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New pedologic, carbon isotope and phytolith analyses along with stratigraphic correlations to nearby archaeological sites record the spatial and temporal distribution of past vegetation patterns in the Sac Valley Archaeological District of southwest Missouri. Radiocarbon ages obtained from a soil core along Bear Creek, CB5, are related to those from Hajic et al. (1998, 2000) indicating that the CB5 location contains correlative middle Rodgers Shelter submember deposits. This relationship also indicates that sedimentation was approximately two times greater at the CB5 locality than at the Big Eddy (23CE426) archaeological site providing much higher temporal resolution for the alluvial history as well as the vegetation proxies during the early to middle Holocene. Most midcontinent climate proxy records include indications of an early Holocene warm period when prairie replaced forests, then a cooler period in which trees dominated the landscape, followed by a warmer middle Holocene period when prairie vegetation was dominant. However, the CB5 δ13C profile of mixed C3/C4 vegetation indicates either that the vegetation at this location was not as sensitive to climate change or that this location was buffered from other influences, e.g. fires, which were critical to the expansion of prairie vegetation. On the other hand, the phytolith assemblages at CB5 indicate that there were periods with abundant C4 grasses even though the δ13C values indicate a dominance of C3 vegetation. This indicates that in the mixed forest/prairie ecotone interpretations of past vegetation from either carbon isotopes or phytolith assemblages alone may not accurately reflect patterns of vegetation. A new core, DDY-KR2, was obtained from the Big Eddy (23CE426) archaeological site and a finer resolution of δ13C values at Big Eddy increased the detail about alluvial activity and revealed subtle changes in the vegetation. The vegetation types suggested by the δ13C values for DDY-KR2 are reflected in the phytolith assemblages validating their usefulness in reconstructing local vegetation history.

Over the past five years, gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS) analyses of phospholipid fatty acids (PLFAs) has been increasingly used to link organic matter (OM) sources with sedimentary bacteria. This technique has been applied across diverse estuarine and coastal sediments, including lower Laguna Madre, TX, an oligotrophic, coastal lagoon dominated by a single OM source, seagrasses; shelf stations, a eutrophic coastal region receiving multiple sources of OM, hypoxic regions that occur seasonally and deep slope and abyssal plain sediments of the Gulf of Mexico (GOM). Previous reports using the Laguna Madre data as examples, have been used to make comparisons of PLFA 16:0 and PLFA 15:0 isotope ratios and PLFA 16:0 and total organic carbon isotope ratios. Deviations from the 1:1 line in the former indicate living or recently senescent sources of organic matter are not predominantly bacterial. Deviations from the 1:1 line in the latter indicate living or recently senescent sources of organic matter differ isotopically from detrital or older OM in sediments. Prior to the work of Goni et al. (1998), carbon isotope ratios of OM in GOM sediments were interpreted as marine in origin. Based on a series of geochemical measurements, Goni et al. suggested that GOM sediments are largely composed of terrestrial organic carbon (OCterr). Furthermore, They went on to show that shelf and slope sediments were primarily C3 and C4 respectively. I report on the preferential utilization of autochthonous OM by sedimentary bacteria at the sediment surface and the shift to recalcitrant, terrestrially derived OM with depth.

Climate change is expected to have significant and uncertain impacts on methane (CH4) emissions from northern peatlands. Biogeochemical models can extrapolate site-specificCH(4) measurements to larger scales and predict responses of CH4 emissions to environmental changes. However, these models include considerable uncertainties and limitations in representing CH4 production, consumption, and transport processes. To improve predictions of CH4 transformations, we incorporated acetate and stable carbon (C) isotopic dynamics associated with CH4 cycling into a biogeochemistry model, DNDC. By including these new features, DNDC explicitly simulates acetate dynamics and the relative contribution of acetotrophic and hydro-genotrophic methanogenesis (AM and HM) to CH4 production, and predicts the C isotopic signature (delta C-13) in soil C pools and emitted gases. When tested against biogeochemical and microbial community observations at two sites in a zone of thawing permafrost in a subarctic peatland in Sweden, the new formulation substantially improved agreement with CH4 production pathways and delta C-13 in emitted CH4 (delta C-13-CH4), a measure of the integrated effects of microbial production and consumption, and of physical transport. We also investigated the sensitivity of simulated delta C-13-CH4 to C isotopic composition of substrates and, to fractionation factors for CH4 production (alpha(AM) and alpha(HM)), CH4 oxidation (alpha(MO)), and plant-mediated CH4 transport (alpha(TP)). The sensitivity analysis indicated that the delta C-13-CH4 is highly sensitive to the factors associated with microbial metabolism (alpha(AM), alpha(HM), and alpha(MO)). The model framework simulating stable C isotopic dynamics provides a robust basis for better constraining and testing microbial mechanisms in predicting CH4 cycling in peatlands.

The upper Homerian Mulde Event was a mass extinction that devastated graptolite diversity and occurred before and during the onset of a major perturbation to the global carbon cycle recorded as a double-peaked positive carbon isotope excursion (CIE). Whereas the Mulde Event and associated CIE are well-documented globally, changes in global sea level associated with the Mulde Event have only been investigated in detail in the West Midlands, England and Gotland, Sweden. A critical step toward understanding both the drivers and results of global climatic change during the Mulde Event is to constrain changes in eustasy. This study integrates carbon isotope chemostratigraphy and conodont biostratigraphy of Homerian strata in Tennessee, Indiana, and Ohio in an effort to determine if a global type-1 sequence boundary is recorded within the ascending limb of the Mulde CIE, and to produce a high-resolution chronostratigraphic framework for Homerian strata in the midcontinent USA. Six sections, two from each state, were measured and described. Five were sampled for carbon isotope chemostratigraphy, and one for conodont biostratigraphy. All sections from Tennessee and Indiana evidently contain the Mulde CIE, whereas the sections from Ohio are less clear due to the truncation of upper Homerian strata. These data demonstrate that a sequence boundary identified herein in Indiana and Tennessee is the same sequence boundary that occurred during the ascending limb of the Mulde Excursion in the West Midlands and Gotland.

Microbes, including Bacteria, are globally important mediators of elemental transformations in the marine water column, but not until recently has their biomass been suggested to contribute significantly to carbon export flux. Here I characterize lipid and carbon isotopic signatures in marine particulate organic matter (POM) explicitly at microbial size scales, and I quantitatively explore how these signatures are transferred down the water column. In the North Pacific Subtropical Gyre (NPSG) an isotopically-enriched pool of submicron POM appears to dominate export to mesopelagic depths, supporting recent observations that bacterioplankton communities contribute to export flux in proportion to their biological abundance. In the Eastern Tropical North Pacific (ETNP) complex pathways emerge for the flux of POM to the deep ocean. I use the largest data set to date for natural \(^{13}C\) signatures of individual water column lipids to reveal that submicron and larger-size suspended POM size classes are isotopically distinct. Results point to de novo production of lipids above and within the oxygen minimum zone. I develop quantitative models to deconvolve the signatures of sinking and in situ sources of these lipids. Results converge on a best-fit model for downward flux in the ETNP that includes both surface-derived and sub-photic zone lipids. Overall results from the modern ocean suggest that approximately half of total suspended POM is submicron in size, much of it is bacterial in origin, and despite the small size of this material, it participates dynamically in water column export flux. These results also suggest some revised interpretations of organic matter signatures in the geologic record. I formulate a quantitative model of marine microbial production and degradation, and reproduce "inverse" isotopic signatures found in lipids and organic matter preserved in Proterozoic sedimentary rocks. Results suggest that the disappearance of this inverse \(^{13}C\) pattern was a consequence of the shift from Bacteria to Eukarya as dominant producers of marine autotrophic biomass. Together, results of this thesis reveal that heterogeneity in the isotopic signatures of marine suspended POM is associated with particle size, and by extension, must be a function of the composition of the total planktonic community. / Earth and Planetary Sciences

Afforestation and reforestation programs utilizing available fields for biofuel production, carbon sequestration, and other uses linked to climate change are looking to tree physiologists to identify species and genotypes best-suited to their purposes. The ideal poplar genotype for use in Canadian programs would be drought-resistant, cold-climate adapted, and fast-growing, thus requiring an understanding of links between a variety of physiological traits linked to growth and productivity. This study examined the basis for variations in water-use efficiency within four selected populations of Populus trichocarpa and Populus balsamifera (2 provenances each). Each species included both a northern and a southern provenance. Correlations between water-use efficiency, nitrogen-use efficiency, ¹³C/¹²C isotope ratio, stomatal conductance, and overall productivity were evaluated. Gas exchange variables measured included net photosynthesis, transpiration rate, stomatal conductance, and intercellular CO₂ content. Water-use efficiency and ¹³C content across all genotypes were highly correlated. Results suggested that variation in water-use efficiency was primarily related to variation in stomatal conductance across all genotypes. Whereas differences in net photosynthesis in this study were not significant between species, P. balsamifera did reveal a higher average stem volume overall. Although variation in stomatal conductance was the major determinant of differences in water-use efficiency, positive correlations were found between ¹³C isotope abundance and net photosynthesis in both P. balsamifera provenances. In this regard, results for the northern P. balsamifera provenance are the most consistent across all gas-exchange and growth trait correlations, in terms of meeting expectations for sink-driven water-use efficiency. The findings in this study suggest the possibility of identifying poplar genotypes with an absence of trade-off between water-use efficiency and nitrogen-use efficiency, notably among genotypes from the northern P. balsamifera provenance, near Gillam.

Afforestation and reforestation programs utilizing available fields for biofuel production, carbon sequestration, and other uses linked to climate change are looking to tree physiologists to identify species and genotypes best-suited to their purposes. The ideal poplar genotype for use in Canadian programs would be drought-resistant, cold-climate adapted, and fast-growing, thus requiring an understanding of links between a variety of physiological traits linked to growth and productivity. This study examined the basis for variations in water-use efficiency within four selected populations of Populus trichocarpa and Populus balsamifera (2 provenances each). Each species included both a northern and a southern provenance. Correlations between water-use efficiency, nitrogen-use efficiency, ¹³C/¹²C isotope ratio, stomatal conductance, and overall productivity were evaluated. Gas exchange variables measured included net photosynthesis, transpiration rate, stomatal conductance, and intercellular CO₂ content. Water-use efficiency and ¹³C content across all genotypes were highly correlated. Results suggested that variation in water-use efficiency was primarily related to variation in stomatal conductance across all genotypes. Whereas differences in net photosynthesis in this study were not significant between species, P. balsamifera did reveal a higher average stem volume overall. Although variation in stomatal conductance was the major determinant of differences in water-use efficiency, positive correlations were found between ¹³C isotope abundance and net photosynthesis in both P. balsamifera provenances. In this regard, results for the northern P. balsamifera provenance are the most consistent across all gas-exchange and growth trait correlations, in terms of meeting expectations for sink-driven water-use efficiency. The findings in this study suggest the possibility of identifying poplar genotypes with an absence of trade-off between water-use efficiency and nitrogen-use efficiency, notably among genotypes from the northern P. balsamifera provenance, near Gillam.

Afforestation and reforestation programs utilizing available fields for biofuel production, carbon sequestration, and other uses linked to climate change are looking to tree physiologists to identify species and genotypes best-suited to their purposes. The ideal poplar genotype for use in Canadian programs would be drought-resistant, cold-climate adapted, and fast-growing, thus requiring an understanding of links between a variety of physiological traits linked to growth and productivity. This study examined the basis for variations in water-use efficiency within four selected populations of Populus trichocarpa and Populus balsamifera (2 provenances each). Each species included both a northern and a southern provenance. Correlations between water-use efficiency, nitrogen-use efficiency, ¹³C/¹²C isotope ratio, stomatal conductance, and overall productivity were evaluated. Gas exchange variables measured included net photosynthesis, transpiration rate, stomatal conductance, and intercellular CO₂ content. Water-use efficiency and ¹³C content across all genotypes were highly correlated. Results suggested that variation in water-use efficiency was primarily related to variation in stomatal conductance across all genotypes. Whereas differences in net photosynthesis in this study were not significant between species, P. balsamifera did reveal a higher average stem volume overall. Although variation in stomatal conductance was the major determinant of differences in water-use efficiency, positive correlations were found between ¹³C isotope abundance and net photosynthesis in both P. balsamifera provenances. In this regard, results for the northern P. balsamifera provenance are the most consistent across all gas-exchange and growth trait correlations, in terms of meeting expectations for sink-driven water-use efficiency. The findings in this study suggest the possibility of identifying poplar genotypes with an absence of trade-off between water-use efficiency and nitrogen-use efficiency, notably among genotypes from the northern P. balsamifera provenance, near Gillam. / Forestry, Faculty of / Graduate

Abstract Amorphous Calcium Carbonate (ACC) is a naturally occurring amorphous form of the widely distributed mineral calcium carbonate (CaCO3). ACC has been found increasingly as a precursor phase, calcium storage site, or strengthening structural phase in a wide array of different biomineralizing organisms. An accurate understanding of the widely used classic carbonate-water paleothermometry relies on formation of CaCO3 minerals and associated oxygen isotope effects. Moreover, ACC has oft been pointed to as a possible reason for non-equilibrium isotope effects, also called vital effects, in biogenic carbonates. It is, therefore, vital to understand whether ACC can reach equilibrium with its surrounding solution, as well as the role of ACC precursors in the isotopic composition and evolution of the final crystalline phase they transform into. This study is designed to answer these questions through the precipitation of stable ACC by two methods, the alkaline method (AM) which utilizes high pH to precipitate ACC, and the silica method (SM) which envelopes precipitating ACC particles in silica vesicles to prevent crystallization. These differently precipitated ACCs are then subjected to several different experimental treatments. This is achieved by monitoring the crystallization by X-ray Diffraction (XRD), and isotopic evolution of the ACC precipitates by Isotope Ratio Mass Spectrometry (IRMS) as they age and concurrently crystallize in parent solution, or in 18O enriched re-equilibration solution. This research indicated a marked difference in the crystallization behaviour, isotopic composition, and isotopic evolution of ACC produced by these two precipitation methods. With the AM method, ACC precipitates (AM-ACC) crystallized more predictably to calcite and maintained δ18O signatures that were slightly lower than the equilibrium CO32- and resisted further isotopic exchange with surrounding solution. We propose that the former is mostly due to an incomplete DIC-water oxygen isotope equilibrium prior to the AM-ACC precipitation and the latter is a result of the high pH of the precipitating solution decreasing the solubility of the precipitated ACC phase, disallowing isotope exchange, and favouring crystallization by solid-state transformation. Conversely, while ACC precipitated using the SM (SM-ACC) yielded much more variable results, both in terms of mineralogical identity upon crystallization, and δ18O values. Isotopic results were much closer to the expected equilibrium δ18O value for calcite, hinting at an expedited oxygen isotope exchange between SM-ACC and parent solution. Furthermore, SM-ACC was capable of isotopic exchange with the 18O enriched re-equilibration solution, a feat corresponding AM-ACC was incapable of. Overall, our experimental results gleaned here that precipitation method or precipitation environment play a critical role in the isotopic evolution of precursor ACC to crystalline CaCO3, suggesting ACC as an important source of the vital effect. / Thesis / Master of Science (MSc)