Proton-transfer-reaction Time-of-flight Mass Spectrometer Research Articles

Aromatic VOCs at Major Road Junctions of a Metropolis in India: Measurements Using TD-GC-FID and PTR-TOF-MS Instruments

Ambient mass concentrations of benzene and toluene were measured at 12 different road junctions of Ahmedabad city in India during the pre-monsoon season of year 2015. A Thermal Desorption-Gas Chromatography-Flame Ionization Detector (TD-GC-FID) technique was used for the analysis of aromatic volatile organic compounds (VOCs) in air samples. In each of both inner and outer ring roads, air samples were collected at 6 sites to investigate the spatial variation of benzene and toluene. The mass concentrations of benzene and toluene show strong site-to-site and day-to-day variations. The average mass concentration of benzene varied in the ranges of 11-35 μg m^(-3) and 4-12 μg m^(-3) along the inner and outer roads, respectively. The mass concentration of toluene varied in the ranges of 43-142 μg m^(-3) and 11-28 μg m^(-3) along the inner and outer roads, respectively. Overall, the mass concentrations of VOCs along the inner road were 3-5 times higher than those measured along the outer road.The mass concentrations of benzene and toluene show good correlation suggesting their common emission sources (mostly vehicular). However, the enhancement ratios of ΔToluene/ΔBenzene (~4.0 μg μg^(-1)) along both the roads were higher than the typical ratios (1.5-3.5 μg μg^(-1)) reported for vehicular emissions. The higher values of ΔToluene/ΔBenzene are due to the emissions of VOCs also from industrial and other non-traffic sources. During the daytime, the lower mass concentrations of VOCs and lower ΔToluene/ΔBenzene (~2 μg μg^(-1)) indicate the role of photochemical aging. The combined diurnal trend of ΔToluene/ΔBenzene agrees well with that measured at central Ahmedabad using the proton-transfer-reaction time of flight mass spectrometer (PTR-TOF-MS). However, compared to weekdays, the mass concentrations of VOCs show reduction and increase during the Sunday and Saturday, respectively. The mass concentration of VOCs and their ratio were towards the higher side of data reported for different urban sites of the world.

Siloxanes Are the Most Abundant Volatile Organic Compound Emitted from Engineering Students in a Classroom

Direct human emissions are known to contribute volatile organic compounds (VOCs) to indoor air via various mechanisms. However, few measurements that determine the emissions of a full suite of occupant-associated VOCs are available. We measured occupant-related VOC emissions from engineering students in a classroom using a proton-transfer-reaction time-of-flight mass spectrometer (PTR-TOF-MS). The dominant compound emitted was a cyclic volatile methylsiloxane (cVMS), decamethylcyclopentasiloxane (D5), which is a major inactive ingredient in some personal care products such as antiperspirants. D5 was found to contribute ∼30% of the total indoor VOC mass concentration as measured by the PTR-TOF-MS. Octamethylcyclotetrasiloxane (D4) and dodecamethylcyclohexasiloxane (D6) were detected at abundances that were 1–2 orders of magnitude lower. The per-person emission rate of these three cVMS declined monotonically from morning into the afternoon, consistent with expectations for emissions from daily morning appli...

PTRwid: A new widget tool for processing PTR-TOF-MS data

Abstract. PTRwid is a fast and user friendly tool that has been developed to process data from proton-transfer-reaction time-of-flight mass spectrometers (PTR-TOF-MS) that use HTOF (high-resolution time-of-flight) mass spectrometers from Tofwerk AG (Switzerland). PTRwid is designed for a comprehensive evaluation of whole laboratory or field-based studies. All processing runs autonomously, and entire laboratory or field campaigns can, in principle, be processed with a few mouse clicks. Unique features of PTRwid include (i) an autonomous and accurate mass scale calibration, (ii) the computation of a "unified mass list" that – in addition to a uniform data structure – provides a robust method to determine the precision of attributed peak masses, and (iii) fast data analysis due to well considered choices in data processing.

Ozone degrades floral scent and reduces pollinator attraction to flowers.

In this work we analyzed the degradation of floral scent volatiles from Brassica nigra by reaction with ozone along a distance gradient and the consequences for pollinator attraction. For this purpose we used a reaction system comprising three reaction tubes in which we conducted measurements of floral volatiles using a proton-transfer-reaction time-of-flight mass spectrometer (PTR-TOF-MS) and GC-MS. We also tested the effects of floral scent degradation on the responses of the generalist pollinator Bombus terrestris. The chemical analyses revealed that supplementing air with ozone led to an increasing reduction in the concentrations of floral volatiles in air with distance from the volatile source. The results revealed different reactivities with ozone for different floral scent constituents, which emphasized that ozone exposure not only degrades floral scents, but also changes the ratios of compounds in a scent blend. Behavioural tests revealed that floral scent was reduced in its attractiveness to pollinators after it had been exposed to 120ppb O3 over a 4.5m distance. The combined results of chemical analyses and behavioural responses of pollinators strongly suggest that high ozone concentrations have significant negative impacts on pollination by reducing the distance over which floral olfactory signals can be detected by pollinators.

A Real-Time Fast-Flow Tube Study of VOC and Particulate Emissions from Electronic, Potentially Reduced-Harm, Conventional, and Reference Cigarettes.

Tobacco-free electronic cigarettes (e-cigarettes), which are currently not regulated by the FDA, have become widespread as a "safe" form of smoking. One approach to evaluate the potential toxicity of e-cigarettes and other types of potentially "reduced-harm" cigarettes is to compare their emissions of volatile organic compounds (VOCs), including reactive organic electrophillic compounds such as acrolein, and particulate matter to those of conventional and reference cigarettes. Our newly designed fast-flow tube system enabled us to analyze VOC composition and particle number concentration in real-time by promptly diluting puffs of mainstream smoke obtained from different brands of combustion cigarettes and e-cigarettes. A proton transfer reaction time-of-flight mass spectrometer (PTRMS) was used to analyze real-time cigarette VOC emissions with a 1 s time resolution. Particles were detected with a condensation particle counter (CPC). This technique offers real-time analysis of VOCs and particles in each puff without sample aging and does not require any sample pretreatment or extra handling. Several important determining factors in VOC and particle concentration were investigated: (1) puff frequency; (2) puff number; (3) tar content; (4) filter type. Results indicate that electronic cigarettes are not free from acrolein and acetaldehyde emissions and produce comparable particle number concentrations to those of combustion cigarettes, more specifically to the 1R5F reference cigarette. Unlike conventional cigarettes, which emit different amounts of particles and VOCs each puff, there was no significant puff dependence in the e-cigarette emissions. Charcoal filter cigarettes did not fully prevent the emission of acrolein and other VOCs.

Wine matrix composition affects temporal aroma release as measured by proton transfer reaction - time-of-flight - mass spectrometry

Background and Aims The aim of this study was to evaluate the influence of the composition of the non-volatile wine matrix on the temporal aroma release profile using an artificial mouth device coupled online to a proton transfer reaction – time-of–flight – mass spectrometer (PTR-ToF-MS). Methods and Results Five wines, white, sparkling, young red, aged red and sweet wines, were lyophilised, de-aromatised and reconstituted to equal ethanol concentration and spiked with eight target aroma compounds and human saliva. Aroma release was monitored in real time by using an artificial mouth coupled to a PTR-ToF-MS. Matrix composition had a considerable influence on the temporal aroma release parameters [maximum intensity: Imax and area under the curve (AUC)] in the first 30 s of aroma monitoring. In general, red wines showed the highest aroma release, sweet wines the lowest. Conclusions The physicochemical characteristics of the aroma compounds and the wine matrix composition play a significant role on the temporal aroma release from wines. The formation of complexes between wine polyphenols and saliva glycoproteins appears to change wine polarity favoring the release of hydrophobic aroma compounds. Significance of the Study This study has highlighted the importance of considering the wine non-volatile composition as a necessary parameter to understand wine aroma perception during the dynamics of wine intake.

Emission of volatile sesquiterpenes and monoterpenes in grapevine genotypes following Plasmopara viticola inoculation in vitro.

The grapevine (Vitis vinifera) is one of the most widely cultivated fruit crops globally, and one of its most important diseases in terms of economic losses is downy mildew, caused by Plasmopara viticola. Several wild Vitis species have been found to be resistant to this pathogen and have been used in breeding programs to introduce resistance traits to susceptible cultivars. Plant defense is based on different mechanisms, and volatile organic compounds (VOCs) play a major role in the response to insects and pathogens. Although grapevine resistance mechanisms and the production of secondary metabolites have been widely characterized in resistant genotypes, the emission of VOCs has not yet been investigated following P. viticola inoculation. A Proton Transfer Reaction-Time of Flight-Mass Spectrometer (PTR-ToF-MS) was used to analyze the VOCs emitted by in vitro-grown plants of grapevine genotypes with different levels of resistance. Downy mildew inoculation significantly increased the emission of monoterpenes and sesquiterpenes by the resistant SO4 and Kober 5BB genotypes, but not by the susceptible V. vinifera Pinot noir. Volatile terpenes were implicated in plant defense responses against pathogens, suggesting that they could play a major role in the resistance against downy mildew by direct toxicity or by inducing grapevine resistance. The grapevine genotypes differed in terms of the VOC emission pattern of both inoculated and uninoculated plants, indicating that PTR-ToF-MS could be used to screen hybrids with different levels of downy mildew resistance. Copyright © 2015 John Wiley & Sons, Ltd.

Apple Flavor: Linking Sensory Perception to Volatile Release and Textural Properties

AbstractIn apples, consumers predominantly use visual, auditory and texture cues as quality/preference indicators and struggle to describe complex olfactory sensations. This study investigated apple cultivar differentiation using analytical and sensory techniques with the goal of achieving more relevant instrumental characterization. Sensory flavor/odor data were compared with volatile organic compounds (VOCs) measured using proton transfer reaction time‐of‐flight mass spectrometer (PTR‐ToF‐MS) and sensory texture data were compared with mechanical‐acoustic textural parameters obtained using a texture analyzer. Both techniques separated cultivars similarly. PTR‐ToF‐MS data separated cultivars into VOC families that correlated to specific sensory attributes (e.g., butanoate esters to lemon flavor/odor). Analytical and sensory firmness were positively correlated where the former differentiated crunchy from hard‐not crunchy cultivars. Sweet taste did not correlate to soluble solids content but was positively correlated to fruity esters which could indicate a taste‐aroma interaction. This study demonstrates the potential to predict sensory attributes of apples using analytical techniques.Practical ApplicationThe description of apple flavor is challenging for both trained panelists and consumers to describe due to the complexity of the multimodal stimulations that occur within the oral and ortho/retro nasal cavity during consumption that induce odor, taste, flavor and sound perception. Therefore, this study looks at objectively characterizing apple cultivars based solely on instrumental techniques that reflect attributes attained from a descriptive sensory analysis of the same cultivars. The current study found apple cultivars were separated into similar groups when sensory and instrumental texture, physicochemical and VOC data were compared. Specific analytical properties that correlated strongly to sensory attributes could be used as predictors of important sensory attributes that differentiated the samples. Hence, the use of these instrumental techniques to characterize apples could be an option to increase throughput.

A novel inlet system for online chemical analysis of semi-volatile submicron particulate matter

Abstract. We herein present a novel modular inlet system designed to be coupled to low-pressure gas analyzers for online chemical characterization of semi-volatile submicron particles. The "chemical analysis of aerosol online" (CHARON) inlet consists of a gas-phase denuder for stripping off gas-phase analytes, an aerodynamic lens for particle collimation combined with an inertial sampler for the particle-enriched flow and a thermodesorption unit for particle volatilization prior to chemical analysis. The denuder was measured to remove gas-phase organics with an efficiency > 99.999% and to transmit particles in the 100–750 nm size range with a 75–90% efficiency. The measured average particle enrichment factor in the subsampling flow from the aerodynamic lens was 25.6, which is a factor of 3 lower than the calculated theoretical optimum. We coupled the CHARON inlet to a proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS) which quantitatively detects most organic analytes and ammonia. The combined CHARON-PTR-ToF-MS setup is thus capable of measuring both the organic and the ammonium fraction in submicron particles in real time. Individual organic compounds can be detected down to levels of 10–20 ng m−3. Two proof-of-principle studies were carried out for demonstrating the analytical power of this new instrumental setup: (i) oxygenated organics and their partitioning between the gas and the particulate phase were observed from the reaction of limonene with ozone and (ii) nicotine was measured in cigarette smoke particles demonstrating that selected organic target compounds can be detected in submicron particles in real time.

Characterization of biomass burning emissions from cooking fires, peat, crop residue, and other fuels with high-resolution proton-transfer-reaction time-of-flight mass spectrometry

Abstract. We deployed a high-resolution proton-transfer-reaction time-of-flight mass spectrometer (PTR-TOF-MS) to measure biomass-burning emissions from peat, crop residue, cooking fires, and many other fire types during the fourth Fire Lab at Missoula Experiment (FLAME-4) laboratory campaign. A combination of gas standard calibrations and composition sensitive, mass-dependent calibration curves was applied to quantify gas-phase non-methane organic compounds (NMOCs) observed in the complex mixture of fire emissions. We used several approaches to assign the best identities to most major "exact masses", including many high molecular mass species. Using these methods, approximately 80–96% of the total NMOC mass detected by the PTR-TOF-MS and Fourier transform infrared (FTIR) spectroscopy was positively or tentatively identified for major fuel types. We report data for many rarely measured or previously unmeasured emissions in several compound classes including aromatic hydrocarbons, phenolic compounds, and furans; many of these are suspected secondary organic aerosol precursors. A large set of new emission factors (EFs) for a range of globally significant biomass fuels is presented. Measurements show that oxygenated NMOCs accounted for the largest fraction of emissions of all compound classes. In a brief study of various traditional and advanced cooking methods, the EFs for these emissions groups were greatest for open three-stone cooking in comparison to their more advanced counterparts. Several little-studied nitrogen-containing organic compounds were detected from many fuel types, that together accounted for 0.1–8.7% of the fuel nitrogen, and some may play a role in new particle formation.

A compact PTR-ToF-MS instrument for airborne measurements of volatile organic compounds at high spatiotemporal resolution

Abstract. 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 ~1000, provides accurate m/z measurements (Δm < 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 (< 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.

Using total OH reactivity to assess isoprene photooxidation via measurement and model

The Tropics provide a reactive atmospheric environment with high levels of biogenic emissions, rapidly growing anthropogenic influence, high solar radiation and temperature levels. The major reactive biogenic emission is isoprene which reacts rapidly with the primary daytime oxidant OH, the hydroxyl radical. This key photooxidation process has recently been the focus of several experimental and computational studies. A novel isoprene degradation mechanism was recently proposed (MIME) supplementing the commonly used MCM 3.2 scheme.This study examined the photooxidation of isoprene in the controlled conditions of the Valencia atmospheric reaction chamber, EUPHORE (EUropean PHOtoREactor). Besides the detection of isoprene and its major oxidation products formaldehyde, methyl vinyl ketone (MVK) and methacrolein (MACR), the total loss rate of OH (total OH reactivity) was measured. The total OH reactivity was compared to the individual measurements of isoprene and its oxidation products to assess the significant contributors to the overall OH loss rate. Measured total OH reactivity showed excellent agreement to the calculation based on individual compounds detected by a Proton-Transfer-Reaction-Time-Of-Flight-Mass-Spectrometer (PTR-TOF-MS). On average 97% of the measured total OH reactivity could be explained by isoprene and its major oxidation products.Total OH reactivity was also compared to various isoprene degradation schemes to evaluate known mechanisms. The MCM 3.2 isoprene mechanism reproduced the temporal degradation of total OH reactivity (and isoprene) reasonably well with a 57% (and 95%) agreement within the model uncertainties and a linear curve fit slope of 0.69 (and 1.02) for a model to measurement correlation. Large discrepancies between modeled values and all observed compounds were found for the recent isoprene oxidation scheme in MIME. Possible mechanistic reasons are discussed and improvements proposed. The subsequently modified version of MIME differed from the measured total OH reactivity only about 12% at the end of the experiment and represented best the overall temporal profile (linear curve fit slope of correlation: 0.95).

Undisturbed and disturbed above canopy ponderosa pine emissions: PTR-TOF-MS measurements and MEGAN 2.1 model results

Abstract. We present the first eddy covariance flux measurements of volatile organic compounds (VOCs) using a proton-transfer-reaction time-of-flight mass spectrometer (PTR-TOF-MS) above a ponderosa pine forest in Colorado, USA. The high mass resolution of the PTR-TOF-MS enabled the identification of chemical sum formulas. During a 30 day measurement period in August and September 2010, 649 different ion mass peaks were detected in the ambient air mass spectrum (including primary ions and mass calibration compounds). Eddy covariance with the vertical wind speed was calculated for all ion mass peaks. On a typical day, 17 ion mass peaks, including protonated parent compounds, their fragments and isotopes as well as VOC-H+-water clusters, showed a significant flux with daytime average emissions above a reliable flux threshold of 0.1 mg compound m−2 h−1. These ion mass peaks could be assigned to seven compound classes. The main flux contributions during daytime (10:00–18:00 LT) are attributed to the sum of 2-methyl-3-buten-2-ol (MBO) and isoprene (50%), methanol (12%), the sum of acetic acid and glycolaldehyde (10%) and the sum of monoterpenes (10%). The total MBO + isoprene flux was composed of 10% isoprene and 90% MBO. There was good agreement between the light- and temperature dependency of the sum of MBO and isoprene observed for this work and those of earlier studies. The above canopy flux measurements of the sum of MBO and isoprene and the sum of monoterpenes were compared to emissions calculated using the Model of Emissions of Gases and Aerosols from Nature (MEGAN 2.1). The best agreement between MEGAN 2.1 and measurements was reached using emission factors determined from site-specific leaf cuvette measurements. While the modeled and measured MBO + isoprene fluxes agree well, the emissions of the sum of monoterpenes is underestimated by MEGAN 2.1. This is expected as some factors impacting monoterpene emissions, such as physical damage of needles and branches due to storms, are not included in MEGAN 2.1. After a severe hailstorm event, 22 ion mass peaks (attributed to six compound classes plus some unknown compounds) showed an elevated flux for the two following days. The sum of monoterpene emissions was 4–23 times higher compared to emissions prior to the hailstorm while MBO emissions remained unchanged. The monoterpene emission (in mg compound m−2) during this measurement period is underestimated by 40% if the effect of this disturbance source is not considered.

Observations of Diurnal to Weekly Variations of Monoterpene-Dominated Fluxes of Volatile Organic Compounds from Mediterranean Forests: Implications for Regional Modeling

The Estate of Castelporziano (Rome, Italy) hosts many ecosystems representative of Mediterranean vegetation, especially holm oak and pine forests and dune vegetation. In this work, basal emission factors (BEFs) of biogenic volatile organic compounds (BVOCs) obtained by Eddy Covariance in a field campaign using a proton transfer reaction-time-of-flight-mass spectrometer (PTR-TOF-MS) were compared to BEFs reported in previous studies that could not measure fluxes in real-time. Globally, broadleaf forests are dominated by isoprene emissions, but these Mediterranean ecosystems are dominated by strong monoterpene emitters, as shown by the new BEFs. The original and new BEFs were used to parametrize the model of emissions of gases and aerosols from nature (MEGAN v2.1), and model outputs were compared with measured fluxes. Results showed good agreement between modeled and measured fluxes when a model was used to predict radiative transfer and energy balance across the canopy. We then evaluated whether changes in BVOC emissions can affect the chemistry of the atmosphere and climate at a regional level. MEGAN was run together with the land surface model (community land model, CLM v4.0) of the community earth system model (CESM v1.0). Results highlighted that tropospheric ozone concentration and air temperature predicted from the model are sensitive to the magnitude of BVOC emissions, thus demonstrating the importance of adopting the proper BEF values for model parametrization.

Production of methyl vinyl ketone and methacrolein via the hydroperoxyl pathway of isoprene oxidation

Abstract. The photo-oxidation chemistry of isoprene (ISOP; C5H8) was studied in a continuous-flow chamber under conditions such that the reactions of the isoprene-derived peroxyl radicals (RO2) were dominated by the hydroperoxyl (HO2) pathway. A proton-transfer-reaction time-of-flight mass spectrometer (PTR-TOF-MS) with switchable H3O+ and NO+ reagent ions was used for product analysis. The products methyl vinyl ketone (MVK; C4H6O) and methacrolein (MACR; C4H6O) were differentiated using NO+ reagent ions. The MVK and MACR yields via the HO2 pathway were (3.8 ± 1.3)% and (2.5 ± 0.9)%, respectively, at +25 °C and < 2% relative humidity. The respective yields were (41.4 ± 5.5)% and (29.6 ± 4.2)% via the NO pathway. Production of MVK and MACR via the HO2 pathway implies concomitant production of hydroxyl ((6.3 ± 2.1)%) and hydroperoxyl ((6.3 ± 2.1)%) radicals, meaning a HOx recycling of (12.6 ± 4.2)% given that HO2 was both a reactant and product. Other isoprene oxidation products, believed to be mostly organic hydroperoxides, also contributed to the ion intensity at the same mass-to-charge (m/z) ratios as the MVK and MACR product ions for HO2-dominant conditions. These products were selectively removed from the gas phase by placement of a cold trap (−40 °C) inline prior to the PTR-TOF-MS. When incorporated into regional and global chemical transport models, the yields of MVK and MACR and the concomitant HOx recycling reported in this study can improve the accuracy of the simulation of the HO2 reaction pathway of isoprene, which is believed to be the fate of approximately half of atmospherically produced isoprene-derived peroxy radicals on a global scale.

Anthropogenic sources of VOC in a football stadium: Assessing human emissions in the atmosphere

Measurements of gas-phase volatile organic compounds (VOCs), aerosol composition, carbon dioxide (CO2), and ozone (O3) were made inside Coface Arena in Mainz, Germany (49°59′3″N, 8°13′27″E) during a football match on April 20 2012. The VOC measurements were performed with a proton-transfer-reaction time-of-flight mass spectrometer (PTR-TOF-MS). Observed VOCs could be classified into several distinct source categories including (1) human respiration/breath, (2) ozonolysis of skin oils, and (3) cigarette smoke/combustion. In this work, we present a detailed discussion on the scale and potential impacts of VOCs emitted as a result of these sources and their contributions on local and larger scales. Human emissions of VOCs have a negligible contribution to the global atmospheric budget (∼1% or less) for all those quantified in this study. However, fluxes as high as 0.02 g m−2 h−1 and 2 × 10−4 g m−2 h−1, for ethanol and acetone respectively are observed, suggesting the potential for significant impact on local air chemistry and perhaps regional scales. This study suggests that even in outdoor environments, situations exist where VOCs emitted as a result of human presence and activity are an important component of local air chemistry.

Comparison of different real time VOC measurement techniques in a ponderosa pine forest

Abstract. Volatile organic compound (VOC) mixing ratios measured by five independent instruments are compared at a forested site dominated by ponderosa pine (Pinus Ponderosa) during the BEACHON-ROCS field study in summer 2010. The instruments included a Proton Transfer Reaction Time of Flight Mass Spectrometer (PTR-TOF-MS), a Proton Transfer Reaction Quadrupole Mass Spectrometer (PTR-MS), a Fast Online Gas-Chromatograph coupled to a Mass Spectrometer (GC/MS; TOGA), a Thermal Dissociation Chemical Ionization Mass Spectrometer (PAN-CIMS) and a Fiber Laser-Induced Fluorescence Instrument (FILIF). The species discussed in this comparison include the most important biogenic VOCs and a selected suite of oxygenated VOCs that are thought to dominate the VOC reactivity at this particular site as well as typical anthropogenic VOCs that showed low mixing ratios at this site. Good agreement was observed for methanol, the sum of the oxygenated hemiterpene 2-methyl-3-buten-2-ol (MBO) and the hemiterpene isoprene, acetaldehyde, the sum of acetone and propanal, benzene and the sum of methyl ethyl ketone (MEK) and butanal. Measurements of the above VOCs conducted by different instruments agree within 20%. The ability to differentiate the presence of toluene and cymene by PTR-TOF-MS is tested based on a comparison with GC-MS measurements, suggesting a study-average relative contribution of 74% for toluene and 26% for cymene. Similarly, 2-hydroxy-2-methylpropanal (HMPR) is found to interfere with the sum of methyl vinyl ketone and methacrolein (MVK + MAC) using PTR-(TOF)-MS at this site. A study-average relative contribution of 85% for MVK + MAC and 15% for HMPR was determined. The sum of monoterpenes measured by PTR-MS and PTR-TOF-MS was generally 20–25% higher than the sum of speciated monoterpenes measured by TOGA, which included α-pinene, β-pinene, camphene, carene, myrcene, limonene, cineole as well as other terpenes. However, this difference is consistent throughout the study, and likely points to an offset in calibration, rather than a difference in the ability to measure the sum of terpenes. The contribution of isoprene relative to MBO inferred from PTR-MS and PTR-TOF-MS was smaller than 12% while GC-MS data suggested an average of 21% of isoprene relative to MBO. This comparison demonstrates that the current capability of VOC measurements to account for OH reactivity associated with the measured VOCs is within 20%.

Monitoring the effect of high pressure and transglutaminase treatment of milk on the evolution of flavour compounds during lactic acid fermentation using PTR-ToF-MS

In this study, the effects of thermal or high hydrostatic pressure (HHP) treatment of a milk base in the absence or presence of a transglutaminase (TGase) protein cross-linking step on the flavour development of yoghurt were investigated. The presence of several tentatively identified volatile flavour compounds (VOCs), both during the enzymatic treatment and the lactic acid fermentation of the milk base, were monitored using a proton transfer reaction time-of-flight mass spectrometer (PTR-ToF-MS). The formation of the major flavour compounds (acetaldehyde, diacetyl, acetoin, and 2-butanone) followed a sigmoidal trend described by the modified Gompertz model. The HHP treatment of milk increased significantly the volatile compound formation rate whereas it did not affect the duration of the lag phase of formation, with the exception of acetaldehyde and diacetyl formation. On the contrary, the TGase cross-linking of milk did not significantly modify the formation rate of the volatile compounds but shortened the duration of the lag phase of their formation.

A high resolution and high sensitivity proton-transfer-reaction time-of-flight mass spectrometer (PTR-TOF-MS)

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.

Development of a PTR-TOFMS instrument for real-time measurements of volatile organic compounds in air

A proton transfer reaction-time-of-flight mass spectrometer (PTR-TOFMS) has been developed for real-time measurements of volatile organic compounds in air. The instrument is designed to be operated with a hollow cathode discharge ion source and an ion drift tube at relatively high pressures. Each component of the system, an ion source, a drift tube, an ion transfer region, and a time-of-flight mass spectrometer, are in detail characterized by a number of laboratory experiments. The optimized instrumental configuration enables us to gain high intensities of hydronium (H 3O +) ions, typically ∼7 × 10 5 counts for 1-min integration at a drift tube pressure of ∼5 Torr. It also suppresses background signals, and interferences from sample air (NO + and O 2 +), which undergo fast reactions with volatile organic compounds, to ∼0.5% of those of H 3O + ions. We find that the use of the custom-built discharge source show higher overall sensitivities than of a commercially available radioactive source. Potentials to detect oxygenated VOCs (aldehydes, ketones, and alcohols), halocarbons, and amines are also suggested. The detection limits for acetaldehyde, acetone, isoprene, benzene, toluene, and p-xylene were determined to be at the sub-ppbv levels for a 1-min integration time. A good linear response at trace levels is certified, but slight sensitivity dependency on water vapor contents is revealed. We finally demonstrate that the instrument can be used for on-line monitoring to detect large variations from emission sources in real-time.