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Using mesoporous silica MCM-41 for in-line enrichment of atmospheric volatile organic compounds.

A mesoporous silica MCM-41 with pore size of 29A was synthesized and assessed for its applicability as a sorbent for in-line trapping of volatile organic compounds (VOCs) from air samples. Several commercially available microporous carbon molecular sieves, i.e., Carbosieve SIII, Carboxen 1000, Carboxen 1003, and Carbotrap purchased from Supelco, were employed to form either single sorbent traps or multi-sorbent traps for comparing adsorption properties with those of the silica MCM-41. A standard gas mixture containing more than 50 target compounds with size varying from C(2) to C(12) was adsorbed by these sorbents and the per carbon response of flame ionization detection (FID) for the target compounds was calculated for obtaining the adsorption profiles. While the multi-carbon sorbents show very uniform adsorption ability across the entire carbon range from C(3) to C(12), the mesoporous silica MCM-41, however, shows little sorption for smaller molecules from C(3) to C(7), but exhibit comparable sorption ability for C(8)-C(12) compounds. Desorption at various temperatures indicates that C(8)-C(12) compounds once trapped can be easily released at moderate temperatures of about 150 degrees C, whereas for carbon sorbents the desorption temperatures for sufficient recovery need to go beyond 300 degrees C due to much tighter hold-up in the microporous structure. Sorption ability for MCM-41 is also reflected on linearity. Compounds with sufficient sorption as suggested by the adequate per carbon response also exhibit excellent precision and linearity with R(2) close to unity, an important requirement for quantitative analysis of ambient VOCs.

Chromatography, Gas↗

Determining the equilibrium partitioning coefficients of volatile organic compounds at an air-water interface.

The single equilibration technique (SET) was adopted to determine the partitioning coefficients (pc) at an air-water interface for volatile organic compounds (VOCs), including ethanol, iso-propanol (IPA), iso-butanol (IBA), methyl ethyl ketone (MEK) and toluene, all extensively used in industrial processes. Standard SET procedures were established. The liquid concentrations (CL) of tested VOCs ranged from 10 to 125 mg l(-1) for alcohols and MEK, and from 0.5 to 20 mg l(-1) for toluene. The temperatures (Tw) of aqueous VOC solutions were maintained at 27, 32, 38 and 42 degrees C to determine the gaseous concentrations at equilibrium (Cg*) and pc of VOCs, using the formula pc=(Cg*/CL). Results reveal that the pc values of all tested components increase slowly with Tw given a constant CL, and that the pc of alcohols and MEK fall as CL increases at a constant Tw. In contrast, the pc of toluene is not significantly impacted by a variation in CL at a constant Tw. However, the effect of CL concentration has seldom been discussed. The heats of liquid and gaseous phase transfer (DeltaHtr) of VOC, and the highly linear regression (with squared correlation coefficients, R2, from 0.901 to 0.999) between lnCg* and Tw(-1) are also evaluated. The experimental results and the VOC mass transfer characteristics are helpful for evaluating the emission of VOC from the water surface of wastewater treatment facilities.

Air↗

A diffusive badge sampler for volatile organic compounds in ambient air and determination using a thermal desorption-GC/MS system.

A sensitive personal badge sampler packed with Carbopack B for ambient levels of volatile organic compounds and an analytical system using a thermal desorption-preconcentration-GC/MS have been developed. The capacity of the new sampler was sufficient for an 8-h sampling period, and the analytical method was sensitive enough for the measurement of sub-ppb levels for a 2-h sampling period. The samplers were compared to diffusive samplers (OVM 3500) for typical environmental concentrations. There was a good correlation between the results obtained with the new samplers and the OVM samplers.

Air Pollutants, Occupational↗

Contribution of the gasoline distribution cycle to volatile organic compound emissions in the metropolitan area of Mexico City.

Gasoline distribution in the metropolitan area of Mexico City (MAMC) represents an area of opportunity for the abatement of volatile organic compound (VOC) emissions. The gasoline distribution in this huge urban center encompasses several operations: (1) storage in bulk and distribution plants, (2) transportation to gasoline service stations, (3) unloading at service stations' underground tanks, and (4) gasoline dispensing. In this study, hydrocarbon (HC) emissions resulting from breathing losses in closed reservoirs, leakage, and spillage from the operations just listed were calculated using both field measurements and reported emission factors. The results show that the contribution of volatile HC emissions due to storage, distribution, and sales of gasoline is 6651 t/year, approximately 13 times higher than previously reported values. Tank truck transportation results in 53.9% of the gasoline emissions, and 31.5% of emissions are generated when loading the tank trucks. The high concentration of emissions in the gasoline transportation and loading operations by tank trucks has been ascribed to (1) highly frequent trips from distribution plant to gasoline stations, and vice versa, to cope with excessive gasoline sales per gasoline station; (2) low leakproofness of tank trucks; and (3) poor training of employees. In addition, the contribution to HC evaporative and exhaust emissions from the vehicles of the MAMC was also evaluated.

Air Pollutants↗

Comparison of two field sampling procedures (En Core and field methanol extraction) for volatile organic compounds.

In-situ Lasagna technology was recently evaluated at a contaminated site at Offutt Air Force Base. The site was contaminated with low levels (<30 mg/kg) of volatile organic compounds (VOCs). Originally, researchers planned to use field methanol extraction for both pre- and post-treatment sampling to evaluate the effectiveness of the technology on contaminant reduction. Precharacterization sampling, however, indicated that concentrations of some contaminants of concern were much lower than expected. Because use of methanol increases the detection limit, it was probable that post-treatment concentrations of these target contaminants would be nondetectable if methanol extraction was used. Project management, therefore, decided to use En Core samplers in addition to field methanol extraction during the pretreatment sampling event. The En Core sampling approach, while yielding a lower detection limit, uses discreet samples along the length of a core, whereas the methanol extraction approach samples the entire length of the core. The concern was that discreet samples may bias results if any "hot spots" were present. The two field sampling procedures, En Core and field methanol extraction, were performed side-by-side during the pretreatment phase of the technology evaluation in order to determine if the concern was valid for this site. Results were compared for four contaminants of concern: trichloroethylene, vinyl chloride, cis-1,2-dichloroethene, and trans-1,2-dichloroethene. The two procedures produced similar results with respect to both the concentration means and the variances, and no bias was evident. This finding supports project management's decision to use only En Core samplers post-treatment due to low concentrations of target contaminants.

Environmental Monitoring↗

An electrospray membrane probe for the analysis of volatile and semi-volatile organic compounds in water.

A new membrane probe incorporating electrospray ionization (ESI) was designed, built and coupled to an ion trap mass spectrometer to detect low levels of semi-volatile organic compounds (SVOCs) in water. Similar to other membrane introduction mass spectrometry (MIMS) systems, the probe contains a capillary polydimethylsiloxane (PDMS) membrane to allow for the preferential permeation of small molecules but, in contrast, the interface uses a liquid/membrane/liquid interface rather than liquid/membrane/gas. The ESI source allows the probe to be operated at atmospheric pressure in positive or negative ionization mode and the lack of fragmentation in ESI allows for the simultaneous screening of many analytes with high sensitivity. The interface allows for the addition of additives to both the external and the internal liquid mobile phases to selectively improve permeation and/or the ionization efficiency of various classes of compounds. Characterization of the probe with methanol as the internal mobile phase showed that the signal for aniline optimized at 60 degrees C and an internal flow rate between 2-5 microL/min. The transfer of analyte through the membrane from water to methanol ensures a strong signal and robust electrospray for both positive and negative ion mode which is not typical when spraying pure water. Detection limits for aniline, pyridine and pentachlorophenol, and for the herbicides alachlor, atrazine, butachlor, metolachlor and simazine, were in the ppb to pptr range.

Environmental Monitoring↗

Multiple headspace solid-phase microextraction for the quantitative determination of volatile organic compounds in multilayer packagings.

The theory of multiple headspace solid-phase microextraction (HS-SPME) and a method based on multiple HS-SPME for the quantitative determination of volatile organic compounds (VOCs) in packaging materials is presented. The method allows the direct analysis of solid samples without using organic solvents to extract analytes. Multiple headspace solid-phase microextraction is a stepwise method proposed to eliminate the influence of the sample matrix on the quantitative analysis of solid samples by HS-SPME. Different amounts of packaging and different volumes of standard solution were studied in order to remove a substantial quantity of analytes from the headspace at each extraction and obtain the theoretical exponential decay of the peak area of the four successive extractions and, thus, the total area was calculated from these four extractions. In addition, two fibres were compared: carboxen-polydimethylsiloxane (CAR-PDMS) and divinylbenzene-carboxen-polydimethylsiloxane (DVB-CAR-PDMS), as they showed differences in the linearity of the exponential decay with the number of extractions depending on the compound. The CAR-PDMS fibre was better for the VOCs with a low molecular mass, whereas the DVB-CAR-PDMS fibre was better for the VOCs with a high molecular mass. Finally, the method was characterised in terms of linearity, detection limit and reproducibility and applied to analyse four multilayer packaging samples with different VOCs contents.

Organic Chemicals↗

Volatile organic compound (VOC) adsorption on material: influence of gas phase concentration, relative humidity and VOC type.

UNLABELLED: This paper presents the results of a factorial experiment design analysis to investigate volatile organic compounds (VOC) adsorption on a ceiling tile. The impacts of three factors, VOC gas phase concentration, relative humidity, and VOC type, as single parameters and as a combination, on adsorption have been investigated. Cyclohexane, toluene, ethyl acetate, isopropyl alcohol and methanol were the five VOCs used in this study. A factor significant level was determined through evaluating its F value and comparing it with the critical value of F distribution at 95% confidence level. It was found that: (i) neither the relative humidity and gas phase concentration nor any interaction effect between them had significant impacts on toluene adsorption on the ceiling tile; (ii) the adsorption isotherm appeared to be linear for the non-polar compounds and non-linear for the semi-polar and polar compounds; (iii) no significant impact of relative humidity on adsorption was observed for most VOC compounds except for methanol; and (iv) the ceiling tile had the highest adsorption capacity toward the polar compounds, followed by the aromatic compounds and aliphatic compounds. In addition, the statistical analysis regarding the experimental results of toluene as a single compound or as a part of a mixture showed that toluene adsorption capacity on the ceiling tile as a single compound was higher than as a part of a mixture. PRACTICAL IMPLICATIONS: Building materials and furnishings may act as source and sink of VOCs in the indoor environment. In this study, a factorial experiment design analysis technique was used to show the impact of three factors, VOC gas phase concentration, relative humidity, and VOC type, as single parameters and as a combination, on the adsorption process (sink effect). The aim was to better understand the interaction between these parameters and to verify the common assumptions made in the model development and measurement of indoor air quality.

Adsorption↗

Development and application of a thermal desorption method for the analysis of polar volatile organic compounds in workplace air.

The application of a newly developed thermal desorption method for the analysis of workplace air to the analysis of polar compounds is reported. The method was validated for both pumped and diffusive sampling of test gases containing polar volatile organic compounds (esters, alcohols, ketones or aldehydes) on adsorption tubes and subsequent analysis of these tubes. Carbosieve SIII, Carboxen 569, Carbopack B and Tenax TA were used as solid adsorbents. Analysis was performed by thermal desorption of the analytes from the adsorbent tubes followed by gas chromatography-flame ionisation detection (GC-FID). It could be demonstrated that thermal desorption-GC-FID is feasible also for the analysis of polar compounds and that problems arising from the high concentration levels of some analytes in workplace air could be solved.

Adsorption↗

A direct quantitative analysis method for monitoring biogenic volatile organic compounds released from leaves of Pelargonium hortorum in situ.

A direct quantitative method is presented that is based upon the use of multiple headspace solid phase microextraction (HS-SPME) to monitor biogenic volatile organic compounds (BVOCs) released from a living leaf of Pelargonium hortorum in situ. Seventeen BVOCs were detected by GC-MS after a single SPME extraction using a CAR/DVB/PDMS fibre. An internal standard was employed to determine the absolute amounts of seven terpenoid compounds released from a P. hortorum leaf. The quantitative analysis was performed over two days, with extraction preformed for 20 min every 3 h. The amount of volatiles extracted varied with the time of day, with two maxima recorded at 14:00 (day 1) and 17:00 (day 2), corresponding to 236 and 277 ng of the seven terpenoids recorded, respectively. These results indicate that multiple HS-SPME in combination with an internal standard is a simple, quick, and quantitative technique for analysising BVOC emissions from a live plant sample.

Calibration↗

Solid-phase dynamic extraction for the enrichment of polar volatile organic compounds from water.

Headspace solid-phase dynamic extraction coupled to gas chromatography-mass spectrometry (HS-SPDE-GC/MS) was evaluated for the trace determination of polar volatile organic compounds (PVOC) from aqueous matrices. The target compounds included 3 ethers and 12 alcohols. Four SPDE needle coatings with different phase polarities and sorption properties (WAX, 1701, PDMS, PDMS/AC) were tested. The effects of extraction temperature, number of extraction cycles, and ionic strength on partitioning of the target compounds have been investigated in detail, including the determination of salting-out constants for the investigated compounds. Lowest method detection limits (MDLs) were obtained with the WAX and the PDMS/AC phase. The WAX phase showed MDLs for ethers in the range of 0.06 microg/L (MTBE) to 0.8 microg/L (1,4-dioxane) and for alcohols between 0.02 microg/L (3-methyl-1-pentanol) and 3.5 microg/L (1-propanol). The evaluated MDLs for ethers with the PDMS/AC were in the range 0.06 microg/L (MTBE) to 1.2 microg/L (1,4-dioxane) and for alcohols between 0.004 microg/L (1-hexanol) and 4.9 microg/L (ethanol). Using either of these two phases, SPDE provides comparable or better sensitivities for the investigated compounds than other enrichment techniques, high sample throughput because of full automation, and short extraction times as well as a high robustness of the extraction phase because of its protection inside the steel needle. SPDE applicability has been demonstrated for the determination of fusel oils in different alcoholic beverages.

Alcohols↗

Measurements of volatile organic compounds in the earth's atmosphere using proton-transfer-reaction mass spectrometry.

Proton-transfer-reaction mass spectrometry (PTR-MS) allows real-time measurements of volatile organic compounds (VOCs) in air with a high sensitivity and a fast time response. The use of PTR-MS in atmospheric research has expanded rapidly in recent years, and much has been learned about the instrument response and specificity of the technique in the analysis of air from different regions of the atmosphere. This paper aims to review the progress that has been made. The theory of operation is described and allows the response of the instrument to be described for different operating conditions. More accurate determinations of the instrument response involve calibrations using standard mixtures, and some results are shown. Much has been learned about the specificity of PTR-MS from inter-comparison studies as well the coupling of PTR-MS with a gas chromatographic interface. The literature on this issue is reviewed and summarized for many VOCs of atmospheric interest. Some highlights of airborne measurements by PTR-MS are presented, including the results obtained in fresh and aged forest-fire and urban plumes. Finally, the recent work that is focused on improving the technique is discussed.

Journal Article↗

Monitoring of indoor volatile organic compounds and polycyclic aromatic hydrocarbons arising from kerosene cooking fuel.

Air samples, representing indoor environments of a kitchen in which a kerosene stove was used were collected and analysed for volatile organic compounds (VOCs) viz., n-hexane, benzene, heptane, toluene, p- and o-xylene and n-decane using a cryogenic preconcentration system and a gas chromatograph with a flame-ionisation detector. Simultaneous outdoor samples were also collected to determine indoor to outdoor (I/O) ratios for each compound. Reversed phase high performance liquid chromatography (HPLC) with ultra violet absorption detection was optimised for separation and quantification of polycyclic aromatic hydrocarbons (PAHs) in air particulate matter. Concentration of total suspended particulate matter (TSPM), benzene soluble organics and the PAHs in air samples collected in indoor environment of some tenements at Trombay, Mumbai where kerosene is used as cooking fuel are discussed in relation to the concentration of the same in outdoor environment in vicinity of the tenement. VOCs and PAHs results from samples collected in kitchens in Trombay are discussed in relation to indoor air pollution.

Air Pollution, Indoor↗

Heterogeneous photocatalysis of aromatic and chlorinated volatile organic compounds (VOCs) for non-occupational indoor air application.

The current study evaluated the technical feasibility of applying TiO2 photocatalysis to the removal of low-ppb concentrations of volatile organic compounds (VOCs) commonly associated with non-occupational indoor air quality issues. A series of experiments was conducted to evaluate five parameters (relative humidity (RH), hydraulic diameter (HD), feeding type (FT) for VOCs, photocatalytic oxidation (PCO) reactor material (RM), and inlet port size (IPS) of PCO reactor) in relation to the PCO destruction efficiencies of the selected target VOCs. None of the target VOCs exhibited any significant dependence on the RH, which is inconsistent with a previous study where, under conditions of low humidity and a ppm toluene inlet level, a drop in the PCO efficiency was reported with a decreasing humidity. However, the other four parameters (HD, RM, FT, and IPS) were found to be important for better VOC removal efficiencies as regards the application of TiO2 photocatalytic technology for cleansing non-occupational indoor air. The PCO destruction of VOCs at concentrations associated with non-occupational indoor air quality issues was up to nearly 100%, and the CO generated during PCO was a negligible addition to indoor CO levels. Accordingly, a PCO reactor would appear to be an important tool in the effort to improve non-occupational indoor air quality.

Air Pollutants↗

Mapping and profile of emission sources for airborne volatile organic compounds from process regions at a petrochemical plant in Kaohsiung, Taiwan.

This work surveyed five process regions inside a petrochemical plant in Taiwan to characterize the profiles of airborne volatile organic compounds (VOCs) and locate emission sources. Samples, taken with canisters, were analyzed with gas chromatography-mass spectrometry according to the TO-14 method. Each region was deployed with 24 sampling sites, sampled twice, and 240 samples in total were measured during the survey period. All of the data were consolidated into a database on Excel to facilitate retrieval, statistical analysis, and presentation in the form of a table or graph, and, subsequently, the profile of VOCs was elucidated. Emission sources were located by mapping the concentration distribution of either an individual or a type of species in terms of contour maps on Surfer. Through the cross-analysis of data, the abundant VOCs included alkenes, dienes, alkanes, and aromatics. A total of 19 emission sources were located from these five regions. The sources for alkanes stood inside first, third aromatic, and fourth naphtha cracking regions, whereas the ones for alkenes were inside two naphtha cracking regions. The sources for dienes were found inside the third naphtha cracking region alone; in contrast, the sources for aromatics were universally traced except inside the third naphtha cracking region. The measured intensity for sources mostly ranged from 1000 to 7000 ppb.

Air Pollutants↗

Characterisation of volatile organic compounds in stemwood using solid-phase microextraction.

Solid-phase microextraction (SPME), hydrodistillation and dynamic headspace combined with GC and GC-MS were applied and compared for the analysis of volatile organic compounds (VOCs) from coniferous wood. The SPME conditions (type of fibre, size of wood sample, temperature and exposure time) were optimised, and more than 100 VOCs and semi-volatile compounds extracted and identified from the sapwood and heartwood of Norway spruce (Picea abies). The total number of mono- and sesquiterpenes eluted and identified was similar for the SPME and hydrodistillation methods, but more semi-volatile compounds were released by hydrodistillation. By applying dynamic headspace at room temperature, it was possible to analyse only the most volatile compounds. The qualitative composition of VOCs was similar in spruce sapwood and heartwood, although Z-beta-ocimene occurred only in sapwood while fenchol was present only in heartwood. SPME sampling coupled with GC, applied here to the analysis of VOCs released from stemwood of firs for the first time, is a convenient, sensitive, fast, solvent-free and simple method for the determination of wood volatiles. The technique requires much smaller sample amounts compared with hydrodistillation, and the total amount of VOCs extracted and identified is higher than that obtained by hydrodistillation or dynamic headspace. The relative ratios of the main mono- and sesquiterpenes and -terpenoids were similar using the SPME-GC and hydrodistillation methods.

Organic Chemicals↗

Extraction and biodegradation of a toxic volatile organic compound (1,2-dichloroethane) from waste-water in a membrane bioreactor.

An extractive membrane bioreactor has been used to treat a synthetic waste-water containing a toxic volatile organic compound, 1,2-dichloroethane (DCE). Biofilms growing on the surface of the membrane tubes biodegrade DCE while avoiding direct contact between the DCE and the aerating gas. This reduces air stripping by more than an order of magnitude (from 30-35% of the DCE entering the system to less than 1%) relative to conventional aerated bioreactors. Over 99% removal of DCE from a waste-water containing 1600 mg l-1 of DCE was achieved at waste-water residence times of 0.75 h. Biodegradation was verified as the removal mechanism through measurements of CO2 and chloride ion evolution in the bioreactor. No DCE was detected in the biomedium over the operating period. The diffusion-reaction phenomena occurring in the biofilm have been described by a mathematical model, which provides calculated solutions that support the experimental results by predicting that all DCE is biodegraded within the biofilm. Experimentally, however, the rate of DCE degradation in the biofilm was found to be independent of O2 concentration, while the model predictions point to O2 being limiting.

Biodegradation, Environmental↗

Distribution of volatile organic compounds in ambient air of Tehran.

Transportation sources have created a major hydrocarbon pollution problem in the ambient air of Tehran. The authors used a Carbotrap tube to determine volatile organic compounds in air. Such compounds can be desorbed thermally and analyzed with gas chromatography-mass spectrometry. Samples were obtained from 8 sites in Tehran at which traffic flow varied between 500 and 2,500 vehicles/hr. A total of 54 hydrocarbons were identified in the ambient air of Tehran, and the average measured concentrations of benzene, toluene, m- and p-xylene, ethyl benzene, and o-xylene were 127.6 microg/m3, 201.1 microg/m3, 110.7 microg/m3, 58.1 microg/m3, and 57.6 microg/m3, respectively (standard deviation = 3.8-51.7 microg/m3). Emissions of individual pollutants in south Tehran exceeded those in north Tehran, and these emissions were higher during the afternoon than during the morning. The geographical parameters and the photochemical reaction also played important roles in the pollution conditions.

Air Pollution↗