Physical Trace Gas Identification with the Photo Electron Ionization Spectrometer (PEIS).

Chemosensor technology for trace gases in the air always aims to identify these compounds and then measure their concentrations. For identification, traceable methods are sparse and relate to large appliances such as mass spectrometers. We present a new method that uses the alternative traceable measurement of the ionization energies of trace gases in a way that can be miniaturized and energetically tuned. We investigate the achievable performance. Since tunable UV sources are not available for photoionization, we take a detour via impact ionization with electrons, which we generate using the photoelectric effect and bring to sharp, defined energies on a nanoscale in the air. Electron impact ionization is thus possible at air pressures of up to 900 hPa. The sensitivity of the process reaches 1 ppm and is equivalent to that of classic PID. With sharpened energy settings, substance identification is currently possible with an accuracy of 30 meV. We can largely explain the experimental observations with the known quantum mechanical models.

Real-Time Investigation of Primary Ship Engine Emissions by Vacuum Resonance-Enhanced Multiphoton Ionization High-Resolution Orbitrap Mass Spectrometry.

The comprehensive chemical description of air pollution is a prerequisite for understanding atmospheric transformation processes and effects on climate and environmental health. In this study, a prototype vacuum photoionization Orbitrap mass spectrometer was evaluated for field-suitability by an online on-site investigation of emissions from a ship diesel engine. Despite remote measurements in a challenging environment, the mass spectrometric performance could fully be exploited. Due to the high resolution and mass accuracy in combination with resonance-enhanced multiphoton ionization, the aromatic hydrocarbon profile could selectively and sensitively be analyzed. Limitations from commonly deployed time-of-flight platforms could be overcome, allowing to unraveling the oxygen- and sulfur-containing compounds. Scan-by-scan evaluation of the online data revealed no shift in exact m/z, assignment statistics with root mean square error (RMSE) below 0.2 ppm, continuous high-resolution capabilities, and good isotopic profile matches. Emissions from three different feed fuels were investigated, namely, diesel, heavy fuel oil (HFO), and very low sulfur fuel oil (VLSFO). Regulations mainly concern the fuel sulfur content, and thus, exhaust gas treatment or new emerging fuels, such as the cycle-oil-based VLSFO, can legally be applied. Unfortunately, despite lower CHS-class emissions, a substantial amount of PAHs is emitted by the VLSFO with higher aromaticity compared to the HFO. Hence, legislative measures might need to take further chemical criteria into account.

Vacuum Laser Photoionization inside the C-trap of an Orbitrap Mass Spectrometer: Resonance-Enhanced Multiphoton Ionization High-Resolution Mass Spectrometry.

State-of-the-art mass spectrometry with ultraviolet (UV) photoionization is mostly limited to time-of-flight (ToF) mass spectrometers with 1000-10 000 m/Δm mass resolution. However, higher resolution and higher spectral dynamic range mass spectrometry may be indispensable in complex mixture characterization. Here, we present the concept, implementation, and initial evaluation of a compact ultrahigh-resolution mass spectrometer with gas-phase laser ionization. The concept is based on direct laser photoionization in the ion accumulation and ejection trap (C-trap) of an Orbitrap mass spectrometer. Resonance-enhanced multiphoton ionization (REMPI) using 266 nm UV pulses from a frequency-quadrupled Nd:YAG laser was applied for selective and efficient ionization of monocyclic and polycyclic aromatic hydrocarbons. The system is equipped with a gas inlet for volatile compounds and a heated gas chromatography coupling. The former can be employed for rapid system m/z-calibration and performance evaluation, whereas the latter enables analysis of semivolatile and higher-molecular-weight compounds. The capability to evaluate complex mixtures is demonstrated for selected petrochemical materials. In these experiments, several hundred to over a thousand compounds could be attributed with a root-mean-square mass error generally below 1 ppm and a mass resolution of over 140 000 at 200 m/z. Isobaric interferences could be resolved, and narrow mass splits, such as 3.4 mDa (SH4/C3), are determined. Single laser shots provided limits of detection in the 20-ppb range for p-xylene and 1,2,4-trimethylbenzene, similar to compact vacuum REMPI-ToF systems.

Puff-Resolved Analysis and Selected Quantification of Chemicals in the Gas Phase of E-Cigarettes, Heat-Not-Burn Devices, and Conventional Cigarettes Using Single-Photon Ionization Time-of-Flight Mass Spectrometry (SPI-TOFMS): A Comparative Study.

INTRODUCTION: A wide array of alternative nicotine delivery devices (ANDD) has been developed and they are often described as less harmful than combustible cigarettes. This work compares the chemical emissions of three ANDD in comparison to cigarette smoke. All the tested ANDD are characterized by not involving combustion of tobacco. AIMS AND METHODS: Single-photon ionization time-of-flight mass spectrometry (SPI-TOFMS) is coupled to a linear smoking machine, which allows a comprehensive, online analysis of the gaseous phase of the ANDD aerosol and the conventional cigarette (CC) smoke. The following devices were investigated in this study: a tobacco cigarette with a glowing piece of coal as a heating source, an electric device for heating tobacco, and a first-generation electronic cigarette. Data obtained from a standard 2R4F research cigarette are taken as a reference. RESULTS: The puff-by-puff profile of all products was recorded. The ANDD show a substantial reduction or complete absence of known harmful and potentially harmful substances compared with the CC. In addition, tar substances (i.e. semivolatile and low volatile aromatic and phenolic compounds) are formed to a much lower extent. Nicotine, however, is supplied in comparable amounts except for the investigated electronic cigarette. CONCLUSIONS: The data show that consumers switching from CC to ANDD are exposed to lower concentrations of harmful and potentially harmful substances. However, toxicological and epidemiological studies must deliver conclusive results if these reduced exposures are beneficial for users. IMPLICATIONS: The comparison of puff-resolved profiles of emissions from different tobacco products, traditional and alternative, may help users switch to lower emission products. Puff-resolved comparison overcomes technical changes, use modes between products and may help in their regulation.

Optically heated ultra-fast-cycling gas chromatography module for separation of direct sampling and online monitoring applications.

This work describes an ultrafast-cycling gas chromatography module (fast-GC module) for direct-sampling gas chromatography/mass spectrometry (GC-MS). The sample can be introduced into the fast-GC module using a common GC injector or any GC × GC modulator. The new fast-GC module offers the possibility to conduct a complete temperature cycle within 30 s. Its thermal mass is minimized by using a specially developed home-built fused silica capillary column stack and a halogen lamp for heat generation, both placed inside a gold-coated quartz glass cylinder. A high airflow blower enables rapid cooling. The new device is highly flexible concerning the used separation column, the applied temperature program, and the integration into existing systems. An application of the fast-GC module is shown in this work by thermal analysis coupled to gas chromatography-mass spectrometry (TA-GC-MS). The continuously evolving gases of the TA are modulated by a liquid CO2 modulator. Because of the rapid cycling of the fast-GC module, it is possible to obtain the best separation while maintaining the online character of the TA. Restrictions in separation and retention time shifting, known from isothermal and normal ramped fast-GC systems, are overcome.

Ambient pressure laser desorption and laser-induced acoustic desorption ion mobility spectrometry detection of explosives.

The development of fast, mobile, and sensitive detection systems for security-relevant substances is of enormous importance. Because of the low vapor pressures of explosives and improvised explosive devices, adequate sampling procedures are crucial. Ion mobility spectrometers (IMSs) are fast and sensitive instruments that are used as detection systems for explosives. Ambient pressure laser desorption (APLD) and ambient pressure laser-induced acoustic desorption (AP-LIAD) are new tools suitable to evaporate explosives in order to detect them in the vapor phase. Indeed, the most important advantage of APLD or AP-LIAD is the capability to sample directly from the surface of interest without any transfer of the analyte to other surfaces such as wipe pads. A much more gentle desorption, compared to classical thermal-based desorption, is possible with laser-based desorption using very short laser pulses. With this approach the analyte molecules are evaporated in a very fast process, comparable to a shock wave. The thermal intake is reduced considerably. The functionality of APLD and AP-LIAD techniques combined with a hand-held IMS system is shown for a wide range of common explosives such as EGDN (ethylene glycol dinitrate), urea nitrate, PETN (pentaerythritol tetranitrate), HMTD (hexamethylene triperoxide diamine), RDX (hexogen), tetryl (2,4,6-trinitrophenylmethylnitramine), and TNT (trinitrotoluene). Detection limits down to the low nanogram range are obtained. The successful combination of IMS detection and APLD/AP-LIAD sampling is shown.

Study on the Discrimination of Possible Error Sources That Might Affect the Quality of Volatile Organic Compounds Signature in Dairy Cattle Using an Electronic Nose.

Electronic nose devices (EN) have been developed for detecting volatile organic compounds (VOCs). This study aimed to assess the ability of the MENT-EGAS prototype-based EN to respond to direct sampling and to evaluate the influence of possible error sources that might affect the quality of VOC signatures. This study was performed on a dairy farm using 11 (n = 11) multiparous Holstein-Friesian cows. The cows were divided into two groups housed in two different barns: group I included six lactating cows fed with a lactating diet (LD), and group II included 5 non-lactating late pregnant cows fed with a far-off diet (FD). Each group was offered 250 g of their respective diet; 10 min later, exhalated breath was collected for VOC determination. After this sampling, 4 cows from each group were offered 250 g of pellet concentrates. Ten minutes later, the exhalated breath was collected once more. VOCs were also measured directly from the feed's headspace, as well as from the environmental backgrounds of each. Principal component analyses (PCA) were performed and revealed clear discrimination between the two different environmental backgrounds, the two different feed headspaces, the exhalated breath of groups I and II cows, and the exhalated breath within the same group of cows before and after the feed intake. Based on these findings, we concluded that the MENT-EGAS prototype can recognize several error sources with accuracy, providing a novel EN technology that could be used in the future in precision livestock farming.

Estrus Detection in a Dairy Herd Using an Electronic Nose by Direct Sampling on the Perineal Region.

Estrus detection is very important for the profitability of dairy herds. Different automatic systems for estrus detection have been developed over the last decades. Our study aimed to assess the ability of the electronic nose (EN) MENT-EGAS prototype to detect estrus, based on odor release from the perineal headspace in dairy cattle by direct sampling. The study was performed in an Italian dairy farm using 35 multiparous Holstein-Friesian cows. The cows were divided into three groups: group I included 10 lactating 5-month pregnant cows, group II included 19 lactating cycling cows, and group III included 6 cows that were artificially inseminated 18 days before the trial. Odors from the perineal headspace were collected using the MENT-EGAS prototype. In group I, odors were collected once a day for 5 consecutive days. In group II, odors were collected twice daily from day 18 until day 1 of the reproductive cycle. In group III, odors were also collected twice daily from the presumable day 18 of gestation until day 22. Principal component analyses (PCA) of the perineal headspace samples were performed. PCA in group I revealed no significant discrimination. PCA in group II revealed clear discrimination between proestrus and estrus, and between estrus and metestrus but no significant discrimination was obtained between proestrus and metestrus. PCA in group III revealed that in four cows the results were similar to group I and in two cows the results were similar to group II. On day 40 of the presumable pregnancy, the ultrasound examination revealed that only the four cows were pregnant and the other two cows were regularly cycling. On the basis of our findings, we conclude that it is possible to accurately detect estrus in dairy cattle from directly collected odor samples using the MENT-EGAS prototype. This represents the first study of estrus detection using an EN detection by direct sampling. EN technologies, such as MENT-EGAS, could be applied in the future in dairy cattle farms as a precise, non-invasive method for estrus detection.

On-line derivatization for resonance-enhanced multiphoton ionization time-of-flight mass spectrometry: detection of aliphatic aldehydes and amines via reactive coupling of aromatic photo ionization labels.

Resonance-enhanced multiphoton ionization time-of-flight mass spectrometry (REMPI-TOFMS) is a powerful technique for the on-line analysis of aromatic compounds with unique features regarding selectivity and sensitivity. Aliphatic compounds, however, are difficult to address by REMPI due to their unfavorable photo ionization properties. This paper describes the proof of concept for an on-line derivatization approach for converting nonaromatic target analytes into specific, photoionizable aromatic derivatives that are readily detectable by REMPI-TOFMS. A multichannel silicone trap or poly(dimethylsiloxane) (PDMS) open tubular capillary was used as a reaction medium for the derivatization of volatile alkyl aldehydes and alkylamines with aromatic "photoionization labels"and to concentrate the resulting aromatic derivatives. The aldehydes formaldehyde, acetaldehyde, acrolein, and crotonal, which when underivatized are poorly detectable by REMPI, were converted into their easily photoionizable phenylhydrazone derivatives by the on-line reaction with phenylhydrazine as reagent. Similarly, the methyl-, ethyl-, propyl-, and butylamines were converted into their REMPI-ionizable benzaldehyde alkylimine derivatives by the on-line reaction with benzaldehyde as reagent. The derivatives were thermally desorbed from the PDMS matrix and transferred into the REMPI-TOFMS for detection. The REMPI-TOFMS detection limits obtained for acetaldehyde; acrolein; crotonal; and methyl-, ethyl-, propyl-, and butylamine using this photo ionization labeling method were in the sub-parts-per-million range and, thus, readily below the permissible exposure limits set by OSHA.