Infrared gas phase spectroscopy is becoming very common in many life science applications. Here we present three types of trace gas detection systems based on CO2 laser and continuous wave (cw) optical parametric oscillator (OPO) in combination with photoacoustic spectroscopy and cw quantum cascade laser (QCL) in combination with wavelength modulation spectroscopy. Examples are included to illustrate the suitability of CO2 laser system to monitor in real time ethylene emission from various dynamic processes in plants and microorganisms as well as from car exhausts. The versatility of an OPO-based detector is demonstrated by simultaneous detection of 13C-methane and 12C-methane (at 3240 nm) at similar detection limits of 0.1 parts per billion by volume. Recent progress on a QCL-based spectrometer using a continuous wave QCL (output power 25 mW, tuning range of 1891–1908 cm-1) is presented and a comparison is made to a standard chemiluminescence instrument for analysis of NO in exhaled breath.
A laser-based ethylene detector was used for on-line monitoring of ethylene released by the phytopathogenic fungus Botrytis cinerea in vitro and in tomato fruit. Ethylene data were combined with the results of a cytological analysis of germination of B. cinerea conidia and hyphal growth. We found that aminoethoxyvinylglycine and aminooxyacetic acid, which are competitive inhibitors of the 1-aminocyclopropane-1-carboxylic acid pathway, did not inhibit the ethylene emission by B. cinerea and that the fungus most likely produces ethylene via the 2-keto-4-methylthiobutyric acid pathway. B. cinerea is able to produce ethylene in vitro, and the emission of ethylene follows the pattern that is associated with hyphal growth rather than the germination of conidia. Ethylene production in vitro depended on the L-methionine concentration added to the plating medium. Higher values and higher emission rates were observed when the concentration of conidia was increased. Compared with the ethylene released by the fungus, the infection-related ethylene produced by two tomato cultivars (cultivars Money Maker and Daniela) followed a similar pattern, but the levels of emission were 100-fold higher. The time evolution of enhanced ethylene production by the infected tomatoes and the cytological observations indicate that ethylene emission by the tomato-fungus system is not triggered by the ethylene produced by B. cinerea, although it is strongly synchronized with the growth rate of the fungus inside the tomato.
[1] Industrial emissions in Houston, Texas, and along the U.S. Gulf Coast are a large source of highly reactive anthropogenic volatile organic compounds (VOCs), principally alkenes, that affect air quality in that region. Nighttime oxidation by either O 3 or NO 3 removes these VOCs. This paper presents a regional analysis of nighttime P-3 flights during the 2006 Texas Air Quality Study (TexAQS) to quantify the loss rates and budgets for both NO 3 and highly reactive VOC. Mixing ratios and production rates of NO 3 were large, up to 400 parts per trillion by volume (pptv) and 1-2 parts per billion by volume (ppbv) per hour, respectively. Budgets for NO 3 show that it was lost primarily to reaction with VOCs, with the sum of anthropogenic VOCs (30-54%) and isoprene (10-50%) being the largest contributors. Indirect loss of NO 3 to N 2 O 5 hydrolysis was of lesser importance (14-28%) but was the least certain due to uncertainty in the aerosol uptake coefficient for N 2 O 5 . Reaction of NO 3 with peroxy radicals was a small but nonzero contribution to NO 3 loss but was also uncertain because there were no direct measurements of peroxy radicals. Net VOC oxidation rates were rapid (up to 2 ppbv VOC h −1 in industrial plumes) and were dominated by NO 3 , which was 3-5 times more important as an oxidant than O 3 . Plumes of high NO 3 reactivity (i.e., short steady state lifetimes, on the order of 1 min) identified the presence of concentrated emissions of highly reactive VOCs from the Houston Ship Channel (HSC), which, depending on the particular VOC, may be efficiently oxidized during overnight transport.
Detection and analysis of volatile compounds in exhaled breath represents an attractive tool for monitoring the metabolic status of a patient and disease diagnosis, since it is non-invasive and fast. Numerous studies have already demonstrated the benefit of breath analysis in clinical settings/applications and encouraged multidisciplinary research to reveal new insights regarding the origins, pathways, and pathophysiological roles of breath components. Many breath analysis methods are currently available to help explore these directions, ranging from mass spectrometry to laser-based spectroscopy and sensor arrays. This review presents an update of the current status of optical methods, using near and mid-infrared sources, for clinical breath gas analysis over the last decade and describes recent technological developments and their applications. The review includes: tunable diode laser absorption spectroscopy, cavity ring-down spectroscopy, integrated cavity output spectroscopy, cavity-enhanced absorption spectroscopy, photoacoustic spectroscopy, quartz-enhanced photoacoustic spectroscopy, and optical frequency comb spectroscopy. A SWOT analysis (strengths, weaknesses, opportunities, and threats) is presented that describes the laser-based techniques within the clinical framework of breath research and their appealing features for clinical use.
Abstract-Although N 2 -fixing cyanobacteria contribute significantly to oceanic sequestration of atmospheric CO 2 , little is known about how N 2 fixation and carbon fixation (primary production) interact in natural populations of marine cyanobacteria. In a developing cyanobacterial bloom in the Baltic Sea, rates of N 2 fixation (acetylene reduction) showed both diurnal and longer-term fluctuations. The latter reflected fluctuations in the nitrogen status of the cyanobacterial population and could be correlated with variations in the ratio of acetylene reduced to 15 N 2 assimilated. The value of this ratio may provide useful information about the release of newly fixed nitrogen by a cyanobacterial population. However, although the diurnal fluctuations in N 2 fixation broadly paralleled diurnal fluctuations in carbon fixation, the longer-term fluctuations in these two processes were out of phase.
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