Browsing by Subject "pyrolysis"

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    Advances in Gas Chromatography, Thermolysis, Mass Spectrometry, and Vacuum Ultraviolet Spectrometry
    (2021-05) Rael, Ashur; Goodpaster, John V.; Manicke, Nicholas E.; Naumann, Christoph A.; Minto, Robert E.
    In the area of forensic chemistry, improved or new analysis methods are continually being investigated. One common and powerful technique used in forensic chemistry is wall-coated open-tubular column (WCOT) gas chromatography with electron ionization single quadrupole mass spectrometry (GC-MS). Improvements to and effectiveness of alternatives to this instrumental platform were explored in an array of parallel inquiries. The areas studied included the column for the chromatographic separation, the universal detection method employed, and the fragmentation method used to enhance molecular identification. Superfine-micropacked capillary (SFµPC) columns may provide an alternative to commercial packed GC columns and WCOT GC columns that combines the benefits of the larger sample capacity of packed columns and the benefits of the excellent separation capabilities and mass spectrometry (MS) flow rate compatibility of WCOT columns. SFµPC columns suffer from high inlet pressure requirements and prior reported work has required specialized instrumentation for their use. Fabrication of and chromatography with SFµPC GC columns was successfully achieved with typical GC-MS instrumentation and within the flow rate limit of a MS. Additionally, the use of higher viscosity carrier gasses was demonstrated to reduce the required inlet pressure for SFµPC GC columns. Recently, a new vacuum ultraviolet spectrometer (VUV) universal detector has been commercialized for GC. The ability of VUV detectors to acquire absorbance spectra from 125 nm to 430 nm poses a potential alternative to MS. As such, GC-VUV provides an exciting potential alternative approach to achieving excellent quantitative and qualitative analysis across a wide range of analytes. The performance of VUV and MS detectors for forensic analysis in terms of quantitative and qualitative analysis was compared. Analysis of alkylbenzenes in ignitable liquids was explored, which can be important evidence from suspected arson fires and are difficult to differentiate with MS. The VUV detector was found to have superior specificity and comparable sensitivity to the MS detector in scan mode. Addition of thermolysis (Th) as an orthogonal fragmentation pathway provides the opportunity to increase the differences between MS fragmentation patterns. Fragmentation has been widely established to aid in identification of molecules with MS by providing characteristic fragments at characteristic relative abundances. However, molecules with very similar structures do not result in sizable spectral differences in all cases with typical MS fragmentation techniques. A series of Th units were fabricated and integrated into GC-Th-MS instruments. Th-MS was conducted with the thermally labile nitrate esters across a range of instrumentation and thermal conditions.
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    Global land-use and carbon emission implications from biochar application to cropland in the United States
    (Elsevier, 2020-06) Dumortier, Jerome; Dokoohaki, Hamze; Elobeid, Amani; Hayes, Dermot J.; Laird, David; Miguez, Fernando E.; School of Public and Environmental Affairs
    Biochar has the potential to increase crop yields when applied to agricultural land. We integrate agronomic and economic simulation models to determine the expected yield increase from biochar applications in the United States. We calculate the location-specific willingness to pay of U.S. farmers to apply biochar to their cropland if biochar increases yields over 20 years. In addition to the potential benefit of higher revenue for farmers, biochar applications also have policy implications if biochar production is combined with bio-fuel production or used to reduce greenhouse gas emissions from indirect land-use change. Thus, the results are then combined with an agricultural outlook model to determine the effects on global land-use change and net carbon emissions. Our results indicate that biochar application is most profitable for croplands in the Southeast U.S. due to the combination of high yield increases and availability of biomass to produce biochar. An increase in U.S. yields above trend by 1% for corn, soybeans, and wheat would decrease net total global emissions by 25–87 Tg of CO2-equivalent.