[Sulzer2012a] "Designer Drugs and Trace Explosives Detection with the Help of Very Recent Advancements in Proton-Transfer-Reaction Mass Spectrometry (PTR-MS)",
: Springer, pp. 366–375, 2012.
At the "Future Security 2011" we presented an overview of our studies on the "Detection and Identification of Illicit and Hazardous Substances with Proton-Transfer-Reaction Mass Spectrometry (PTR-MS)" including first results on explosives, chemical warfare agents and illicit and prescribed drugs detection. Since then we have considerably extended these preliminary studies to the detection of defined traces of some of the most common explosives, namely TNT, PETN, TATP, and DATP deposited into aluminum foam bodies, and to the detection of a number of novel and widely unknown designer drugs: ethylphenidate, 4-fluoroamphetamine and dimethocaine. Moreover, we have dramatically improved our time-of-flight based PTR-MS instruments by substantially increasing their sensitivity and hence lowering the detection limit, making them even more suitable and applicable to threat agents with extremely low vapour pressures. Data from measurements on certified gas standards are presented in order to underline these statements. The data demonstrate that, in comparison to the first generation instruments, a gain of one order of magnitude in terms of sensitivity and detection limit has been obtained.
[Warneke2007] "Determination of urban volatile organic compound emission ratios and comparison with an emissions database",
Journal of geophysical research
, vol. 112, no. D10: American Geophysical Union, pp. D10S47, 2007.
During the NEAQS-ITCT2k4 campaign in New England, anthropogenic VOCs and CO were measured downwind from New York City and Boston. The emission ratios of VOCs relative to CO and acetylene were calculated using a method in which the ratio of a VOC with acetylene is plotted versus the photochemical age. The intercept at the photochemical age of zero gives the emission ratio. The so determined emission ratios were compared to other measurement sets, including data from the same location in 2002, canister samples collected inside New York City and Boston, aircraft measurements from Los Angeles in 2002, and the average urban composition of 39 U.S. cities. All the measurements generally agree within a factor of two. The measured emission ratios also agree for most compounds within a factor of two with vehicle exhaust data indicating that a major source of VOCs in urban areas is automobiles. A comparison with an anthropogenic emission database shows less agreement. Especially large discrepancies were found for the C2-C4 alkanes and most oxygenated species. As an example, the database overestimated toluene by almost a factor of three, which caused an air quality forecast model (WRF-CHEM) using this database to overpredict the toluene mixing ratio by a factor of 2.5 as well. On the other hand, the overall reactivity of the measured species and the reactivity of the same compounds in the emission database were found to agree within 30%.
[Juerschik2010] "Direct aqueous injection analysis of trace compounds in water with proton-transfer-reaction mass spectrometry (PTR-MS)",
International Journal of Mass Spectrometry
, vol. 289, no. 2: Elsevier, pp. 173–176, 2010.
Here we present proof-of-principle investigations on a novel inlet system for proton-transfer-reaction mass spectrometry (PTR-MS) that allows for the analysis of trace compounds dissolved in water. The PTR-MS technique offers many advantages, such as real-time analysis, online quantification, no need for sample preparation, very low detection limits, etc.; however it requires gas phase samples and therefore liquid samples cannot be investigated directly. Attempts to measure trace compounds in water that have been made so far are mainly headspace analysis above the water surface and membrane inlet setups, which both are well suitable for certain applications, but also suffer from significant disadvantages. The direct aqueous injection (DAI) technique which we will discuss here turns out to be an ideal solution for the analysis of liquid samples with PTR-MS. We show that we can detect trace compounds in water over several orders of magnitude down to a concentration level of about 100 pptw, while only consuming about 100 μl of the sample. The response time of the setup is about 20 s and can therefore definitely be called “online”. Moreover the method is applicable to the analysis of all substances and not limited by the permeability of a membrane.
[Velasco2007] "Distribution, magnitudes, reactivities, ratios and diurnal patterns of volatile organic compounds in the Valley of Mexico during the MCMA 2002 & 2003 field campaigns",
Atmospheric Chemistry and Physics
, vol. 7, no. 2: Copernicus GmbH, pp. 329–353, 2007.
A wide array of volatile organic compound (VOC) measurements was conducted in the Valley of Mexico during the MCMA-2002 and 2003 field campaigns. Study sites included locations in the urban core, in a heavily industrial area and at boundary sites in rural landscapes. In addition, a novel mobile-laboratory-based conditional sampling method was used to collect samples dominated by fresh on-road vehicle exhaust to identify those VOCs whose ambient concentrations were primarily due to vehicle emissions. Four distinct analytical techniques were used: whole air canister samples with Gas Chromatography/Flame Ionization Detection (GC-FID), on-line chemical ionization using a Proton Transfer Reaction Mass Spectrometer (PTR-MS), continuous real-time detection of olefins using a Fast Olefin Sensor (FOS), and long path measurements using UV Differential Optical Absorption Spectrometers (DOAS). The simultaneous use of these techniques provided a wide range of individual VOC measurements with different spatial and temporal scales. The VOC data were analyzed to understand concentration and spatial distributions, diurnal patterns, origin and reactivity in the atmosphere of Mexico City. The VOC burden (in ppbC) was dominated by alkanes (60%), followed by aromatics (15%) and olefins (5%). The remaining 20% was a mix of alkynes, halogenated hydrocarbons, oxygenated species (esters, ethers, etc.) and other unidentified VOCs. However, in terms of ozone production, olefins were the most relevant hydrocarbons. Elevated levels of toxic hydrocarbons, such as 1,3-butadiene, benzene, toluene and xylenes, were also observed. Results from these various analytical techniques showed that vehicle exhaust is the main source of VOCs in Mexico City and that diurnal patterns depend on vehicular traffic in addition to meteorological processes. Finally, examination of the VOC data in terms of lumped modeling VOC classes and its comparison to the VOC lumped emissions reported in other photochemical air quality modeling studies suggests that some alkanes are underestimated in the emissions inventory, while some olefins and aromatics are overestimated.