Browsing by Subject "In situ thermal DRIFTS"

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    Development of coupled mid-infrared spectroscopic and thermal analytical approaches for the characterization and modeling of soil organic matter dynamics of arable soils
    (2013) Demyan, Michael Scott; Cadisch, Georg
    Soil organic matter (SOM) is a large part of the global carbon cycle both as a stock, as a source of fluxes (gaseous, dissolved, or sediments) to other stocks, and is also an important component of soil fertility and likewise plant productivity. Due to the growing need for additional data for both global studies related to climate change and soil fertility, additional information is needed not only on the total quantity of SOM, but its distribution within time and space and also its quality. In this study the use of mid-infrared spectroscopy in different applications was explored as an indicator of soil quality or composition, to measure the distribution of quality in different soils and fractions, and how these new methods could be used for SOM model parameterizations compared to other methods for both short and medium term model simulations. Firstly, certain mid-infrared active functional groups as measured with diffuse reflectance spectroscopy (DRIFTS) were studied in a long term fertilization experiment (Bad Lauchstädt) to ascertain the suitability of these different functional groups as indicators of the long term impacts of different fertilizer applications and also in various SOM fractions as separated by size-density approaches. Secondly, a coupled mid-infrared thermally evolved gas analysis was combined with in-situ monitoring of changes in vibrational functional groups to assign different qualities to different temperature ranges during a thermal oxidation experiment to 700 °C. Lastly, these two approaches were compared to traditional SOM fractionation as more rapid alternatives to parameterizing SOM pool sizes in the Century multi-compartment SOM model applied to arable soils at sites in the Kraichgau and Swabian Alb areas in Southwest Germany. In the long-term experiment (Bad Lauchstädt) it was found that certain vibrational functional groups (i.e. aliphatic (2930 1/cm) and aromatic (1620 1/cm)) in bulk soil varied (P < 0.05) according to long-term farmyard manure (FYM) and/or mineral fertilizer application. The application of 30 Mg/ha every second year of FYM increased the proportion of aliphatics as compared to aromatics, while the opposite was true for the control treatment (without any mineral and FYM fertilizer). The ratio of the aromatic to aliphatic relative peak areas were found to be positively related to the ratio of stabilized (SOC in heavy density fractions and clay size fraction) to labile SOC (light density fraction). This indicated that this peak area ratio (aromatic to aliphatic) is an indicator for the relative contribution of stabile to labile SOM as a stability index. In the next phase of the methodological development, evolved gas analysis (EGA) was used during a programmed heating of soil samples to 700°C to link EGA characteristics with SOM. An additional methodological step was the utilization of in-situ diffuse reflectance (in situT DRIFTS) measurements during heating as an indicator of the nature of SOM being decomposed at different temperatures. Thermal stability was found to be affected by experimental conditions and also sample type. The heating rate, amount of C in the sample, and volume of the sample in the heating chamber changed the rate and overall shape of the CO2 evolution curve and needed to be optimized when comparing different SOM fractions. In the long term experiment of Bad Lauchstädt, a decreasing thermal stability as measured by temperature of maximum CO2 evolution was found in the order from control > mineral fertilizer > manure > manure and mineral fertilizer. Furthermore, after a 490 day soil incubation at 20°C the thermal stability of SOC increased, but only slightly. In the in-situT DRIFTS method, the intensity of previously identified vibrational functional groups decreased (degraded) at different temperatures. The functional groups decreased in the order of aliphatic, alcoholic, and carboxylates, and at higher temperatures, also aromatic groups decreased. These findings were used as rules for fitting multiple peaks to the total evolved CO2 curve to derive SOM pools of different reactivity. Pools derived from the measured fractions of mid-infrared functional groups (aliphatic, carboxylate/aromatic, aromatic), evolved gas analysis (CO2) fitted peaks (centered at 320, 380, 540°C), and size-density fractionation (particulate organic matter, heavy density fraction, silt and clay fraction) in addition to a long-term equilibrium model run, were used to parameterize the SOM pools of the Century model as implemented in the Land Use Change Assessment tool (LUCIA) and compared to measured soil surface CO2 fluxes and soil organic carbon (SOC) contents after 2 years. The best fits for the short term study were found to be the SOM fractionation DRIFTS and EGA pool initialization methods, but the differences over two years were very small for the three different parameterization methods and generally CO2 fluxes were underestimated. A 20 year simulation, keeping all rate constants the same, on the other hand, showed large changes in both the SOC (14 Mg/ha, 0 to 30 cm) and the distribution in the pools. As compared to the 2010 baseline SOC, the DRIFTS, EGA-1, and SOM fractionation methods were closest in the Kraichgau site, while the equilibrium method was closest in the Swabian Alb. Overall, DRIFT mid-infrared spectroscopy showed its utility as a rapid assessment of the general distribution of stable to labile SOM in bulk soil. Additionally, when coupled with EGA and in-situ DRIFTS measurements, the integrated method can provide additional information during the thermal degradation of SOM during heating. All methods investigated found changes as a result of soil fertilization management, and between SOM fractions. Lastly, it was shown that such information can be used for direct SOM model inputs, although the methods should be tested on further land uses and soil types. These mid-infrared thermally coupled spectroscopic techniques represent an advance in the use of mid-infrared spectroscopy in the field of detailed SOM characterization for modeling SOM dynamics.