No description available.

Thesis (Ph.D.)--University of Delaware, 2007. / Principal faculty advisor: Chin-Pao Huang, Dept. of Civil & Environmental Engineering. Includes bibliographical references.

Thesis (M.S.)--University of Wisconsin--Madison, 1967. / eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

No description available.

To decrease carbon dioxide emissions into the atmosphere for climate change mitigation it is necessary to modify existing practices in processes where greenhouse gases are emitted. Due to the extremely large volumes of carbon dioxide produced globally, it is generally accepted that although carbon dioxide conversion and utilisation will contribute in the long term, in the short to medium term it will be necessary to capture and store carbon dioxide emissions to progress towards a low carbon future. Current industrial capture processes incur large energy and thus economic penalties. Storage in geological formations requires robust confidence in storage security to be publically accepted. Therefore the objective of this work was to study carbon dioxide capture and storage in processes directly confronting these two major challenges. Carbon dioxide adsorption on oxide materials for advanced carbon capture processes with lower energetic and economic penalties was investigated. Water was shown to play a crucial role in determining the presence of reactive sites, the speciation of carbonates formed and increased sorbent utilisation. A high surface area oxide with specifically exposed facets was prepared and the impact of these facets on carbon dioxide uptake performance was assessed. Volumetric gas adsorption and isotherm modelling supported the presence of two distinct adsorption sites. To enhance confidence in storage security it is necessary to understand storage processes that result in stable products. An apparatus capable of obtaining geological storage conditions was developed and carbonate formation and surface hydration at high pressure was investigated. By locating individual reactive cations on the surface of silica, silicate mineral analogues were prepared. It was shown that carbonate speciation was dependent on the reactive cation and the presence or absence of water.

Diss. (sammanfattning) Alnarp : Sveriges lantbruksuniv. / Härtill 5 uppsatser.

Thesis (Ph. D.)--Ohio State University, 2008.

Northern peatlands are a globally important soil carbon (C) store, and aquatic systems draining peatland catchments receive a high loading of dissolved and particulate forms of C from the surrounding terrestrial environment. Once incorporated into the aquatic environment, internal processes occur to modify the C pool. Of these, photo-processing preferentially targets terrestrially derived C and therefore might have a significant effect on the C budget of peatland draining aquatic systems. The overarching aim of this study was to investigate photochemical processing of C in Scottish peatland draining aquatic systems in order to determine the importance of this pathway in aquatic biogeochemical cycles. For initial laboratory experiments, water samples from a peatland headwater stream (Auchencorth Moss, SE Scotland) were collected. Laboratory based irradiation experiments were conducted at a range of temperatures, and different filtration treatments, including unfiltered samples, were employed to understand the fraction of C most susceptible to photo-processing. UV irradiation and temperature had a significant effect on DOC and gas headspace concentrations, with Q10 values of ~1.42 and ~1.65 derived for CO2 and CO photoproduction in unfiltered samples, respectively. However, filtration treatment did not induce significant changes in gaseous C production between light and dark samples, indicating that the experimental conditions favoured breakdown of DOC rather than POC to CO2 and CO. In all light treatments a small but significant increase in CH4 concentration was detected. These data were compared to results from experiments conducted in ambient light and temperature conditions. DOC normalised CO2 photoproduction was an order of magnitude lower than in laboratory conditions, although relative abundances of C species within overall budgets were similar and these experiments demonstrated that ambient exposure is sufficient to generate photo-processing of aquatic peatland C. Overall these data show that peatland C, particularly the < 0.2 μm fraction, is highly photoreactive and that this process is temperature sensitive. Further laboratory irradiation experiments were conducted on filtered water samples collected over a 13-month period from two contrasting aquatic systems. The first was the headwater stream draining Auchencorth Moss peatland with high DOC concentrations. The second was a low DOC reservoir (Loch Katrine, C Scotland) situated in a catchment with a high percentage peat cover. Samples were collected monthly from May 2014 to May 2015 and from the stream system during two rainfall events. Significant variation was seen in the photochemical reactivity of DOC between the two systems, with total irradiation induced change typically two orders of magnitude greater and DOC normalised CO2 production a factor of two higher in the headwater stream samples. This is attributed to longer water residence times in the reservoir rendering a higher proportion of the DOC recalcitrant to photo-processing. Overall the magnitude of photo-induced C losses was significantly positively correlated with DOC concentration in the headwater stream, which varied seasonally with highest concentrations detected in late autumn and winter. Rainfall events were identified as important in replenishing the stream system with photoreactive material, with lignin phenol data indicating mobilisation of fresh DOC from woody vegetation in the upper catchment during a winter rainfall event. Whilst these data clearly demonstrate that peatland catchments generate significant volumes of photoreactive DOC, the degree to which it is processed in the aquatic environment is unclear. Field investigations were undertaken to address this uncertainty. In-situ experiments with unfiltered water samples in light and dark conditions were conducted in two contrasting open water peatland pool systems. At the high DOC site (Red Moss of Balerno, SE Scotland), DOC concentrations in surface light exposed samples decreased by 18% compared to dark controls over 9 days and light treatments were enriched in CO2 and CH4. Photochemical processing was evident in δ13C-DOC and δ13C-DIC signatures of light exposed samples, which were enriched and depleted, respectively, relative to dark controls (+0.23 ‰ and -0.38 ‰) after 9 days of surface exposure. At the low DOC site (Cross Lochs, Forsinard, N Scotland) net production of DOC occurred in both light and dark samples over the experiment duration, in part due to POC breakdown. δ13C-DIC signatures indicated photolysis had occurred in light exposed samples (-1.98 ‰), whilst δ13C-DOC data suggest an absence of photo-processing, as the signatures in both treatments were similar. Accounting for light attenuation through the water column, 46 ± 4.9 and 8.7 ± 0.5 g C-CO2 eq m−2 yr−1 was processed by photochemical and microbial activity in peatland pools within the catchments at the high and low DOC sites, respectively. At both sites, light driven processing was responsible for a considerable percentage (34 and 51%) of gaseous C production when compared to equivalent estimates of microbial C processing and thus should be considered a key driver of peatland pool biogeochemical cycles. It is clear from this study that temperature, seasonal cycles, rainfall events and water residence time provide strong controls on the photoreactivity of aquatic C in Scottish peatland systems. The photo-processing pathway has the potential to alter the C balance of peatland catchments with a high percentage coverage of aquatic systems. Under climate change scenarios where light, temperature and rainfall conditions are expected to change, this process may become increasingly important in aquatic C cycling, particularly if the upward trend in DOC concentrations in northern aquatic systems continues.

The chemical speciation of trace metals controls their potential bioavailability and therefore toxicity to exposed organisms. Despite previous studies demonstrating the ameliorative effects of dissolved organic carbon (DOC) on metal toxicity, the effectiveness of ligands from varying sources and of potentially variable composition in controlling speciation has not been studied in detail in estuarine waters. In addition, the effect of DOC on radionuclide contaminants in combination with trace metals has not been investigated in any waters. This is of particular interest in the estuarine environment, where both anthropogenic and natural ligands, and contaminants that pose a potential threat to ecosystem health, can be present. Competitive ligand exchange adsorptive cathodic stripping voltammetry (CLE-AdCSV) with complexation capacity titrations was employed to determine the speciation of dissolved Cu and Zn, two metals that possess revised environmental quality standards (EQS) which now account for potential metal bioavailability. Dissolved metal concentrations in the < 0.4 and < 0.2 μm filter fractions of samples from the Tamar Estuary were determined during seasonal transects made over a calendar year. Samples were taken over a full salinity range (0-35) and from locations thought to contain DOC from a variety of sources (e.g. terrigenous, biogenic, sewage). No seasonal trends in metal speciation were identified, but a semi-quantitative assessment of DOC type using 3-D fluorimetry showed domination of humic and fulvic type ligands in the upper estuary, and biogenic-type ligands in the lower estuary, the former appearing the most important in controlling Cu and Zn complexation. Filter size fraction differences showed a major portion of the dissolved metal is associated with the 0.2 ≥ 0.4 μm fraction, indicating an importance of larger molecule ligands in controlling potentially bioavailable metal. Sample ligand concentrations ([L_x]) ranged from 1-372 nM (Cu) and 3-412 nM (Zn), and metal-ligand conditional stability constants (log K_(ML_x )) from 10.5-13.5 (Cu) and 7.5-10 (Zn), which are similar to reported literature. Calculated free metal ion concentrations ([M2+]) of 0.3 – 109 nM (Zn) and 1.4 x 10-13 – 7.3 x 10-11 M (Cu) compared well (92% showed no significant differences (P = 0.02)) with direct measurements of [Zn2+] made for the first time in estuarine waters using “Absence of Gradients and Nernst Equilibrium Stripping” (AGNES) after optimisation for estuarine waters. AGNES fully complements CLE-AdCSV in terms of analytical capability and shows that methods are now available that are capable of directly determining [Zn2+] in estuarine waters for use in environmental monitoring studies. Calculations made using the chemical equilibrium speciation programme Visual MINTEQ (VM) showed [Cu2+] and [Zn2+] could be predicted to within one order of magnitude of measured values when log K_(ML_x ) and [L_x] are determined and input into the model. This was in contrast to poor agreement between measured and predicted [M2+] when VM was used with the NICA-Donnan complexing model, which assumes a set portion of the total DOC concentration input is fulvic acid that actively complexes metals. These results corroborate a lack of identification of a relationship between metal speciation in the Tamar samples and DOC concentration, highlighting that knowledge of DOC type, log K_(ML_x )and L_x are important when assessing environmental risk, setting EQSs and for accurate modeling of [Cu2+]. Finally, a combined chemical and biological study investigating the effects of mixtures of DOC, Zn and the radionuclide tritium (3H) on the marine mussel presents the first evidence of a protective effect of Zn on DNA damage caused by 3H. The association of 3H with DOC remains elusive and an assessment of DOC type is recommended for future research, but the study emphasises the importance of investigating mixture effects in order to avoid inaccurate risk assessment and potentially costly site remediation.

Stomatal conductance and mesophyll conductance for CO2 transport are two key components of diffusive limitations of photosynthesis, since they restrict CO2 flux from the leaf surface to the sub-stomatal cavity and from there to the sites of carboxylation. This thesis summarizes our findings in the field of nature of mesophyll conductance to CO2 transport and its regulation per se and in respect to stomatal conductance.