[Grabmer2006] "VOC emissions from Norway spruce ( Picea abies L.[Karst]) twigs in the field�Results of a dynamic enclosure study",
, vol. 40: Elsevier, pp. 128–137, 2006.
During the 2002 summer intensive field campaign of BEWA2000 a proton-transfer-reaction mass spectrometer (PTR-MS) was used for online determination of volatile organic compounds (VOC) emitted by Norway spruce (Picea abies L. [Karst]) twigs in a dynamic sampling enclosure. Emissions of isoprenoids (isoprene and monoterpenes) and oxygenated VOC (OVOC; acetaldehyde, acetone, methanol, and ethanol) were investigated. Emissions showed clear diurnal patterns with high daytime emission rates amounting to 1.8 μg C g−1 dwt h−1 for the sum of monoterpenes and in the range of 0.1 to 0.6 μg C g−1 dwt h−1 for isoprene>acetone>ethanol>methanol. Data were used to validate existing models on isoprene and monoterpene emissions and to discuss environmental and physiological factors affecting VOC emissions. Isoprene and acetaldehyde emission rates were best modelled applying the Guenther 1993 temperature and solar radiation algorithm. Emissions of monoterpenes, acetone and ethanol were best described by a temperature-only exponential algorithm. Using these model approaches a maximum emission variability of 66% was covered (isoprene). Poor r2 values ranging from 0.15 to 0.42 were typical for oxygenated VOC emission modelling indicating the need for model improvement e.g. development of process-based models describing the emission as a result of biochemical de novo synthesis as well as physico-chemical transport properties inside the leaves.
[Eerdekens2009] "VOC measurements within a boreal forest during spring 2005: on the occurrence of elevated monoterpene concentrations during night time intense particle concentration events",
Atmos. Chem. Phys
, vol. 9, no. 21, pp. 8331–8350, 2009.
In this study we present measurements of selected trace gases and aerosols made in a boreal forest during the BACCI-QUEST IV intensive field campaign in Hyytiälä, Finland in April 2005. Springtime diel and vertical variations of VOCs are discussed in connection with the variations in other trace gases and with the prevailing meteorological conditions. A daytime and a nighttime event have been analysed in detail. The nighttime particle event occurred synchronously with huge increases in monoterpenes, while the second event type involved nucleation and was anti-correlated with sulphuric acid. Here we discuss the possible origins of these two distinct forms of aerosol production at the Hyytiälä site using the measurement data, air mass back trajectories and the optical stereoisomery of monoterpenes. Optical stereoisomery is used in source identification to distinguish between unnatural and natural monoterpene emissions.
 "VOC-OHM: A new technique for rapid measurements of ambient total OH reactivity and volatile organic compounds using a single proton transfer reaction mass spectrometer",
International Journal of Mass Spectrometry
, vol. 374, pp. 55–63, Dec, 2014.
Measurements of total hydroxyl radical (OH) reactivity and volatile organic compounds (VOC) are necessary for improving our understanding of reactive emissions and atmospheric oxidation in air pollution and atmospheric chemistry studies. Proton transfer reaction mass spectrometers (PTR-MS) can measure ambient VOCs and the total ambient OH reactivity. However, till date this has always required deployment of two PTR-MS instruments, wherein one instrument measures ambient VOCs and the other instrument measures the total OH reactivity using the comparative reactivity method (CRM). Due to material (e.g. power, space) or financial constraints, deploying two PTR-MS instruments is not always possible and yet it is desirable to quantify both VOCs and OH reactivity. Here, we present a novel hyphenated technique christened VOC-OHM (for Volatile Organic Compounds–OH reactivity Measurement) that enables rapid ambient measurements of both VOCs and total OH reactivity using a single PTR-MS. The technique can provide more specificity for identification of compounds using a PTR-QMS through an estimate of the rate coefficient of the major isobaric contributor with the hydroxyl radical as shown in the case of m/z = 69 for isoprene and furan, which are nominal isobars but have rate coefficients that differ by one order of magnitude. It also demonstrates a new safer and portable substitute for pressurized zero air bottles that have been required thus far in CRM OH reactivity deployments. VOC–OHM successfully couples the typical VOC and CRM experimental set ups without undermining the PTR-MS's ability to measure either parameter. The design of the VOC–OHM system, its validation, optimization and results of field tests are described in detail. The VOC–OHM system measures the ambient VOCs and OH reactivity every hour for ∼20 min durations each, with an ambient data gap of ∼13 min in between. Thus rapid temporal changes in the ambient chemical composition and reactivity are easily quantified. The sampling periods and VOC speciation achieved using VOC–OHM can be customized depending on user preferences, providing more options for the majority of users possessing a single PTR-MS.
 "Volatile Biomarkers in Breath Associated With Liver Cirrhosis - Comparisons of Pre- and Post-liver Transplant Breath Samples",
, Jul, 2015.
Background: The burden of liver disease in the UK has risen dramatically and there is a need for improved diagnostics. Aims: To determine which breath volatiles are associated with the cirrhotic liver and hence diagnostically useful. Methods: A two-stage biomarker discovery procedure was used. Alveolar breath samples of 31 patients with cirrhosis and 30 healthy controls were mass spectrometrically analysed and compared (stage 1). 12 of these patients had their breath analysed after liver transplant (stage 2). Five patients were followed longitudinally as in-patients in the posttransplant period. Results: Seven volatileswere elevated in the breath of patients versus controls. Of these, five showed statistically significant decrease post-transplant: limonene, methanol, 2-pentanone, 2-butanone and carbon disulfide. On an individual basis limonene has the best diagnostic capability (the area under a receiver operating characteristic curve (AUROC) is 0.91), but this is improved by combining methanol, 2-pentanone and limonene (AUROC curve 0.95). Following transplant, limonene shows wash-out characteristics. Conclusions: Limonene,methanol and 2-pentanone are breathmarkers for a cirrhotic liver. This study raises the potential to investigate these volatiles asmarkers for early-stage liver disease. Bymonitoring the wash-out of limonene following transplant, graft liver function can be non-invasively assessed.
 "Volatile compound changes during shelf life of dried Boletus edulis: comparison between SPME-GC-MS and PTR-ToF-MS analysis.",
J Mass Spectrom
, vol. 50, pp. 56–64, Jan, 2015.
<p>Drying process is commonly used to allow long time storage of valuable porcini mushrooms (Boletus edulis). Although considered a stable product dried porcini flavour changes during storage. Monitoring of volatile compounds during shelf life may help to understand the nature of the observed changes. In the present work two mass spectrometric techniques were used to monitor the evolution of volatile compounds during commercial shelf life of dried porcini. Solid phase microextraction (SPME) coupled to gas chromatography - mass spectrometry (GC-MS) allowed the identification of 66 volatile compounds, 36 of which reported for the first time, monitored during the commercial shelf life of dried porcini. Proton transfer reaction - time of flight - mass spectrometry (PTR-ToF-MS) , a direct injection mass spectrometric technique, was shown to be a fast and sensitive instrument for the general monitoring of volatile compound evolution during storage of dried porcini. Furthermore, PTR-ToF-MS grants access to compounds whose determination would otherwise require lengthy pre-concentration and/or derivatization steps such as ammonia and small volatile amines. The two techniques, both used for the first time to study dried porcini, provided detailed description of time evolution of volatile compounds during shelf life. Alcohols, aldehydes, ketones and monoterpenes diminish during the storage while carboxylic acids, pyrazines, lactones and amines increase. The storage temperature modifies the rate of the observed changes influencing the final quality of the dried porcini. We showed the advantages of both techniques, suggesting a strategy to be adopted to follow time evolution of volatile compounds in food products during shelf life, based on the identification of compounds by GC-MS and the rapid time monitoring by PTR-ToF-MS measurements in order to maximize the advantages of both techniques.</p>
[Ruth2008] "Volatile flavour retention in food technology and during consumption: Juice and custard examples",
, vol. 106, no. 4: Elsevier, pp. 1385–1392, 2008.
In this study two aspects of the influence of water on flavour retention were evaluated. The first part of the study was focused on the influence of dehydration and subsequent reconstitution of mandarin juices, which was examined by headspace Proton Transfer Reaction Mass Spectrometry. The different treatments were discriminated by their mass spectra with help of Principal Component Analysis. The second part of the study concerned intranasal volatile flavour retention during food consumption. Volatile flavour concentrations were measured at four intranasal locations in nine subjects during consumption of custard desserts. Differences between the locations indicated various degrees of retention of volatile flavour compounds by the watery mucous in the nasal tract.
[Shaw2007] "Volatile organic compound emissions from dairy cows and their waste as measured by proton-transfer-reaction mass spectrometry.",
Environ Sci Technol
, vol. 41, no. 4: Department of Environmental Science, Policy, and Management, University of California, Berkeley, Hilgard Hall, Berkeley, California 94720, USA. email@example.com, pp. 1310–1316, Feb, 2007.
California dairies house approximately 1.8 million lactating and 1.5 million dry cows and heifers. State air regulatory agencies view these dairies as a major air pollutant source, but emissions data are sparse, particularly for volatile organic compounds (VOCs). The objective of this work was to determine VOC emissions from lactating and dry dairy cows and their waste using an environmental chamber. Carbon dioxide and methane were measured to provide context for the VOCs. VOCs were measured by proton-transfer-reaction mass spectrometry (PTR-MS). The compounds with highest fluxes when cows plus waste were present were methanol, acetone + propanal, dimethylsulfide, and m/z 109 (likely 4-methyl-phenol). The compounds with highest fluxes from fresh waste (urine and feces) were methanol, m/z 109, and m/z 60 (likely trimethylamine). Ethanol fluxes are reported qualitatively, and several VOCs that were likely emitted (formaldehyde, methylamine, dimethylamine) were not detectable by PTR-MS. The sum of reactive VOC fluxes measured when cows were present was a factor of 6-10 less than estimates historically used for regulatory purposes. In addition, ozone formation potentials of the dominant VOCs were -10% those of typical combustion or biogenic VOCs. Thus dairy cattle have a comparatively small impact on ozone formation per VOC mass emitted.
[Ni2012] "Volatile organic compounds at swine facilities: a critical review.",
, vol. 89, no. 7: Department of Agricultural and Biological Engineering, Purdue University, West Lafayette, IN 47907, USA. firstname.lastname@example.org, pp. 769–788, Oct, 2012.
Volatile organic compounds (VOCs) are regulated aerial pollutants that have environmental and health concerns. Swine operations produce and emit a complex mixture of VOCs with a wide range of molecular weights and a variety of physicochemical properties. Significant progress has been made in this area since the first experiment on VOCs at a swine facility in the early 1960s. A total of 47 research institutions in 15 North American, European, and Asian countries contributed to an increasing number of scientific publications. Nearly half of the research papers were published by U.S. institutions. Investigated major VOC sources included air inside swine barns, in headspaces of manure storages and composts, in open atmosphere above swine wastewater, and surrounding swine farms. They also included liquid swine manure and wastewater, and dusts inside and outside swine barns. Most of the sample analyses have been focusing on identification of VOC compounds and their relationship with odors. More than 500 VOCs have been identified. About 60% and 10% of the studies contributed to the quantification of VOC concentrations and emissions, respectively. The largest numbers of VOC compounds with reported concentrations in a single experimental study were 82 in air, 36 in manure, and 34 in dust samples. The relatively abundant VOC compounds that were quantified in at least two independent studies included acetic acid, butanoic acid (butyric acid), dimethyl disulfide, dimethyl sulfide, iso-valeric, p-cresol, propionic acid, skatole, trimethyl amine, and valeric acid in air. They included acetic acid, p-cresol, iso-butyric acid, butyric acid, indole, phenol, propionic acid, iso-valeric acid, and skatole in manure. In dust samples, they were acetic acid, propionic acid, butyric acid, valeric acid, p-cresol, hexanal, and decanal. Swine facility VOCs were preferentially bound to smaller-size dusts. Identification and quantification of VOCs were restricted by using instruments based on gas Chromatography (GC) and liquid chromatography (LC) with different detectors most of which require time-consuming procedures to obtain results. Various methodologies and technologies in sampling, sample preparation, and sample analysis have been used. Only four publications reported using GC based analyzers and PTR-MS (proton-transfer-reaction mass spectrometry) that allowed continuous VOC measurement. Because of this, the majority of experimental studies were only performed on limited numbers of air, manure, or dust samples. Many aerial VOCs had concentrations that were too low to be identified by the GC peaks. Although VOCs emitted from swine facilities have environmental concerns, only a few studies investigated VOC emission rates, which ranged from 3.0 to 176.5mgd(-1)kg(-1) pig at swine finishing barns and from 2.3 to 45.2gd(-1)m(-2) at manure storages. Similar to the other pollutants, spatial and temporal variations of aerial VOC concentrations and emissions existed and were significantly affected by manure management systems, barn structural designs, and ventilation rates. Scientific research in this area has been mainly driven by odor nuisance, instead of environment or health concerns. Compared with other aerial pollutants in animal agriculture, the current scientific knowledge about VOCs at swine facilities is still very limited and far from sufficient to develop reliable emission factors.
[DeGouw2006] "Volatile organic compounds composition of merged and aged forest fire plumes from Alaska and western Canada",
Journal of geophysical research
, vol. 111, no. D10: American Geophysical Union, pp. D10303, 2006.
The NOAA WP-3 aircraft intercepted aged forest fire plumes from Alaska and western Canada during several flights of the NEAQS-ITCT 2k4 mission in 2004. Measurements of acetonitrile (CH3CN) indicated that the air masses had been influenced by biomass burning. The locations of the plume intercepts were well described using emissions estimates and calculations with the transport model FLEXPART. The best description of the data was generally obtained when FLEXPART injected the forest fire emissions to high altitudes in the model. The observed plumes were generally drier than the surrounding air masses at the same altitude, suggesting that the fire plumes had been processed by clouds and that moisture had been removed by precipitation. Different degrees of photochemical processing of the plumes were determined from the measurements of aromatic VOCs. The removal of aromatic VOCs was slow considering the transport times estimated from the FLEXPART model. This suggests that the average OH levels were low during the transport, which may be explained by the low humidity and high concentrations of carbon monoxide and other pollutants. In contrast with previous work, no strong secondary production of acetone, methanol and acetic acid is inferred from the measurements. A clear case of removal of submicron particle volume and acetic acid due to precipitation scavenging was observed.
[Filella2007] "Volatile organic compounds emissions in Norway spruce (Picea abies) in response to temperature changes",
, vol. 130, no. 1: Wiley Online Library, pp. 58–66, 2007.
Volatile organic compound (VOC) emissions from Norway spruce (Picea abies) saplings were monitored in response to a temperature ramp. Online measurements were made with a proton transfer reaction – mass spectrometer under controlled conditions, together with plant physiological variables. Masses corresponding to acetic acid and acetone were the most emitted VOCs. The emission rates of m137 (monoterpenes), m59 (acetone), m33 (methanol), m83 (hexanal, hexenals), m85 (hexanol) and m153 (methyl salicylate, MeSa) increased exponentially with temperature. The emission of m61 (acetic acid) and m45 (acetaldehyde), however, increased with temperature only until saturation around 30°C, closely following the pattern of transpiration rates. These results indicate that algorithms that use only incident irradiance and leaf temperature as drivers to predict VOC emission rates may be inadequate for VOCs with lower H, and consequently higher sensitivity to stomatal conductance.
[Fall1999] "Volatile organic compounds emitted after leaf wounding: on-line analysis by proton-transfer-reaction mass spectrometry",
Journal of Geophysical Research
, vol. 104, no. D13: American Geophysical Union, pp. 15963–15, 1999.
Volatile organic compounds (VOCs) released from vegetation, including wound-induced VOCs, can have important effects on atmospheric chemistry. The analytical methods for measuring wound-induced VOCs, especially the hexenal family of VOCs (hexenals, hexenols, and hexenyl esters), are complicated by their chemical instability and the transient nature of their formation after leaf and stem wounding. Here we demonstrate that formation and emission of hexenal family compounds can be monitored on-line using proton-transfer-reaction mass spectrometry (PTR-MS), avoiding the need for preconcentration or chromatography. These measurements allow direct analysis of the rapid emission of the parent compound, (Z)-3-hexenal, within 1–2 s of wounding of aspen leaves and then its disappearance and the appearance of its metabolites including (E)-2-hexenal, hexenols, and hexenyl acetates. Similar results were seen in wounded beech leaves and clover. The emission of hexenal family compounds was proportional to the extent of wounding, was not dependent on light, occurred in attached or detached leaves, and was greatly enhanced as detached leaves dried out. Emission of (Z)-3-hexenal from detached drying aspen leaves averaged 500 μg C g−1 (dry leaf weight). Leaf wound compounds were not emitted in a nitrogen atmosphere but were released within seconds of reintroduction of oxygen; this indicates that there are not large pools of hexenyl compounds in leaves. The PTR-MS method also allows the simultaneous detection of less abundant hexanal family VOCs including hexanal, hexanol, and hexyl acetate and VOCs formed in the light (isoprene) or during anoxia (acetaldehyde). PTR-MS may be a useful tool for the analysis of VOC emissions resulting from grazing, herbivory, and other physical damage to vegetation, from harvesting of crops, and from senescing leaves.
[Galbally2007] "Volatile organic compounds in marine air at Cape Grim, Australia",
, vol. 4, no. 3: CSIRO, pp. 178–182, 2007.
Measurements were made of volatile organic compounds (VOCs) at Cape Grim using proton transfer reaction mass spectrometry (PTR-MS) during the Precursors to Particles (P2P) Campaign from 10 February to 1 March 2006. Approximately 14 days of clean air data were obtained along with 4 days of data from when polluted air, first from a smoke plume from a fire on Robbins Island adjacent to the station and then air from Victoria, was present. This paper deals with the results obtained in clean air, the focus of the P2P campaign. The protonated masses and probable VOCs measured in the clean marine air were: methanol, 33; acetonitrile, 42; acetaldehyde, 45; acetone, 59; isoprene, 69; methylvinyl ketone/methacrolein (MVK/MACR), 71; methylethyl ketone, 73; and benzene, 79. The measurements at Cape Grim were in some cases near the detection limit and an analytical challenge. The range of concentrations detected in clean maritime air, the relationship to the limited range of previous measurements in marine air in the Northern Hemisphere tropics, and the physical, chemical and biological processes controlling these compounds in the marine air are discussed. The methanol concentrations observed at Cape Grim are consistent with global modelling, incorporating sources that are mainly of vegetation origin. Isoprene has recently been implicated as a precursor to cloud condensation nuclei over the Southern Ocean. In this snapshot of observations at Cape Grim, Tasmania, isoprene and the isoprene oxidation products MVK and MACR appeared to be absent in air from the Southern Ocean. However, isoprene has a very short atmospheric lifetime and the spatial distribution of its emissions may be very heterogeneous. The concentrations of the other VOCs in marine air at Cape Grim, acetonitrile, acetaldehyde, acetone, methylethyl ketone and benzene, were typically a factor of four lower than that observed over the remote tropical ocean in the Northern Hemisphere. The lower concentrations of carbonyls and their precursor hydrocarbons may indicate a limitation on ozone production potential in the Southern Hemisphere compared with the Northern Hemisphere troposphere.
 "Volatile organic compounds in truffle (Tuber magnatum Pico): comparison of samples from different regions of Italy and from different seasons.",
, vol. 5, pp. 12629, 2015.
<p>In this paper volatile organic compounds (VOCs) from Tuber magnatum fruiting bodies were analyzed using a PTR-TOF-MS instrument. The aim was to characterize the VOC's profile of the fruiting bodies and identify if any VOCs were specific to a season and geographical areas. Multiple factorial analysis (MFA) was carried out on the signals obtained by MS. Experiments using ITS region sequencing proved that the T. magnatum life cycle includes the formation of fruiting bodies at two different times of the year. The VOCs profiles diverge when different seasonal and geographical productions are considered. Using PTR-TOF-MS, compounds present at levels as low pptv were detected. This made it possible to determine both the origin of fruiting bodies (Alba and San Miniato) and the two biological phases of fruiting bodies formation in San Miniato truffles.</p>
[Weise2012] "Volatile organic compounds produced by the phytopathogenic bacterium Xanthomonas campestris pv. vesicatoria 85-10.",
Beilstein J Org Chem
, vol. 8: University of Rostock, Institute of Biological Sciences, Albert-Einstein-Str. 3, 18059 Rostock, Germany., pp. 579–596, 2012.
Xanthomonas campestris is a phytopathogenic bacterium and causes many diseases of agricultural relevance. Volatiles were shown to be important in inter- and intraorganismic attraction and defense reactions. Recently it became apparent that also bacteria emit a plethora of volatiles, which influence other organisms such as invertebrates, plants and fungi. As a first step to study volatile-based bacterial-plant interactions, the emission profile of Xanthomonas c. pv. vesicatoria 85-10 was determined by using GC/MS and PTR-MS techniques. More than 50 compounds were emitted by this species, the majority comprising ketones and methylketones. The structure of the dominant compound, 10-methylundecan-2-one, was assigned on the basis of its analytical data, obtained by GC/MS and verified by comparison of these data with those of a synthetic reference sample. Application of commercially available decan-2-one, undecan-2-one, dodecan-2-one, and the newly synthesized 10-methylundecan-2-one in bi-partite Petri dish bioassays revealed growth promotions in low quantities (0.01 to 10 ?mol), whereas decan-2-one at 100 ?mol caused growth inhibitions of the fungus Rhizoctonia solani. Volatile emission profiles of the bacteria were different for growth on media (nutrient broth) with or without glucose.
[Gros2011] "Volatile organic compounds sources in Paris in spring 2007. Part I: qualitative analysis",
, vol. 8, no. 1: CSIRO, pp. 74–90, 2011.
High-time-resolution measurements of volatile organic compounds (VOCs) were performed in the Paris city centre in spring 2007. The studied region was influenced mainly by air masses of two origins: (1) from the Atlantic Ocean, and (2) from north-eastern Europe. Although the baseline levels (i.e. those not influenced by local emissions) of non-methane hydrocarbons (NMHC) and CO were only slightly impacted by changes in the air-mass origin, oxygenated compounds such as acetone and methanol showed much higher baseline levels in continentally influenced air masses. This suggests that NMHC and CO mixing ratios were mainly influenced by local-to-regional-scale sources whereas oxygenated compounds had a more significant continental-scale contribution. This highlights the importance of measuring VOCs instead of NMHC alone in source classification studies. The period of Atlantic air influence was used to characterise local pollution, which was dominated by traffic-related emissions, although traffic represents the source of only one third of total VOCs emissions in the local inventory. In addition to traffic-related sources, additional sources were identified; in particular, emissions from dry-cleaning activities were identified by the use of a specific tracer (i.e. tetrachloroethylene).
 "Volatile organic compounds (VOCs) in soils",
Biology and Fertility of Soils
, vol. 46, pp. 199–213, Feb, 2010.
<p>Soils may act as sources or sinks of volatile organic compounds (VOCs). Many of the formed VOCs are produced by microorganisms, and it would be a challenge to investigate soil microbial communities by studying their VOC profile. Such “volatilomics” would have the advantage of avoiding extraction steps that are often a limit in genomic or proteomic approaches. Abundant literature on microbially produced VOCs is available, and in particular novel detection methods allow additional insight. The aim of this paper was to give an overview on the current knowledge of microbial VOC emissions from soils.</p>
[Benjamin2013] "Volatile release and structural stability of β-lactoglobulin primary and multilayer emulsions under simulated oral conditions.",
, vol. 140, no. 1-2: Riddet Institute, Palmerston North, New Zealand. email@example.com, pp. 124–134, Sep, 2013.
The relationship between emulsion structure and the release of volatile organic compounds (VOCs) was investigated using a model mouth system under oral conditions (tongue mastication, artificial saliva, pH and salt). The VOCs were monitored on-line by proton transfer reaction mass spectrometry (PTR-MS). Two types of emulsion system were compared: primary and multilayer oil-in-water (P-O/W, M-O/W) emulsions consisting of soy oil coated by β-lactoglobulin and pectin layers. The P-O/W emulsions showed intensive flocculation at pH 5 and above 200 mM NaCl where the electrostatic repulsive charge was at a minimum. Bridging and depletion flocculation were mostly observed for P-O/W emulsions containing artificial saliva with 1 wt% mucin. The VOC release was found to increase when the emulsion droplets flocculated, thus changing the oil volume phase distribution. The adsorbed pectin layer stabilised the emulsion structure under conditions of short-time oral processing, and hindered the release of hydrophobic VOCs.