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    Microbial respiration and natural attenuation of benzene contaminated soils investigated by cavity enhanced Raman multi-gas spectroscopy
    (Cambridge : Soc., 2015) Jochum, Tobias; Michalzik, Beate; Bachmann, Anne; Popp, Jürgen; Frosch, Torsten
    Soil and groundwater contamination with benzene can cause serious environmental damage. However, many soil microorganisms are capable to adapt and are known to strongly control the fate of organic contamination. Innovative cavity enhanced Raman multi-gas spectroscopy (CERS) was applied to investigate the short-term response of the soil micro-flora to sudden surface contamination with benzene regarding the temporal variations of gas products and their exchange rates with the adjacent atmosphere. 13C-labeled benzene was spiked on a silty-loamy soil column in order to track and separate the changes in heterotrophic soil respiration – involving 12CO2 and O2 – from the natural attenuation process of benzene degradation to ultimately form 13CO2. The respiratory quotient (RQ) decreased from a value 0.98 to 0.46 directly after the spiking and increased again within 33 hours to a value of 0.72. This coincided with the maximum 13CO2 concentration rate (0.63 μmol m−2 s−1), indicating the highest benzene degradation at 33 hours after the spiking event. The diffusion of benzene in the headspace and the biodegradation into 13CO2 were simultaneously monitored and 12 days after the benzene spiking no measurable degradation was detected anymore. The RQ finally returned to a value of 0.96 demonstrating the reestablished aerobic respiration.
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    All-in-one: a versatile gas sensor based on fiber enhanced Raman spectroscopy for monitoring postharvest fruit conservation and ripening
    (Cambridge : Soc., 2016) Jochum, Tobias; Rahal, Leila; Suckert, Renè J.; Popp, Jürgen; Frosch, Torsten
    In today's fruit conservation rooms the ripening of harvested fruit is delayed by precise management of the interior oxygen (O2) and carbon dioxide (CO2) levels. Ethylene (C2H4), a natural plant hormone, is commonly used to trigger fruit ripening shortly before entering the market. Monitoring of these critical process gases, also of the increasingly favored cooling agent ammonia (NH3), is a crucial task in modern postharvest fruit management. The goal of this work was to develop and characterize a gas sensor setup based on fiber enhanced Raman spectroscopy for fast (time resolution of a few minutes) and non-destructive process gas monitoring throughout the complete postharvest production chain encompassing storage and transport in fruit conservation chambers as well as commercial fruit ripening in industrial ripening rooms. Exploiting a micro-structured hollow-core photonic crystal fiber for analyte gas confinement and sensitivity enhancement, the sensor features simultaneous quantification of O2, CO2, NH3 and C2H4 without cross-sensitivity in just one single measurement. Laboratory measurements of typical fruit conservation gas mixtures showed that the sensor is capable of quantifying O2 and CO2 concentration levels with accuracy of 3% or less with respect to reference concentrations. The sensor detected ammonia concentrations, relevant for chemical alarm purposes. Due to the high spectral resolution of the gas sensor, ethylene could be quantified simultaneously with O2 and CO2 in a multi-component mixture. These results indicate that fiber enhanced Raman sensors have a potential to become universally usable on-site gas sensors for controlled atmosphere applications in postharvest fruit management.
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    Direct raman spectroscopic measurements of biological nitrogen fixation under natural conditions: An analytical approach for studying nitrogenase activity
    (Columbus, Ohio : American Chemical Society, 2016) Jochum, Tobias; Fastnacht, Agnes; Trumbore, Susan E.; Popp, Jürgen; Frosch, Torsten
    Biological N2 fixation is a major input of bioavailable nitrogen, which represents the most frequent factor limiting the agricultural production throughout the world. Especially, the symbiotic association between legumes and Rhizobium bacteria can provide substantial amounts of nitrogen (N) and reduce the need for industrial fertilizers. Despite its importance in the global N cycle, rates of biological nitrogen fixation have proven difficult to quantify. In this work, we propose and demonstrate a simple analytical approach to measure biological N2 fixation rates directly without a proxy or isotopic labeling. We determined a mean N2 fixation rate of 78 ± 5 μmol N2 (g dry weight nodule)-1 h-1 of a Medicago sativa-Rhizobium consortium by continuously analyzing the amount of atmospheric N2 in static environmental chambers with Raman gas spectroscopy. By simultaneously analyzing the CO2 uptake and photosynthetic plant activity, we think that a minimum CO2 mixing ratio might be needed for natural N2 fixation and only used the time interval above this minimum CO2 mixing ratio for N2 fixation rate calculations. The proposed approach relies only on noninvasive measurements of the gas phase and, given its simplicity, indicates the potential to estimate biological nitrogen fixation of legume symbioses not only in laboratory experiments. The same methods can presumably also be used to detect N2 fluxes by denitrification from ecosystems to the atmosphere. (Figure Presented).