Studies were performed to characterize the physical nature of the air-ice interface, and to clarify its role in processes that occur there. A glancing-angle Raman probe was developed to monitor hydrogen bonding at atmospheric interfaces; we saw enhanced hydrogen-bonding on ice compared to on water. Using glancing-angle laser-induced fluorescence (LIF), we determined that small acids and bases dissociated to similar extents at air-water and air-ice interfaces, but aromatic compounds were less well solvated at air-ice interfaces, resulting in self-association even at low surface coverages. We measured uptake kinetics of organic compounds using LIF and Raman spectroscopy. The uptake kinetics can be adequately fit by a single-exponential growth equation, but in order to properly describe the self-association of aromatics observed at the air-ice interface, equations accounting for self-association should be incorporated into the uptake model. A simple model was developed for naphthalene which included terms for self-association; good fits to the observed growth of intensity from monomeric and self-associated naphthalene were obtained. Direct photolysis of aromatics was faster at air-ice interfaces than in bulk ice or aqueous solution. While red shifts in the absorption spectra of benzene and naphthalene at air-ice interfaces could explain their enhanced reactivity there, the enhanced anthracene photolysis kinetics on ice are likely due to enhanced absorption cross sections or photolysis quantum yields, or to a different photolysis mechanism there. Oxidation rates of aromatics by photo-formed hydroxyl radicals are suppressed at air-ice interfaces, but not in bulk ice. Similarly, gas-phase OH reacts rapidly with aromatics at air-water interfaces, but no reaction is observed at air-ice interfaces. Conversely, the reactivity of ozone toward phenanthrene is enhanced there. This is not due to temperature effects or to enhanced partitioning of ozone to ice. Ozonation of bromide is also more rapid at air-ice interfaces than at air-water interfaces at environmentally relevant bromide concentrations. This enhancement could be due to exclusion of bromide to the air-ice interface during freezing. The rapid reactions of ozone with bromide and phenanthrene at air-ice interfaces suggest that both reactions could be atmospherically important.

Methane fluxes were calculated from measurements carried out at a temperate upland forest in Central Ontario using the eddy covariance method over five months in the summer and fall seasons of 2011. Measurements were made by an off-axis integrated cavity output spectrometer Fast Greenhouse Gas Analyzer (FGGA) which simultaneously measured methane (CH4), carbon dioxide (CO2), and water at 10 Hz sampling rates. Observed methane fluxes showed net uptake of methane over the measurement period with an average uptake flux value (±standard deviation of the mean) of -2.7±0.13 nmol m-2 s-1. Methane fluxes showed a diurnal pattern of increased uptake during the day and increasing uptake with seasonal progression. There was also a significant correlation in methane fluxes with soil water content and wind speed. Comparison of the FGGA measurements to those using a static chamber method and canister sampling showed close agreement in flux and mixing ratio values respectively.

The carbon metabolism in costal sediments is of major importance for the global carbon cycle. Costal sediments are also subjected to physical forcing generating water fluxes above and through the sediments, but how the physical affect the carbon metabolism is currently poorly known. In this study, the effect of advective pore water flow on degradation of organic matter in permeable sandy sediment was investigated in a laboratory study during wintertime. Sediments were collected from both brackish water (Askö) and from a fresh water stream (Getå Stream). In two chamber experiments, with and without advective pore water flow, the degradation of organic matter was measured through carbon dioxide analysis from water and headspace. In Askö sediments mineralization rates ranged from 3.019 - 5.115 mmol C m-2 d-1 and 3.139 mmol C m-2 d-1 with and without advective pore water flow, respectively. Those results correspond with results from earlier studies of carbon mineralization rates in sediment in the North Sea and the Baltic Sea. There were no significant differences between the two groups in the Askö sediment. In Getå Stream sediments mineralization rates ranged between 4.059 mmol C m-2 d-1 and 6.806 mmol C m-2 d-1 with and without advective flow, respectively. The mineralization rates for Getå Stream correspond with earlier studies of carbon mineralization rates in a stream in New Hampshire.

The Earth’s surface contains of 71% oceans and a large part of the global carbon cycle takes place in the oceans. In the aquatic environment, the sediment-water interface plays an important role for the mineralisation of organic material. One factor that can affect the mineralisation is resuspension. Resuspension cause mixing of surface sediments and bottom water and result in a redistribution of the sediment when it settles again. Resuspension also increases the transport of oxygen into the sediment, reduces the diffusive boundary layer surrounding particles, and enhance the nutrient uptake. Resuspension can be induced by both wave action and bottom currents and is a common physical process in both shallow coastal areas and in the deep ocean. Human impacts, such as dredging and trawling, can also cause resuspension. The effect of resuspension on mineralisation of organic material was studied in two experiments ex situ during December to April 2004/2005. The aim for Experiment 1 was to investigate how the intensity of the resuspension event affects the degradation rate. The aim for Experiment 2 was to investigate how different concentrations of resuspended sediment affect the degradation rate of organic matter. Sediment samples were collected in December and late March at a marine field station, Askö, Sweden. Sediment and bottom water were transferred to and incubated in sealed bottles. For Experiment 1, resuspension was created in bottles with a specially designed rotary table, creating different intensity of water movements. In Experiment 2, bottles with different concentrations of sediment were put on an ordinary rotary table. The mineralisation rates were in both experiments monitored by daily sampling of sediment-water slurry, and analysed for total inorganic carbon by a gas chromatography with a thermal detector, GC-TCD. Results from Experiment 1 did not show any clear patterns regarding inorganic carbon formation. Experiment 2 did show clear patterns for two of six replicates of mineralisation of organic material. For these replicates the mineralisation rate were low according to previous studies. However, the sediment concentration seems to not affect the mineralisation rate. For both experiments, valuable information on how to better design experiments to investigate the importance of resuspension and the effect of mineralisation of organic material was yielded. Hence, further studies are needed to continue the investigation of the importance of resuspension for the mineralisation rate of organic material, and its impacts on the nutrient fluxes in the oceans.

Methane fluxes were calculated from measurements carried out at a temperate upland forest in Central Ontario using the eddy covariance method over five months in the summer and fall seasons of 2011. Measurements were made by an off-axis integrated cavity output spectrometer Fast Greenhouse Gas Analyzer (FGGA) which simultaneously measured methane (CH4), carbon dioxide (CO2), and water at 10 Hz sampling rates. Observed methane fluxes showed net uptake of methane over the measurement period with an average uptake flux value (±standard deviation of the mean) of -2.7±0.13 nmol m-2 s-1. Methane fluxes showed a diurnal pattern of increased uptake during the day and increasing uptake with seasonal progression. There was also a significant correlation in methane fluxes with soil water content and wind speed. Comparison of the FGGA measurements to those using a static chamber method and canister sampling showed close agreement in flux and mixing ratio values respectively.

Recent research has shown that the Arctic may be a sink for mercury, however, the fate of this deposited mercury in the environment is not known. The objective of this project was to determine the factors affecting methyl mercury (MeHg) production in Arctic organic soil on the Truelove Lowlands, Devon Island, Canada. In the field we observed a steady decrease in MeHg over time, with MeHg concentration at many sampling locations declining below detection limits. This decrease did not correlate to any chemical or biophysical parameter measured. During the study the Lowlands appeared to be mildly reducing with dissolved Fe(II) being present in the porewater, however, no correlation was observed between MeHg production and the variables measured. The dissolved organic matter concentration of the porewater was quite high, the pH was circumneutral and it would seem that in the absence of more highly reducing conditions that mercury would be unavailable for methylation.<p> It seems likely under field conditions MeHg was much more bioavailable then inorganic mercury. This would lead to a higher rate of demethylation then methylation and a net decrease in MeHg. Little research has been done on demethylation and the effect of environmental conditions on demethylation, especially in arctic environments. However, it is possible that the rate of demethylation was not affected by changes in temperature or any other parameter measured over the course of the field study. <p> Laboratory microcosm studies using saturated soil from the organic horizons demonstrated little potential for unspiked organic soil to produce significant amounts of MeHg. The spiked treatment, however, had an eight fold increase in MeHg concentration and the sterile treatment showed no change in MeHg concentration over 40 days of freeze (-5 0C) and 59 days of thaw (4 oC). <p> Our data suggests that a combination of atmospheric and in-situ processes maintain a cycle of MeHg production (spring) and loss (summer) in arctic soils. It would seem that Arctic wetland soils are not a significant source of MeHg to the Arctic ecosystem and that snowmelt is the dominant source.

The link between anthropogenic emissions of CO2 with increased atmospheric CO2 levels and, in turn, with increased global temperature has been well established and accepted. Using aqueous ammonia to capture CO2 and produce an inexpensive nitrogen fertilizer, ammonium bicarbonate (ABC) has been thought as a feasible approach to CO2 sequestration. Due to the different concentrations of reactants and reaction conditions, different carbon-ammonium composites can be produced. In view of achieving a maximum of NH3 utilization in the capture of CO2, the product of ABC will be ideal. Hence the ABC in the products needs to be identified. Various analytical techniques were used to distinguish the ABC. FTIR, DSC, TGA and XRD techniques were used to qualitatively distinguish the ammonium bicarbonate from the ammonium salts. The carbon, hydrogen and nitrogen element analysis and Near Infrared (NIR) techniques were used as quantitative analysis of ABC. The AOTF-NIR Free Space spectrometer is an ideal tool for real-time, on-line measurements of ABC. Sample 01050401 and Sample 01060401 from the CO2 Scrubbing experiment by aqueous ammonia at WKU were determined by these techniques as ammonium bicarbonate and have very good quality as fertilizer in accordance with GB -3559-92 Agriculture Ammonium Bicarbonate National Standard of China. During fertilizer storage and application, an amount of ABC will decompose into NH3, H2O and CO2. Long-effect ABC (LEABC) is a product of co-crystallized dicyanodiamide (DCD) and ABC. In order to evaluate ABC fertilizer efficiency and its contribution to permanent carbon fixation, tests with Thermogravimetric Analysis (TGA) were conducted. The experiments by TGA indicated that the temperature and air flow rate have much less effect on the evaporation of the LEABC than on the ABC. Kinetic studies of ABC and LEABC gave their Activation Energy. At the 7.5% conversion rate, LEABC’s Activation Energy is 111.9 kJ/mole, which is greater than ABC’s Activation Energy 93.6 kJ/mole. The difference in Activation Energy explains the reason of different stability of ABC and LEABC.

Studies were performed to characterize the physical nature of the air-ice interface, and to clarify its role in processes that occur there. A glancing-angle Raman probe was developed to monitor hydrogen bonding at atmospheric interfaces; we saw enhanced hydrogen-bonding on ice compared to on water. Using glancing-angle laser-induced fluorescence (LIF), we determined that small acids and bases dissociated to similar extents at air-water and air-ice interfaces, but aromatic compounds were less well solvated at air-ice interfaces, resulting in self-association even at low surface coverages. We measured uptake kinetics of organic compounds using LIF and Raman spectroscopy. The uptake kinetics can be adequately fit by a single-exponential growth equation, but in order to properly describe the self-association of aromatics observed at the air-ice interface, equations accounting for self-association should be incorporated into the uptake model. A simple model was developed for naphthalene which included terms for self-association; good fits to the observed growth of intensity from monomeric and self-associated naphthalene were obtained. Direct photolysis of aromatics was faster at air-ice interfaces than in bulk ice or aqueous solution. While red shifts in the absorption spectra of benzene and naphthalene at air-ice interfaces could explain their enhanced reactivity there, the enhanced anthracene photolysis kinetics on ice are likely due to enhanced absorption cross sections or photolysis quantum yields, or to a different photolysis mechanism there. Oxidation rates of aromatics by photo-formed hydroxyl radicals are suppressed at air-ice interfaces, but not in bulk ice. Similarly, gas-phase OH reacts rapidly with aromatics at air-water interfaces, but no reaction is observed at air-ice interfaces. Conversely, the reactivity of ozone toward phenanthrene is enhanced there. This is not due to temperature effects or to enhanced partitioning of ozone to ice. Ozonation of bromide is also more rapid at air-ice interfaces than at air-water interfaces at environmentally relevant bromide concentrations. This enhancement could be due to exclusion of bromide to the air-ice interface during freezing. The rapid reactions of ozone with bromide and phenanthrene at air-ice interfaces suggest that both reactions could be atmospherically important.

An approach to arsenic and selenium removal from fly ash is studied. This research includes a comparison of the leaching ability of ammonium oxalate, ammonium citrate, ammonium nitrate and EDTA to extract arsenic and selenium; use of common agricultural waste as a source of oxalate anion to remove arsenic and selenium from fly ash and estimation of additional calcium effects on arsenic and selenium leaching behaviors. This research shows that extraction strength order is EDTA > ammonium oxalate > ammonium citrate > ammonium nitrate > water, achieving arsenic extraction efficiencies of 94.18%, 84.17%, 4.50%, 2.89% and 0.18%, respectively; achieving selenium extraction efficiencies of 96.14%, 96.26%, 84.34%, 26.60% and 0.71%,respectively, in single-stage extraction. Tall fescue is applied as a source of natural oxalate resource and is able to remove over 70% of arsenic and selenium from fly ash. Additional calcium is found to make 82.20% of total arsenic in free oxalate leachate drop to 1.65% of total arsenic in free oxalate and free calcium leachate. All samples were analyzed using HG-AFS. Hopefully, this research will be helpful when a large scale, cheap and sustainable fly ash clean-up approach is needed for power plants prior to landfilling. Also, calcium effects will enable arsenic and selenium to move to the solid phase and could possibly solve the problem of toxic wastewater generated from the clean-up process. The enriched toxic solid waste could be used for pesticide applications.

Heavy metal contamination is a serious concern throughout the world. Increased concentrations in drinking water have many negative impacts on human health. Limestone is an inexpensive and simple media for removing high concentrations of heavy metals from drinking water supplies. Ferric based media is commonly used to remove zinc, cadmium, lead, arsenic and other heavy metals. The drinking water standards set by the US EPA for cadmium, zinc and arsenic are 0.005 mg/L, 5 mg/L and 0.010 mg/L respectively. Bangladesh, parts of India, China and the United States have high concentrations of arsenic in drinking water. Although many technologies exist for heavy metal removal, most of these are complicated and are associated with high costs making them ineffective and unfavorable to be used in impoverished areas. We propose a novel method that combines the benefits of limestone with the capacity of ferric media in an iron-coated limestone based material. Samples of water with various concentrations of zinc and cadmium were prepared and batch tests were performed using both uncoated and iron coated limestone and are compared in removal efficiency. Kinetics studies showed that zinc is removed to a maximum level after 24 hours, while cadmium takes only 15 minutes. The effect of pH on removal of heavy metals was also studied. Metals are analyzed using Inductively Coupled Plasma Emission Spectroscopy (ICP-ES). Limestone is readily available and is also easy to coat with iron, making this material a cost effective and affordable method to be used by developing countries.