Monitoring Of Volatile Organic Compounds Research Articles

Extending the dynamic range of proton transfer reaction time‐of‐flight mass spectrometers by a novel dead time correction

Proton transfer reaction time-of-flight mass spectrometry (PTR-TOF-MS) allows for very fast simultaneous monitoring of volatile organic compounds (VOCs) in complex environments. In several applications, food science and food technology in particular, peaks with very different intensities are present in a single spectrum. For VOCs, the concentrations range from the sub-ppt all the way up to the ppm level. Thus, a large dynamic range is necessary. In particular, high intensity peaks are a problem because for them the linear dependency of the detector signal on VOC concentration is distorted. In this paper we present, test with real data, and discuss a novel method which extends the linearity of PTR-TOF-MS for high intensity peaks far beyond the limit allowed by the usual analytical correction methods such as the so-called Poisson correction. Usually, raw data can be used directly without corrections with an intensity of up to about 0.1 ions/pulse, and the Poisson correction allows the use of peaks with intensities of a few ions/pulse. Our method further extends the linear range by at least one order of magnitude. Although this work originated from the necessity to extend the dynamic range of PTR-TOF-MS instruments in agro-industrial applications, it is by no means limited to this area, and can be implemented wherever dead time corrections are an issue.

Holographic Detection of Hydrocarbon Gases and Other Volatile Organic Compounds

There is a need to develop sensors for real-time monitoring of volatile organic compounds (VOCs) and hydrocarbon gases in both external and indoor environments, since these compounds are of growing concern in human health and welfare. Current measurement technology for VOCs requires sophisticated equipment and lacks the prospect for rapid real-time monitoring. Holographic sensors can give a direct reading of the analyte concentration as a color change. We report a technique for recording holographic sensors by laser ablation of silver particles formed in situ by diffusion. This technique allows a readily available hydrophobic silicone elastomer to be transformed into an effective sensor for hydrocarbon gases and other volatile compounds. The intermolecular interactions present between the polymer and molecules are used to predict the sensor performance. The hydrophobicity of this material allows the sensor to operate without interference from water and other atmospheric gases and thus makes the sensor suitable for biomedical, industrial, or environmental analysis.

Application of ion mobility spectrometry for the detection of human urine

The aim of the present study was to evaluate the suitability of ion mobility spectrometry (IMS) for the detection of human urine as an indication of human presence during urban search and rescue operations in collapsed buildings. To this end, IMS with a radioactive ionization source and a multicapillary column was used to detect volatile organic compounds (VOCs) emitted from human urine. A study involving a group of 30 healthy volunteers resulted in the selection of seven volatile species, namely acetone, propanal, 3-methyl-2-butanone, 2-methylpropanal, 4-heptanone, 2-heptanone and octanal, which were detected in all samples. Additionally, a preliminary study on the permeation of urine volatiles through the materials surrounding the voids of collapsed buildings was performed. In this study, quartz sand was used as a representative imitating material. Four compounds, namely 3-methyl-2-butanone, octanal, acetone and 2-heptanone, were found to permeate through the sand layers during all experiments. Moreover, their permeation times were the shortest. Although IMS can be considered as a potential technique suitable for the detection, localization and monitoring of VOCs evolved from human urine, further investigation is necessary prior to selecting field chemical methods for the early location of trapped victims.

PTR‐TOF‐MS and data‐mining methods for rapid characterisation of agro‐industrial samples: influence of milk storage conditions on the volatile compounds profile of Trentingrana cheese

Proton transfer reaction-mass spectrometry (PTR-MS), a direct injection mass spectrometric technique based on an efficient implementation of chemical ionisation, allows for fast and high-sensitivity monitoring of volatile organic compounds (VOCs). The first implementations of PTR-MS, based on quadrupole mass analyzers (PTR-Quad-MS), provided only the nominal mass of the ions measured and thus little chemical information. To partially overcome these limitations and improve the analytical capability of this technique, the coupling of proton transfer reaction ionisation with a time-of-flight mass analyser has been recently realised and commercialised (PTR-TOF-MS). Here we discuss the very first application of this new instrument to agro-industrial problems and dairy science in particular. As a case study, we show here that the rapid PTR-TOF-MS fingerprinting coupled with data-mining methods can quickly verify whether the storage condition of the milk affects the final quality of cheese and we provide relevant examples of better compound identification in comparison with the previous PTR-MS implementations. In particular, 'Trentingrana' cheese produced by four different procedures for milk storage are compared both in the case of winter and summer production. It is indeed possible to set classification models with low prediction errors and to identify the chemical formula of the ion peaks used for classification, providing evidence of the role that this novel spectrometric technique can play for fundamental and applied agro-industrial themes.

Proton transfer reaction rate coefficients between H 3O + and some sulphur compounds

Volatile sulphur compounds (VSCs) are key compounds in many fields of basic and applied science and technology, such as environmental sciences, food science, geochemistry, petrochemistry, agriculture, biology and medicine. Proton transfer reaction mass spectrometry (PTR-MS) allows for on-line monitoring of volatile organic compounds (VOCs) and, in particular, of VSCs with ultra low detection limits and a fast response time. In principle, with PTR-MS, absolute quantification of VOC concentrations without calibration is possible, provided the branching ratios are known. However, for this, the reaction rate coefficients between VOCs and the hydronium ion have also to be known. Several well-established theories may be used to determine ion-neutral molecule reaction rate coefficients. In the case of H 3O +–VOC reactions proceeding in a PTR-MS drift tube, a key factor to be considered is the centre-of-mass energy, which is generally much higher than the thermal energy, due to the additional translational (drift) energy of the ion. Nevertheless, it is common practice to employ collision theories that do not show an explicit dependence on the centre-of-mass energy. First we review basic aspects of ion-neutral reactions in the PTR-MS drift tube and various methods to calculate reaction rate coefficients. Next, we calculate, on the basis of quantum chemical methods and different theoretical approaches for ion-molecule collisions, reaction rate coefficients between selected sulphur compounds and H 3O +. Finally, we discuss proper methods for the calculations of ion-neutral molecule reaction rate coefficients in the context of PTR-MS and the corresponding experimental parameters involved.

Volatile aldehydes in libraries and archives

Volatile aldehydes are produced during degradation of paper-based materials. This may result in their accumulation in archival and library repositories. However, no systematic study has been performed so far. In the frame of this study, passive sampling was carried out at ten locations in four libraries and archives. Despite the very variable sampling locations, no major differences were found, although air-filtered repositories were found to have lower concentrations while a non-ventilated newspaper repository exhibited the highest concentrations of volatile aldehydes (formaldehyde, acetaldehyde, furfural and hexanal). Five employees in one institution were also provided with personal passive samplers to investigate employees’ exposure to volatile aldehydes. All values were lower than the presently valid exposure limits. The concentration of volatile aldehydes, acetic acid, and volatile organic compounds (VOCs) in general was also compared with that of outdoor-generated pollutants. It was evident that inside the repository and particularly inside archival boxes, the concentration of VOCs and acetic acid was much higher than the concentration of outdoor-generated pollutants, which are otherwise more routinely studied in connection with heritage materials. This indicates that further work on the pro-degradative effect of VOCs on heritage materials is necessary and that monitoring of VOCs in heritage institutions should become more widespread.

Compact semi-automatic incident sampler for personal monitoring of volatile organic compounds in occupational air

Suddenly occurring and time limited chemical exposures caused by unintended incidents might pose a threat to many workers at various work sites. Monitoring of exposure during such occasional incidents is challenging. In this study a compact, low-weight and personal semi-automatic pumped unit for sampling of organic vapor phase compounds from occupational air during sporadic and suddenly occurring incidents has been developed, providing simple activation by the worker potentially subjected to the sudden occurring exposures when a trained occupational hygienist is not available. The sampler encompasses a tube (glass or stainless steel) containing an adsorbent material in combination with a small membrane pump, where the adsorbent is capped at both ends by gas tight solenoid valves. The sampler is operated by a conventional 9 V battery which tolerates long storage time (at least one year), and is activated by pulling a pin followed by automatic operation and subsequent closing of valves, prior to shipping to a laboratory. The adjustable sampling air flow rate and the sampling time are pre-programmed with a standard setting of 200 mL min(-1) and 30 min, respectively. The average airflow in the time interval 25-30 min compared to average airflow in the interval 2-7 min was 92-95% (n = 6), while the flow rate between-assay precisions (RSD) for six different samplers on three days each were in the range 0.5-3.7%. Incident sampler recoveries of VOCs from a generated VOC atmosphere relative to a validated standard method were between 95 and 102% (+/-4-5%). The valves that seal the sampler adsorbent during storage have been shown to prevent an external VOC atmosphere (500 mg m(-3)) to enter the adsorbent tube, in addition to that the sampler adsorbent is storable for at least one month due to absence of ingress of contaminants from internal parts. The sampler was also suitable for trapping of semi-volatile organophosphates.

Commuter exposure to BTEX in public transportation modes in Bangkok, Thailand

Measurements and monitoring of volatile organic compounds (VOCs) have been conducted in the metropolitan Bangkok. However, in-vehicle levels of VOCs are still lacking. This study investigated VOCs concentrations in four public transportation modes in Bangkok, Thailand during two rush hour periods (7:00–9:00 a.m. and 4:00–7:00 p.m.). The four modes included an air-conditioned bus (A/C bus), non-air-conditioned bus (non-A/C bus), electric sky train, and a passenger boat traveling along the canal. Comparison among three important bus routes was also studied. In-vehicle air samples were collected using charcoal sorbent tubes and then analyzed by a gas chromatography-mass spectrometer. Results showed that the transportation modes significantly influenced the abundance of in-vehicle benzene, toluene, ethylbenzene, and m,p-xylene (BTEX). Median concentrations of BTEX were 11.7, 103, 11.7, and 42.8 μg/m 3 in A/C bus; 37.1, 174, 14.7, and 55.4 μg/m 3 in non-A/C bus; 2.0, 36.9, 0.5, and 0.5 μg/m 3 in sky train; and 3.1, 58.5, 0.5, and 6.2 μg/m 3 in boat, respectively. Wilcoxon rank sum test indicated that toluene and m,p-xylene in the sky trains were statistically lower than that in the other three modes at a p-value of 0.05. There were statistical differences in TEX concentrations among the bus routes in the non-A/C buses. In addition, the benzene to toluene ratios implied that tail-pipe emissions were important contributor to the abundance of in-vehicle VOCs.

Improved mass accuracy in PTR-TOF-MS: Another step towards better compound identification in PTR-MS

Proton transfer reaction mass spectrometry (PTR-MS) provides on-line monitoring of volatile organic compounds (VOCs) with a low detection threshold and a fast response time. Commercially available set-ups are usually based on quadrupole analysers that, due to the unit mass resolution, do not provide useful analytical information besides the nominal mass of the ions detected. Recently new instruments based on time-of-flight (PTR-TOF-MS) analysers have been proposed and commercialized. They provide higher mass resolution and thus improve the analytical information contained in the spectra. Mass accuracy, however, is an issue that has not been considered in great detail in the published papers on PTR-TOF-MS so far. We show here that the mass accuracy obtained by a commercial apparatus can be improved by proper data analysis. In particular, internal calibration based on an improved algorithm allows for a mass accuracy that suffices for elemental determination in the most common situations. Achieving good mass accuracy is a fundamental step for further exploiting the analytical potential of PTR-MS.

Environmental and biological monitoring of volatile organic compounds in the workplace

The exposure of workers to volatile organic compounds (VOCs) in the workplace has been evaluated in four different occupations, namely: house painters, varnishing workers, car painters and petrol station workers. The study was carried out by analyzing the ambient air within the workers’ breathing zone as well as the alveolar air of these workers, which was selected as the biomarker of exposure. Twenty six VOCs were measured in the air samples. Nearly all target VOCs were found in the ambient air of the workplaces assessed, usually involving in the most abundant compounds, toluene, o-xylene and N-butyl acetate, concentrations between 60 and 51 110 μg m −3. The same VOCs were found in the alveolar air of workers after their work shift, at concentrations whose amount depended on the compound and occupation involved. Toluene, at concentrations between 90 and 29 840 μg m −3, o-xylene, between 30 and 12 285 μg m −3, and N-butyl acetate, between 10 and 8045 μg m −3, were also the most abundant compounds found in the alveolar air of workers after exposure. The post-work concentrations of VOCs in alveolar air correlated significantly with ambient air concentrations, obtaining correlation coefficients over 0.9 for the compounds studied. Furthermore, a general trend towards greater absorption of benzene derivatives by the human body (the average percentage of absorption is 50%) than that of esters (average percentage of 20%) has been observed in the data obtained throughout the study.

Low temperature headspace desorption of volatile organic compounds trapped in air sampling solid-supports

Environmental context. The monitoring of volatile organic compounds (VOCs) in air is of great importance for air quality on both local and global scales. The determination of VOCs can be carried out by gas chromatography–mass spectrometry (GC-MS) after active or passive sampling and (high temperature) thermal desorption. An attractive alternative would be to combine GC-MS with headspace (HS) systems as it allows simpler, faster, low temperature desorption. We present here the first report of HS-GC-MS for the determination of VOCs in air sampled using solid supports. Abstract. The use of a headspace (HS) for low temperature desorption of VOCs, previously sorbed from indoor air on solid supports, has been evaluated in order to improve the GC-MS determinations in environmental studies. Graphitised carbon black (GCB), Porapak and Tenax were considered in this study. The HS injector does not allow temperatures higher than 150°C, so there is no a complete desorption of VOCs. However highly volatile compounds were completely desorbed from Porapak and Tenax, but compounds of low volatility showed a strong retention with recoveries of 71–100% for Porapak and 59–100% for Tenax. All studied VOCs were quantitatively desorbed from GCB. Only 100 μL of the HS volume is injected in the chromatographic system. So in spite of the reduced sensitivity we are able to make replicate analyses on the same sampler. Additional experiments were performed using the proposed methodology for the analysis of aforementioned supports in passive and active sampling modes. In short, the proposed methodology reduces the energy consumed and makes it possible to determine the VOCs in air with reduced cost media. The developed methodology permits the determination of 32 VOCs with limits of detection values around 1 μg m–3 when actively sampling air at 50 mL min–1 for 2 h and using 100 mg solid sorbent.

Real-life application of a QCM-based e-nose: quantitative characterization of different plant-degradation processes

Continuous surveillance of composting processes would enable a feedback loop to be obtained for both analysis and process control. For this purpose, we designed e-noses based on a six-electrode quartz-crystal microbalance (QCM) array coated with affinity materials and molecularly imprinted polymers (MIP). They enable quantitative monitoring of volatile organic compounds (VOCs) emitted directly in a compost bin and are highly suitable tools for achieving on-line characterization of the degradation processes occurring. During grass and pine composting (duration 14 days and 40 days, respectively), we observed concentrations of up to 250 ppm of esters, 700 ppm of alcohols, 250 ppm of terpenes, and 90% relative humidity directly on-line with such a system and could validate the data off-line by GC-MS. The sensor also gave direct insight into the differences between the two composting batch types. Besides duration, during grass composting larger amounts of alcohols are emitted whereas relative amount of terpenes is twice as high for pine composting. Detailed correlation of the sensor and the GC-MS data allows approximate estimation of the sensitivity of the sensor materials towards analyte classes such as, e.g., aliphatic alcohols or terpenes.

Monitoring of volatile organic compounds in non-residential indoor environments

A weekly monitoring campaign of volatile organic compounds (VOC), with single sampling of 24 h, was carried out in non-residential indoor environments such as libraries, pharmacies, offices, gymnasiums, etc., in order to evaluate the VOC concentrations to which people are exposed. Moreover, an outdoor sample was coupled to each indoor site to point out the influence of indoor sources. They were sampled with Radiello diffusive samplers for thermal desorption and analyzed by GC-MS. As already described in other papers, the VOC levels of most of the indoor sites were higher than that observed in the corresponding outdoor sites. For example, some sites showed a level of pollution that is ten times higher than their corresponding outdoor site. The monitored environments that had higher concentrations of the investigated VOC were the pharmacies, a newspaper stand, a copy center, and the coffee shops. Analysis of the weekly average concentrations of each pollutant and the use of literature allowed pointing out some site-specific characteristics that singled out possible sources of VOC. These results were verified analyzing the indoor-outdoor ratio (I/O) too. Newspaper stands were characterized by very high concentrations of toluene and pharmacies were characterized by high concentrations of aromatic compounds. Indoor air pollution caused by volatile organic compounds (VOC) might affect human health at home as well as in public and commercial buildings. The main VOC sources in indoor environments are human activities, personal care products, smoking, house cleaning products, building products, and outside pollution. To preserve human health it is necessary to evaluate the average concentrations of VOC to which people are exposed and to identify the main sources of indoor pollution by means of suitable indoor monitoring campaigns in several environments. These investigations allow pointing out the characteristic critical situations of some indoor environments or some other types of environments.

On-Line Monitoring of Microbial Volatile Metabolites by Proton Transfer Reaction-Mass Spectrometry

A method for analysis of volatile organic compounds (VOCs) from microbial cultures was established using proton transfer reaction-mass spectrometry (PTR-MS). A newly developed sampling system was coupled to a PTR-MS instrument to allow on-line monitoring of VOCs in the dynamic headspaces of microbial cultures. The novel PTR-MS method was evaluated for four reference organisms: Escherichia coli, Shigella flexneri, Salmonella enterica, and Candida tropicalis. Headspace VOCs in sampling bottles containing actively growing cultures and uninoculated culture medium controls were sequentially analyzed by PTR-MS. Characteristic marker ions were found for certain microbial cultures: C. tropicalis could be identified by several unique markers compared with the other three organisms, and E. coli and S. enterica were distinguishable from each other and from S. flexneri by specific marker ions, demonstrating the potential of this method to differentiate between even closely related microorganisms. Although the temporal profiles of some VOCs were similar to the growth dynamics of the microbial cultures, most VOCs showed a different temporal profile, characterized by constant or decreasing VOC levels or by single or multiple peaks over 24 h of incubation. These findings strongly indicate that the temporal evolution of VOC emissions during growth must be considered if characterization or differentiation based on microbial VOC emissions is attempted. Our study may help to establish the analysis of VOCs by on-line PTR-MS as a routine method in microbiology and as a tool for monitoring environmental and biotechnological processes.

Issues in VOC monitoring and reporting

Volatile Organic Compounds (VOCs) present a particularly unique testing dilemma sincethere are a large number of different compounds defined as VOCs, The process of accuratelyand consistently measuring the quantity of total VOCs emitted is a matter of concern to policymakers and researchers,Each method has advantages and disadvantages relative to the other methods, The choice ofmeasurement and reporting techniques depends on the purpose that the data will serve, Due todiffering analytical limitations for each of the VOC test methods, all sources may not be ableto use the same method/ procedures to monitor and report,Because of the wide variety of compounds of interest coupled with the lack of standardizedsampling and analysis procedures, detennination of pollutants in ambient air is a complextask, Many toxic organics can be sampled and analyzed by several techniques, with differentinterferences and detection limitations, No uniforn1 averaging period is defined for ambientvoe measurement,

Field monitoring of volatile organic compounds using passive air samplers in an industrial city in Japan

Highly portable, sensitive, and selective passive air samplers were used to investigate ambient volatile organic compound (VOC) levels at multiple sampling sites in an industrial city, Fuji, Japan. We determined the spatial distributions of 27 species of VOCs in three campaigns: Mar (cold season), May (warm season), and Nov (mild season) of 2004. In all campaigns, toluene (geometric mean concentration, 14.0 μg/m 3) was the most abundant VOC, followed by acetaldehyde (4.76 μg/m 3), and formaldehyde (2.58 μg/m 3). The spatial distributions for certain VOCs showed characteristic patterns: high concentrations of benzene and formaldehyde were typically found along major roads, whereas high concentrations of toluene and tetrachloroethylene (PCE) were usually found near factories. The spatial distribution of PCE observed was extremely consistent with the diffusion pattern calculated from Pollutant Release and Transfer Register data and meteorological data, indicated that passive air samplers are useful for determining the sources and distributions of ambient VOCs.

A comparison of gas- and liquid-loaded sorbent standards for the calibration of measurements of volatile organic compounds

The monitoring of volatile organic compounds (VOCs) at environmental levels is commonly carried out in the field using Perkin-Elmer-type sorbent-based passive or active samplers. Measurements of important trace species, such as benzene, toluene and xylenes, are often calibrated using thermal desorption standards that are liquid loaded onto the sorbent. This method is normally adopted over the method of gas loading of standards, on the grounds of ease of application and cost. We report a comparison between sorbent standards prepared by both methods using the sorbent Carbopack X and show that under the conditions used here the two show good agreement with each other. We also present work using liquid-loaded standards on the sorbents Tenax and Chromosorb-106, prepared with the solvents cyclohexane and methanol. The results indicate that, to obtain 100% recovery of the determinands from the desorbed samplers, issues such as type of solvent and sorbent combination together with purge flow should be considered.

Real-time continuous monitoring methods for airborne VOCs

Several volatile organic compounds (VOCs) have adverse health effects and contribute to reactions promoting photochemical smog. The estimated world-wide average emissions of VOCs are about 1809 million tons/year. This overview focuses on the most commonly used methods for real-time monitoring of VOCs in ambient air, including differential optical absorption spectroscopy (limit of detection (LOD) ∼2.6 μg/m 3), low-pressure chemical ionization/tandem mass spectrometry (MS 2) (LOD ∼2.0 μg/m 3), atmospheric pressure chemical ionization/MS 2 (LOD ∼38.3 μg/m 3) and proton-transfer reaction MS (LOD ∼0.3 μg/m 3). Finally, we present the results from some comparative studies of atmospheric aromatic hydrocarbon measurements involving real-time monitoring methods and gas chromatography-related conventional techniques.

Terpene emission in tissue culture

Tissue cultured plants’ vessel headspace is subject to changes during subculture, and the analysis of its variation offers a non-destructive approach for monitoring plant physiology. Among the volatile organic compounds (VOCs) that can be released by plants and be potentially recovered in the airspace of plant tissue cultures, terpenes are very important since they can offer a snapshot of the physiological status of the plant under in vitro cultivation. Terpenes are synthesized from carbon directly shunted from the photosynthetic carbon fixation cycle and their emission is under genetic and environmental control. The experiments described in this paper propose the evaluation of the plant terpene profile in the culture’s headspace as an early indicator of plant stress through the characterization of plant terpene production. Monitoring of terpene emission as a plant response to mechanical stress such as plant wounding showed an increased isoprene and monoterpene emission rates in the first hour after cutting. The comparison of headspace composition of cultures of two fruit rootstocks, Colt and GF677, showed the former having higher emissions of isoprene, α-pinene and limonene than the latter. A decreasing emission trend was observed during subculture, apparently as a result of culture aging. The in vitro headspace analysis of different myrtle (Myrtus communis L.) clones showed a specific and distinctive terpene emission profile. VOC monitoring of in vitro culture headspace is discussed as a non-destructive approach useful for its relation with major physiological activities of culture and for the determination of the potential production of terpenes.

Ambient air monitoring with Auto-gas chromatography running in trigger mode

Speciated volatile organic compounds (VOC), either as ozone precursors or air toxics in the air, are commonly monitored by triggered canister method or continuous ozone precursor analyzer (commonly known as Auto-gas chromatography (GC)) method. In the triggered canister method, a canister sample is collected when a total non-methane organic compound (TNMOC) concentration exceeds a pre-determined trigger level. The canister sample is then analyzed in a lab in a later time. In the Auto-GC method, an online GC runs in a “continuous” mode with a sampling and analysis cycle of 1 h. Within the cycle hour, samples are collected only during the first 40 min. A new approach of Auto-GC running in trigger mode is developed in this study. This new approach uses Auto-GC but operates it in a trigger mode similar to the triggered canister sampling method. Compared to the triggered canister sample method, this system provides near real-time speciated VOC data, which are critical for responding to a high VOC concentration episode. Although the canister system generally costs less, its cost advantage may diminish if trigger events are frequent and the monitoring duration is long. Compared to continuous Auto-GC, triggered GC has its niche—it is better for capturing transient plumes with a small footprint. The continuous GC either misses a transient plume if the plume does not arrive at the sampling site during the sampling cycle or flattens the plume concentration peak by dilution with non-plume air sample. Field experience with this system for fenceline VOC monitoring is presented. The sampling and calibration strategy for trigger mode operation is described. The chromatograph retention time drift issues are discussed. The system performance is evaluated, including the method detection limit, precision and accuracy. The trigger mode configuration for VOC fenceline or near source monitoring in this work proved effective for local and transient plume identification.