The past few years have seen an upsurge in the use of renewable biomass as a source of energy due to growing concerns over greenhouse gas emissions caused by the combustion of fossil fuels and the need for energy independence due to depleting fossil fuel resources. Although coal will continue to be a major source of energy for many years, there is still great interest in replacing part of the coal used in energy generation with renewable biomass. Combustion converts inherent chemical energy of carbonaceous feedstock to only thermal energy. On the other hand, partial oxidation processes like gasification convert chemical energy into thermal energy as well as synthesis gas which can be easily stored or transported using existing infrastructure for downstream chemical conversion to higher value specialty chemicals as well as production of heat, hydrogen, and power. Devolatilization or pyrolysis plays an important role during gasification and is considered to be the starting point for all heterogeneous gasification reactions. Pyrolysis kinetic modeling is, therefore, an important step in analyzing interactions between blended feedstocks. The thermal evolution profiles of different coal-biomass blends were investigated at various heating rates using thermogravimetric analysis. Using MATLAB, complex models for devolatilization of the blends were solved for obtaining and predicting the global kinetic parameters. Parallel first order reactions model, distributed activation energy model and matrix inversion algorithm were utilized and compared for this purpose. Using these global kinetic parameters, devolatilization rates of unknown fuel blends gasified at unknown heating rates can be accurately predicted using the matrix inversion method. A unique laboratory scale auto-thermal moving bed gasifier was also designed and constructed for studying the thermochemical conversion of coal-biomass blends. The effect of varying operating parameters was analyzed for optimizing syngas production. In addition, stable carbon isotope analysis using Gas Chromatography-Combustion-Isotope Ratio Mass Spectrometry (GC-C-IRMS) was used for qualitatively and quantitatively measuring individual contributions of coal and biomass feedstocks for generation of carbonaceous gases during gasification. The predictive models utilized and experimental data obtained via these methods can provide valuable information for analyzing synergistic interactions between feedstocks and also for process modeling and optimization.

No / Gas chromatography (GC), GC-mass spectrometry (GC-MS) and GC-combustion-isotope ratio MS (GC-C-IRMS) analyses of absorbed and surface lipid residues preserved in potsherds were used to explore the extent of pig product processing exploitation in the later British Neolithic Grooved Ware tradition. Assessments were made regarding whether porcine lipids were associated with specific Grooved Ware traits, i.e. decoration, substyle, geographical area and type of site. Two hundred and twenty-two Grooved Ware potsherds were analysed, 70% of which contained lipid concentrations considered significant (>5 μg g−1). All the lipid residues were dominated by animal fats, although plant and beeswax were also detected in a small number of extracts. δ13C values of the major fatty acid components of degraded animal fats (C16:0 and C18:0) were determined for 126 extracts and used to assign ruminant or porcine origins to the residues; 16% of these were found to have a predominantly porcine isotope signature. Statistical associations with pig exploitation were shown to exist with substyle, geographical area and site type, whereas, no relationship was seen between decoration and the type of commodity processed. Intact triacylglycerols were preserved in 19% of the sherds; half of these had distributions consistent with the identifications based on δ13C values, the remainder differed either due to the presence of mixed commodities or because lower molecular weight homologues had been lost due to degradation. In addition to the detection of pig exploitation, results from lipid residue analysis showed a good correlation with faunal assemblages, suggesting that stable isotope analysis may be used as a proxy for animal exploitation at sites where bones have not survived.

This thesis investigates the relationship between climate, agriculture and social change in South Asia’s Bronze Age urban Indus Civilisation. Specifically, my research tests the hypothesis that an abrupt weakening of the Indian Summer Monsoon ca 2100 cal BC led to increasing crop water stress, and hence potentially contributed to the Civilisation’s decline by reducing food supply. This hypothesis is frequently invoked in discussions of the Civilisation’s end, yet until now, has not been empirically tested. Using material excavated from several Indus settlements, this study uses a novel combination of isotopic techniques to directly test the connection between climate change and agricultural stress. These techniques are first, oxygen isotope analysis of faunal bones and teeth; and second, stable carbon isotope analysis of crop remains. The oxygen analyses provide detailed records of monsoon intensity at a local, human scale, while the carbon analyses provide an empirical test of whether crop water stress increased. Applied in parallel across a diverse suite of Indus sites, these techniques together provide an archaeologically and ecologically-nuanced analysis of climatic impacts. The archaeological analyses are supported by a methodological study, which investigates how water status relates to the stable carbon isotope signature in barley (Hordeum vulgare) and the Indian jujube (Ziziphus mauritiana) along a climatic transect in north-western India today. Overall, the isotopic results suggest that at the sites sampled here, climate change probably had minimal impacts on crop water availability. This does not necessarily mean that climate change had no impacts on agriculture across the greater Indus sphere, and indeed there are hints that there may have been climatic stress in more vulnerable settings. However, at the sites studied here, any hydrological consequences of climate change—including the 4.2 ka event—appear to have had neither a lasting nor a pervasive impact on the adequacy of crop water supply. This is an important finding, and necessitates a clear refinement of how we think about climatic sensitivity, climatic vulnerability, and climatic impacts across—and indeed beyond—the greater Indus.

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