Quantification Of Trace Gases Research Articles

Calculated rate coefficients between CI-MS reagent ions and organosulfur compounds causing food taints and off-flavours

Volatile sulfur compounds play a crucial role in the aroma profile of food and fermented beverages. We explore chemical-ionization mass spectrometry (CI-MS) ion-molecule reaction kinetics of commonly used reagent ions to a list of volatile organic sulfur compounds (VOSCs). We compute the rate coefficients of ion-molecule reactions, useful for the accurate identification and quantification of trace gases, using capture collision models based on the electric dipole moment and polarizability of the neutral VOSCs. To this aim, we evaluate molecular properties, such as the electric dipole moment, polarizability, proton affinity (PA), and ionization energy (IE) for each VOSC, by means of hybrid density functional theory (DFT) simulations. The PA and IE values are useful in the selection of appropriate reagent ions to be used in CI-MS. We thoroughly investigate collision rate coefficients at effective temperatures and internal energies, as relevant for highly energetic proton transfer reaction mass spectrometry (PTR-MS) drift tube conditions. The data provided will be valuable for the rapid quantification of VOSCs in food and fermented beverages.

Quantification of Methane and Ammonia Emissions in a Naturally Ventilated Barn by Using Defined Criteria to Calculate Emission Rates.

Simple SummaryDefined criteria for the application of the CO2 balance method in a naturally ventilated barn provided reliable data. This specification enabled the acquisition and quantification of CH4 and NH3 in a naturally ventilated dairy barn, as well as detecting decreasing NH3 emissions affected by supplementing an Acacia mearnsii condensed tannin extract to a dairy cattle ration. Moreover, long-term measurements were possible and can be used to examine feed-related mitigation strategies at a barn level in the future.Extensive experimentation on individual animals in respiration chambers has already been carried out to evaluate the potential of dietary changes and opportunities to mitigate CH4 emissions from ruminants. Although it is difficult to determine the air exchange rate of open barn spaces, measurements at the herd level should provide similarly reliable and robust results. The primary objective of this study was (1) to define a validity range (data classification criteria (DCC)) for the variables of wind velocity and wind direction during long-term measurements at barn level; and (2) to apply this validity range to a feeding trial in a naturally cross-flow ventilated dairy barn. The application of the DCC permitted quantification of CH4 and NH3 emissions during a feeding trial consisting of four periods. Differences between the control group (no supplement) and the experimental group fed a ration supplemented with condensed Acacia mearnsii tannins (CT) became apparent. Notably, CT concentrations of 1% and 3% of ration dry matter did not reduce CH4 emissions. In contrast, NH3 emissions decreased 34.5% when 3% CT was supplemented. The data confirm that quantification of trace gases in a naturally ventilated barn at the herd level is possible.

A study of enzymatic activity in cell cultures via the analysis of volatile biomarkers

Aldehyde dehydrogenase (ALDH) enzymes are responsible for the metabolism of aldehydes, including acetaldehyde (AA), and are linked to disease. We describe a method to study ALDH activity in cell cultures involving the measurement of AA concentrations in the gas/vapour phase. This has been achieved using selected ion flow tube mass spectrometry (SIFT-MS), developed for the rapid quantification of trace gases in humid media. Human cells of the hepG2 hepatocellular carcinoma cell line and primary bone marrow-derived mesenchymal stem cells (hMSCs) depleted AA from the culture media, but the application of ALDH inhibitors diethylaminobenzaldehyde (DEAB) and disulfiram (DSF), suppressed this depletion or in some cases resulted in elevated AA concentrations. Further, the cells were shown to reduce the dimethyl sulphoxide (DMSO) to dimethyl sulphide, which is mediated by methionine sulfoxide reductase A (MsrA) enzymes. Interestingly, this process was also inhibited by DEAB and DSF. The results of this study indicate that SIFT-MS gas phase analysis could be applied to the study of volatile metabolites of intracellular enzyme reactions, this having potential utility in disease research and drug discovery.

Current status of midinfrared quantum and interband cascade lasers for clinical breath analysis

State-of-the-art quantum- and interband-cascade-based chemical sensors may be effective new tools for the identification and quantification of trace gases in human breath for clinical uses. Increased or decreased concentrations of these molecules are associated with the pathogenesis of a large number of diseases. Current technologies enable breath analyses to be performed on a single breath and the results are available in real time. Critical parameters including sensor sensitivity, selectivity, real-time monitoring capability, robustness, cost, size, and weight determine the progress made toward the development and availability of commercial diagnostic material.

Increase of acetone emitted by urine in relation to ovulation

Selected ion flow tube mass spectrometry allows trace gas quantification in exhaled breath and in the air/vapor above liquids (headspace) down to the 10 parts-per-billion level. During selected ion flow tube mass spectrometry investigation of the volatile compounds emitted by urine, high acetone levels were incidentally identified in the headspace of urine from healthy female volunteers around their mid-cycle. Hence, this study was designed to measure urine headspace acetone levels throughout the menstrual cycle. Using selected ion flow tube mass spectrometry we measured daily urine headspace acetone concentrations of seven ovulating (group 1) and three postmenopausal volunteers (group 2). A several-fold increase in urine headspace acetone level was detected 2-3 days after the predicted day of ovulation in 5 of the 7 volunteers in group 1. No such rise was detected in group 2. This study provides the basis for future research to understand the reason for and the potential utility of this phenomenon.

Quantitative analysis of ammonia on the breath of patients in end-stage renal failure

The distinctive odor of the breath of patients with renal failure, usually termed the fetor, is frequently described as ammoniacal, and its potency is generally believed to reflect the uremic state [11. Previous attempts at breath analysis in these patients has, however, been directed at compounds other than ammonia, such as dimethylamine and trimethylamine, and have been at best semiquantitative in their approach [2]. This reflects the considerable methodological difficulties surrounding the accurate measurement of these compounds on breath. When they are present in low concentrations as part of complex mixtures, the value of conventional methods such as gas chromatography and mass spectrometry is limited because they usually require that the breath is pre-concentrated [3—SI. The selected ion flow tube (SIFT) technique is ideally suited for the accurate measurement of trace gases, particularly when present in complex mixtures [6—81. In contrast to conventional mass spectrometry, in which ionization of the trace gas molecules is achieved by electron bombardment, resulting in molecular cracking that yields spectra that are difficult to interpret, the SIFT technique exploits the method of chemical ionization. Molecules (M) present on the breath are soft ionized utilizing a precursor ion, such as H3O, which usually results in a single product, MH, which can then be detected by a mass spectrometer, thus allowing identification and quantification of trace gases with a sensitivity of 10 to 20 ppb from a single breath exhalation

THE SELECTED ION FLOW TUBE (SIFT)—A NOVEL TECHNIQUE FOR BIOLOGICAL MONITORING

We describe the use of our selected ion flow tube (SIFT) technique for the rapid detection and quantification of trace gases in atmospheric air, with special reference to the analysis of human breath. It is based on the chemical ionization of the breath trace gases to the exclusion of the major breath gases, using 'soft' proton transfer from H3O+ ions. Breath samples can either be introduced into the SIFT from bags or by direct breathing into the apparatus, the advantage of the latter approach being that surface active gases such as ammonia and many organic vapours which adsorb onto bag surfaces can be more accurately quantified. We present examples of the analysis of laboratory air, the breath of a non-smoker and of a smoker taken from bag samples, and illustrate the rapid time response of the technique by showing the time profile of acetone on breath during direct breathing into the apparatus. The current partial pressure sensitivity of our SIFT method is within the range 30 ppb to in excess of 100 ppm, but with further development the device could be made more sensitive, 1 ppb being well within reach. A transportable SIFT device is under development which will have applications in environmental, medical and biological research, health and safety monitoring, and in clinical diagnosis.

The selected ion flow tube (SIFT)—A novel technique for biological monitoring

We describe the use of our selected ion flow tube (SIFT) technique for the rapid detection and quantification of trace gases in atmospheric air, with special reference to the analysis of human breath. It is based on the chemical ionization of the breath trace gases to the exclusion of the major breath gases, using ‘soft’ proton transfer from H3O+ ions. Breath samples can either be introduced into the SIFT from bags or by direct breathing into the apparatus, the advantage of the latter approach being that surface active gases such as ammonia and many organic vapours which adsorb onto bag surfaces can be more accurately quantified. We present examples of the analysis of laboratory air, the breath of a non-smoker and of a smoker taken from bag samples, and illustrate the rapid time response of the technique by showing the time profile of acetone on breath during direct breathing into the apparatus. The current partial pressure sensitivity of our SIFT method is within the range 30 ppb to in excess of 100 ppm, but with further development the device could be made more sensitive, 1 ppb being well within reach. A transportable SIFT device is under development which will have applications in environmental, medical and biological research, health and safety monitoring, and in clinical diagnosis.