<p>Herein, we report on the development of a compact proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS) for airborne measurements of volatile organic compounds (VOCs). The new instrument resolves isobaric ions with a mass resolving power (m/Δm) of &nbsp;1000, provides accurate m/z measurements (Δm &lt; 3 mDa), records full mass spectra at 1 Hz and thus overcomes some of the major analytical deficiencies of quadrupole-MS-based airborne instruments. 1 Hz detection limits for biogenic VOCs (isoprene, α total monoterpenes), aromatic VOCs (benzene, toluene, xylenes) and ketones (acetone, methyl ethyl ketone) range from 0.05 to 0.12 ppbV, making the instrument well-suited for fast measurements of abundant VOCs in the continental boundary layer. The instrument detects and quantifies VOCs in locally confined plumes (&lt; 1 km), which improves our capability of characterizing emission sources and atmospheric processing within plumes. A deployment during the NASA 2013 DISCOVER-AQ mission generated high vertical- and horizontal-resolution in situ data of VOCs and ammonia for the validation of satellite retrievals and chemistry transport models.</p>

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.

In this paper, we report the results of treating commercial samples of pork meat with ozone in order to determine whether such treatment reduces microbial growth and hence extends the shelf lifetime of such products. The technique of Proton-Transfer-Reaction Mass Spectrometry (PTR-MS) was used to study volatile emissions with the signal detected at mass 63 (assumed to be a measure for dimethylsulphide) being used as a diagnostic of bacterial activity. Such a signal was found to strongly increase with time for an untreated meat sample whereas ozone-treated meat samples showed much reduced emissions—suggesting that the microbial activity had been greatly suppressed by ozone treatment. An independent analysis, however, revealed that microbial counts were very high, independent of the treatment.

Proton-transfer-reaction mass spectrometry (PTR-MS) developed about 10 years ago is used today in a wide range of scientific and technical fields allowing real-time on-line measurements of volatile organic compounds in air with a high sensitivity and a fast response time. Most instruments employed so far use quadrupole filters to analyze product ions generated in the reaction drift tube. Due to the low mass resolution of the quadrupoles used this has the disadvantage that identification of trace gases under study is not unambiguous. Here we report the development of a new version of PTR-MS instruments using a time-of-flight mass spectrometer, which is capable of measuring VOCs at ultra-low concentrations (as low as a few pptv) under high mass resolution (as high as 6000 m/Δm in the V-mode) with a mass range of beyond 100 000 amu. This instrument was constructed by interfacing the well characterized and recently improved Ionicon hollow cathode ion source and drift tube section with a Tofwerk orthogonal acceleration reflectron time-of-flight mass spectrometer. We will first discuss the set-up of this new PTR-TOF-MS mass spectrometer instrument, its performance (with a sensitivity of several tens of cps/ppbv) and finally give some examples concerning urban air measurements where sensitivity, detection limit and mass resolution is essential to obtain relevant data.

Proton-transfer-reaction mass-spectrometry (PTR-MS) developed in the 1990s is used today in a wide range of scientific and technical fields. PTR-MS allows for real-time, online determination of absolute concentrations of volatile (organic) compounds (VOCs) in air with high sensitivity (into the low pptv range) and a fast response time (in the 40–100 ms time regime). Most PTR-MS instruments employed so far use an ion source consisting of a hollow cathode (HC) discharge in water vapour which provides an intense source of proton donor H3O+ ions. As the use of other ions, e.g. NO+ and O2+, can be useful for the identification of VOCs and for the detection of VOCs with proton affinities (PA) below that of H2O, selected ion flow tube mass spectrometry (SIFT-MS) with mass selected ions has been applied in these instances. SIFT-MS suffers, however, from at least two orders lower reagent ion counts rates and therefore SIFT-MS suffers from lower sensitivity than PTR-MS. Here we report the development of a PTR-MS instrument using a modified HC ion source and drift tube design, which allows for the easy and fast switching between H3O+, NO+ and O2+ ions produced in high purity and in large quantities in this source. This instrument is capable of measuring low concentrations (with detection limits approaching the ppqv regime) of VOCs using any of the three reagent ions investigated in this study. Therefore this instrument combines the advantages of the PTR-MS technology (the superior sensitivity) with those of SIFT-MS (detection of VOCs with PAs smaller than that of the water molecule and the capability to distinguish between isomeric compounds). We will first discuss the setup of this new PTR+SRI-MS mass spectrometer instrument, its performance for aromates, aldehydes and ketones (with a sensitivity of up to nearly 1000 cps/ppbv and a detection limit of about several 100 ppqv) and finally give some examples concerning the ability to distinguish structural isomeric compounds.

We have developed an objective method for the determination of a herb extract's quality based on headspace measurements by proton-transfer-reaction mass spectrometry (PTR-MS); this quality was checked by a sensory analysis until now. This novel method enables the company ‘Bionorica’ to ensure that they are only selling high-quality products and therefore avoid complaints of the customer. The method could be also used for controlling and optimising the production process.

The evolution of the microbial spoilage population for air- and vacuum-packaged meat (beef and pork) stored at 4°C was investigated over 11 days. We monitored the viable counts (mesophilic total aerobic bacteria, Pseudomonas spp., Enterobacteriaceae, lactic acid bacteria, and Enterococcus spp.) by the microbiological standard technique and by measuring the emission of volatile organic compounds (VOCs) with the recently developed proton transfer reaction mass spectrometry system. Storage time, packaging type, and meat type had statistically significant (P < 0.05) effects on the development of the bacterial numbers. The concentrations of many of the measured VOCs, e.g., sulfur compounds, largely increased over the storage time. We also observed a large difference in the emissions between vacuum- and air-packaged meat. We found statistically significant strong correlations (up to 99%) between some of the VOCs and the bacterial contamination. The concentrations of these VOCs increased linearly with the bacterial numbers. This study is a first step toward replacing the time-consuming plate counting by fast headspace air measurements, where the bacterial spoilage can be determined within minutes instead of days.