made at a low zenith angle Z, in the range 0°  <  |Z|  <  20°. We conjecture that this improvement is due to the relationship between sunlight incidence and the ?activation?deactivation? of scalar sinks and sources vertically distributed in the forest. Finally, we evaluated the relaxation coefficient of relaxed eddy accumulation: it is also affected by zenith angle, with considerable improvement in the range 0°  <  |Z|  <  20°, and its values fall within the range reported in the literature for the unstable surface layer. In general, our results indicate the possibility of better stability-derived flux estimates for low zenith angle ranges.

Scalar turbulent behavior in the roughness sublayer of an Amazonian forest.

An important current problem in micrometeorology is the characterization of turbulence in the roughness sublayer (RSL), where most of the measurements above tall forests are made. There, scalar turbulent fluctuations display significant departures from the predictions of Monin?Obukhov similarity theory (MOST). In this work, we analyze turbulence data of virtual temperature, carbon dioxide, and water vapor in the RSL above an Amazonian forest (with a canopy height of 40?m), measured at 39.4 and 81.6?m above the ground under unstable conditions. We found that dimensionless statistics related to the rate of dissipation of turbulence kinetic energy (TKE) and the scalar variance display significant departures from MOST as expected, whereas the vertical velocity variance follows MOST much more closely. Much better agreement between the dimensionless statistics with the Obukhov similarity variable, however, was found for the subset of measurements made at a low zenith angle Z, in the range 0°??

Cálculo espectral de la irradiación solar directa, difusa y global en Heredia, Costa Rica (ING)

A clear sky solar spectral model which describes the irradiation flux has been tested experimentally in Heredia, Costa Rica. A description of the model and comparisons with radiation data are presented. The model computes spectral fluxes of direct, diffuse and global solar irradiation incident on a horizontal surface. Necessary inputs include latitude, altitude, and surface albedo as characteristics of a location as well as the atmospheric characteristics: turbidity, precipitable water vapor, and total ozone content. The results evidence a satisfactory agreement.

Gas exchange rates at different vapor pressure deficits and water relations of 'Pera' sweet orange plants with citrus variegated chlorosis (CVC)

Net photosynthesis (A) and transpiration rates (E), stomatal conductance (g), water use efficiency (WUE), intrinsic water use efficiency (IWUE) and internal leaf CO2 concentration (C) in response to different vapor pressure deficit (1.2 and 2.5 kPa) were investigated in 'Pera' sweet orange plants affected by citrus variegated chlorosis (CVC), a disease caused by Xylella fastidiosa. All plants were well watered and leaf water potential (Pw) was also measured by the psychrometric technique. Results showed that healthy plants responded to higher vapor pressure deficit (VPD), lowering its net photosynthesis and transpiration rates, and stomatal conductance. However, diseased plants presented no clear response to VPD, showing lower A, E and g for both VPDs studied and very similar values to these variables in healthy plants at the highest VPD. Internal leaf CO2 concentration also decreased for healthy plants when under the highest VPD, and surprisingly, the same pattern of response was found in plants with CVC. These results, the lower Psi(w) and higher WUE values for diseased plants, indicated that this disease may cause stomatal dysfunction and affect the water resistance through xylem vessels, which ultimately may play some role in photosynthetic metabolism. (C) 2003 Elsevier B.V. B.V. All rights reserved.

Isothermal (liquid + liquid) equilibrium data at T = 313.15 K and isobaric (vapor + liquid + liquid) equilibrium data at 101.3 kPa for the ternary system (water + 1-butanol + p-xylene)

The (vapor + liquid), (liquid + liquid) and (vapor + liquid + liquid) equilibria of the ternary system (water + 1-butanol + p-xylene) have been determined. (Water + 1-butanol + p-xylene) is a type 2 heterogeneous ternary system with partially miscible (water + 1-butanol) and (water + p-xylene) pairs. By contrast, (1-butanol + p-xylene) is totally miscible under atmospheric conditions. This paper examines the (vapor + liquid) equilibrium in both heterogeneous and homogeneous regions at 101.3 kPa of pressure. (Liquid + liquid) equilibrium data at T = 313.15 K have also been determined, and for comparison, the obtained experimental data have been calculated by means of several thermodynamic models: UNIQUAC, UNIFAC and NRTL. Some discrepancies were found between the (vapor + liquid + liquid) correlations; however, the models reproduced the (liquid + liquid) equilibrium data well. The obtained data reveal a ternary heterogeneous azeotrope with mole fraction composition: 0.686 water, 0.146 1-butanol and 0.168 p-xylene.

Development of fundamental equations for vapor and liquid water /

AD 253 800.

Research and development of thin film vapor compression, saline water conversion system /

Mode of access: Internet.

Strategies for the management and treatment of coal seam gas associated water

Coal seam gas (CSG) is a growing industry in Queensland and represents a potential major employer and deliverer of financial prosperity for years to come. CSG is a natural gas composed primarily of methane and is found trapped underground in coal beds. During the gas extraction process, significant volumes of associated water are also produced. This associated water could be a valuable resource, however, the associated water comprises of various salt constituents that make it problematic for beneficial use. Consequently, there is a need to implement various water treatment strategies to purify the associated water to comply with Queensland’s strict guidelines and to mitigate environmental risks. The resultant brine is also of importance as ultimately it also has to be dealt with in an economical manner. In some ways it can be considered that the CSG industry does not face a water problem, as this has inherent value to society, but rather has a “salt issue” to solve. This study analyzes the options involved in both the water treatment and salt recovery processes. A brief overview of the constituents present in Queensland CS water is made to illustrate the challenges involved and a range of treatment technologies discussed. Water treatment technologies examined include clarification (ballasted flocculation, dissolved air flotation, electrocoagulation), membrane filtration (ultrafiltration), ion exchange softening and desalination (ion exchange, reverse osmosis desalination and capacitance deionization). In terms of brine management we highlighted reinjection, brine concentration ponds, membrane techniques (membrane distillation, forward osmosis), thermal methods, electrodialysis, electrodialysis reversal, bipolar membrane electrodialysis, wind assisted intensive evaporation, membrane crystallization, eutectic freeze crystallization and vapor compression. As an entirety this investigation is designed to be an important tool in developing CS water treatment management strategies for effective management in Queensland and worldwide.