Comparing satellite and ground-based observations of paroxysmal degassing events at Etna volcano, Italy

Mount Etna, Italy, is one of the most active volcanoes in the world, and is also regarded as one of the strongest volcanic sources of sulfur dioxide (SO2) emissions to the atmosphere. Since October 2004, an automated ultraviolet (UV) spectrometer network (FLAME) has provided ground-based SO2 measurements with high temporal resolution, providing an opportunity to validate satellite SO2 measurements at Etna. The Ozone Monitoring Instrument (OMI) on the NASA Aura satellite, which makes global daily measurements of trace gases in the atmosphere, was used to compare SO2 amount released by the volcano during paroxysmal lava-fountaining events from 2004 to present. We present the first comparison between SO2 emission rates and SO2 burdens obtained by the OMI transect technique and OMI Normalized Cloud-Mass (NCM) technique and the ground-based FLAME Mini-DOAS measurements. In spite of a good data set from the FLAME network, finding coincident OMI and FLAME measurements proved challenging and only one paroxysmal event provided a good validation for OMI. Another goal of this work was to assess the efficacy of the FLAME network in capturing paroxysmal SO2 emissions from Etna, given that the FLAME network is only operational during daylight hours and some paroxysms occur at night. OMI measurements are advantageous since SO2 emissions from nighttime paroxysms can often be quantified on the following day, providing improved constraints on Etna’s SO2 budget.

Open top chambers and infrared lamps : a comparison of heating efficacy and CO₂/CH₄ dynamics in a Lake Superior coastal peatland

Experimental warming provides a method to determine how an ecosystem will respond to increased temperatures. Northern peatland ecosystems, sensitive to changing climates, provide an excellent setting for experimental warming. Storing great quantities of carbon, northern peatlands play a critical role in regulating global temperatures. Two of the most common methods of experimental warming include open top chambers (OTCs) and infrared (IR) lamps. These warming systems have been used in many ecosystems throughout the world, yet their efficacy to create a warmer environment is variable and has not been widely studied. To date, there has not been a direct, experimentally controlled comparison of OTCs and IR lamps. As a result, a factorial study was implemented to compare the warming efficacy of OTCs and IR lamps and to examine the resulting carbon dioxide (CO2) and methane (CH4) flux rates in a Lake Superior peatland. IR lamps warmed the ecosystem on average by 1-2 #°C, with the majority of warming occurring during nighttime hours. OTC's did not provide any long-term warming above control plots, which is contrary to similar OTC studies at high latitudes. By investigating diurnal heating patterns and micrometeorological variables, we were able to conclude that OTCs were not achieving strong daytime heating peaks and were often cooler than control plots during nighttime hours. Temperate day-length, cloudy and humid conditions, and latent heat loss were factors that inhibited OTC warming. There were no changes in CO2 flux between warming treatments in lawn plots. Gross ecosystem production was significantly greater in IR lamp-hummock plots, while ecosystem respiration was not affected. CH4 flux was not significantly affected by warming treatment. Minimal daytime heating differences, high ambient temperatures, decay resistant substrate, as well as other factors suppressed significant gas flux responses from warming treatments.

Numerical study on the curling and warping of hardened rigid pavement slabs

In-service hardened concrete pavement suffers from environmental loadings caused by curling and warping of the slab. Traditionally, these loadings are computed on the basis of treating the slab as an elastic material, and of evaluating separately the curling and warping components. This dissertation simulates temperature distribution and moisture distribution through the slabs by use of a developed numerical model that couples the heat transfer and moisture transport. The computation of environmental loadings treats the slab as an elastic-viscous material, which considers the relaxation behavior and Pickett effect of the concrete. The heat transfer model considers the impacts of solar radiation, wind speed, air temperature, pavement slab albedo, etc. on the pavement temperature distribution. This dissertation assesses the difference between documented models that aim to predict pavement temperature, highlighting their pros and cons. The moisture transport model is unique for the documented models; it mimics the wetting and drying events occurring at the slab surface. These events are estimated by a proposed statistical algorithm, which is verified by field rainfall data. Analysis of the predicted results examines on the roles of the local air RH (relative humidity), wind speed, rainy pattern in the moisture distribution through the slab. The findings reveal that seasonal air RH plays a decisive role on the slab‘s moisture distribution; but wind speed and its daily variation, daily RH variation, and seasonal rainfall pattern plays only a secondary role. This dissertation sheds light on the computation of environmental loadings that in-service pavement slabs suffer from. Analysis of the computed stresses centers on the stress relaxation near the surface, stress evolution after the curing ends, and the impact of construction season on the stress‘s magnitude. An unexpected finding is that the total environmental loadings at the cyclically-stable state divert from the thermal stresses. At such a state, the total stress at the daytime is roughly equal to the thermal stress; whereas the total stress during the nighttime is far greater than the thermal stress. An explanation for this phenomenon is that during the night hours, the decline of the slab‘s near-surface temperature leads to a drop of the near-surface RH. This RH drop results in contraction therein and develops additional tensile stresses. The dissertation thus argues that estimating the environmental loadings by solely computing the thermally-induced stresses may reach delusive results. It recommends that the total environmental loadings of in-service slabs should be estimated by a sophisticated model coupling both moisture component and temperature component.

MODELING DYNAMICS OF OZONE AND NITROGEN OXIDES AT SUMMIT, GREENLAND WITH A 1-D PROCESS-SCALE MODEL

This work presents a 1-D process scale model used to investigate the chemical dynamics and temporal variability of nitrogen oxides (NOx) and ozone (O3) within and above snowpack at Summit, Greenland for March-May 2009 and estimates surface exchange of NOx between the snowpack and surface layer in April-May 2009. The model assumes the surface of snowflakes have a Liquid Like Layer (LLL) where aqueous chemistry occurs and interacts with the interstitial air of the snowpack. Model parameters and initialization are physically and chemically representative of snowpack at Summit, Greenland and model results are compared to measurements of NOx and O3 collected by our group at Summit, Greenland from 2008-2010. The model paired with measurements confirmed the main hypothesis in literature that photolysis of nitrate on the surface of snowflakes is responsible for nitrogen dioxide (NO2) production in the top ~50 cm of the snowpack at solar noon for March – May time periods in 2009. Nighttime peaks of NO2 in the snowpack for April and May were reproduced with aqueous formation of peroxynitric acid (HNO4) in the top ~50 cm of the snowpack with subsequent mass transfer to the gas phase, decomposition to form NO2 at nighttime, and transportation of the NO2 to depths of 2 meters. Modeled production of HNO4 was hindered in March 2009 due to the low production of its precursor, hydroperoxy radical, resulting in underestimation of nighttime NO2 in the snowpack for March 2009. The aqueous reaction of O3 with formic acid was the major sync of O3 in the snowpack for March-May, 2009. Nitrogen monoxide (NO) production in the top ~50 cm of the snowpack is related to the photolysis of NO2, which underrepresents NO in May of 2009. Modeled surface exchange of NOx in April and May are on the order of 1011 molecules m-2 s-1. Removal of measured downward fluxes of NO and NO2 in measured fluxes resulted in agreement between measured NOx fluxes and modeled surface exchange in April and an order of magnitude deviation in May. Modeled transport of NOx above the snowpack in May shows an order of magnitude increase of NOx fluxes in the first 50 cm of the snowpack and is attributed to the production of NO2 during the day from the thermal decomposition and photolysis of peroxynitric acid with minor contributions of NO from HONO photolysis in the early morning.