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PubMed2004

Emission modelling and validation of VOCs' source strengths in air-conditioned office premises.

An emission model for indoor volatile organic compounds (VOCs) based on mass balance considerations has been presented and validated under steady state conditions. Comparison were made for the measured and predicted concentrations of 37 selected VOCs and TVOC through a case intervention study on the filters of the ventilation system in a new commercial air-conditioned office building. The intervention involved replacing media filters with electronic and carbon filtration. TVOC and 37 compounds selected for their health and comfort impact, representation of major chemical classes that occur in indoor air and their utility as markers of pollution sources were studied. The concentration levels predicted by the model were compared with actual measurements. Twenty-five target compounds and the TVOC were adequately described by the model where the measured concentrations were in agreement with the predicted concentrations. Modeling of the remaining 12 compounds was found to be affected by the emission rates that were occupant related.

Air Conditioning↗
PubMed2005

Origin of 2-ethylhexanol as a VOC.

2-Ethylhexanol has been identified as a volatile organic compound (VOC) that contributes to the deterioration of indoor air quality. Plasticizers are common components of dust and building materials and are shown to be degraded by a variety of bacteria and fungi to produce 2-ethylhexanol and other metabolites. Of these, the 2-ethylhexanol has significant volatility and was observed in appreciable quantities. The degree to which 2-ethylhexanol is observed as a VOC in air samples would be limited by the fact that many of the microorganisms that are capable of producing this compound are also able to oxidize it to 2-ethylhexanoic acid, which is much less volatile. It is argued that an abiotic degradation mechanism of plasticizers that results in the generation of 2-ethylhexanol is unlikely and, if this did occur, other metabolites should have been observed. Thus, the microbial degradation of plasticizers is the most likely source of 2-ethylhexanol in indoor air.

Air Microbiology↗
PubMed2005

Combustion of chlorinated volatile organic compounds (VOCs) using bimetallic chromium-copper supported on modified H-ZSM-5 catalyst.

The paper reports on the performance of chromium or/and copper supported on H-ZSM-5(Si/Al = 240) modified with silicon tetrachloride (Cr1.5/SiCl4-Z, Cu1.5/SiCl4-Z and Cr1.0Cu0.5/SiCl4-Z) as catalysts in the combustion of chlorinated VOCs (Cl-VOCs). A reactor operated at a gas hourly space velocity (GHSV) of 32,000 h(-1), a temperature between 100 and 500 degrees C with 2500 ppm of dichloromethane (DCM), trichloromethane (TCM) and trichloroethylene (TCE) is used for activity studies. The deactivation study is conducted at a GHSV of 3800 h(-1), at 400 degrees C for up to 12 h with a feed concentration of 35,000 ppm. Treatment with silicon tetrachloride improves the chemical resistance of H-ZSM-5 against hydrogen chloride. TCM is more reactive compared to DCM but it produces more by-products due to its high chlorine content. The stabilization of TCE is attributed to resonance effects. Water vapor increases the carbon dioxide yield through its role as hydrolysis agent forming reactive carbocations and acting as hydrogen-supplying agent to suppress chlorine-transfer reactions. The deactivation of Cr1.0Cu0.5/SiCl4-Z is mainly due to the chlorination of its metal species, especially with higher Cl/H feed. Coking is limited, particularly with DCM and TCM. In accordance with the Mars-van Krevelen model, the weakening of overall metal reducibility due to chlorination leads to a loss of catalytic activity.

Air Pollutants, Occupational↗
PubMed2006

Spatial and temporal trends of volatile organic compounds (VOC) in a rural area of northern Spain.

Ambient concentrations of volatile organic compounds (VOCs) were measured at 40 rural sampling points in Navarre (northern Spain). Air samples were collected by means of sorbent passive sampling and analyzed by thermal desorption (TD) and gas chromatography/mass-selective detector (GC/MSD). A total of 140 VOCs were identified during the study, which was carried out between May to October 2004 for a total of a 10 biweekly sampling campaigns. Concentrations of benzene, toluene, ethylbenzene, m/p-xylenes, o-xylene (BTEX) and 1,3,5-trimethylbenzene were determined in order to investigate their temporal and spatial distributions. Geostatistical analysis pointed to traffic as the main emission source of these compounds. Supporting this idea, BTEX and nitrogen oxides concentrations were found to be highly significantly correlated (r = 0.495, P = 0.001), whereas a strong negative correlation between BTEX and ozone was also observed (r = -0.355, P = 0.025). The concentrations for the BTEX group were similar to the values that have been previously reported for other rural areas.

Air↗
PubMed2002

Identification of atmospheric volatile organic compounds (VOCs), polycyclic aromatic hydrocarbons (PAHs) and carbonyl compounds in Hong Kong.

Volatile organic compounds (VOCs), polycyclic aromatic hydrocarbons (PAHs) and carbonyl compounds are the major organic pollutants in the atmosphere. Emissions from motor vehicles have been one of the primary pollution sources in the metropolitan area of Hong Kong. A 12-month monitoring program for VOCs, PAHs and carbonyl compounds was performed at a roadside urban station at Hong Kong Polytechnic University (HKPU) in order to determine the correlations of each selected pollutant. The monitoring program ran from 16 April 1999 to 10 April 2000 for a period of 1 year, and a 2-week winter intensive sampling was carried out during January 2000. Traditionally, emission sources are identified from organic compounds in air particulates. Since many of the gaseous and particulate phases of organic compounds are from the same sources, correlations between the major exhausts are to be expected. Therefore, it would be more effective to apportion the sources using the combined gaseous and particulate phases of organic compounds. Correlations of selected pollutants within two other toxic air pollutants (TAPs) monitoring stations in Tsuen Wan (TW) and Central/Western (CW) were analyzed. Good correlations were found between pollutants that came from vehicle exhaust, especially in intensive sampling periods at HKPU roadside station. This was because the washing out effect for particulates during rainy days and photochemical degradation during high solar radiation were minimized in wintertime.

Air Pollutants↗
PubMed2001

Analysis of a GC/MS thermal desorption system with simultaneous sniffing for determination of off-odor compounds and VOCs in fumes formed during extrusion coating of low-density polyethylene.

A thermal desorption equipment introducing volatile organic compounds (VOCs) into the gas chromatographic/ mass spectrometric system (GC/MS) with simultaneous sniffing (SNIFF) is a suitable method for identifying the volatile organic off-odor compounds formed during the extrusion coating process of low-density polyethylene. Fumes emitted during the extrusion coating process of three different plastic materials were collected at two different temperatures (285 and 315 degrees C) from an outgoing pipe and near an extruder. The VOCs of fumes were analyzed by drawing a known volume of air through the adsorbent tube filled with a solid adsorbent (Tenax GR). The air samples were analyzed by using a special thermal desorption device and GC/MS determination. The simultaneous sniffing was carried out to detect off-odors and to assist in the identification of those compounds that contribute to tainting and smelling. The amounts of off-odor carbonyl compounds and the total content of the volatile organic compounds were determined. The most odorous compounds were identified as carboxylic acids while the majority of the volatile compounds were hydrocarbons. The detection and quantification of carboxylic acids were based on the characteristic ions of their mass spectra. The higher the extrusion temperature the more odors were detected. An important observation was that the total concentration of volatiles was dependent not only on the extrusion temperature but also on the plastic material.

Journal Article↗
PubMed2001

Purge-and-membrane mass spectrometry, a screening method for analysis of VOCs from soil samples.

Purge-and-membrane mass spectrometry (PAM-MS) is a combination of dynamic headspace sampling and membrane extraction. A new and simple purge-and-membrane sampler is introduced and its basic testing results for the analysis of VOCs in soil samples are reported. Soil moisture had no effect on desorption times in the case of sand, but the desorption times increased when the content of organic matter in the soil sample (garden soil) increased. The longest desorption times were measured with dry garden soil samples. For both types of samples, minor differences in desorption peak areas were observed between 10 and 20% moisture. Detection limits of the VOCs varied in the range 2-150 microg/kg, depending on the soil type. Good linearity (correlation coefficient > 0.990) was observed in the range 0.5-50 mg/kg. Aging of the spiked soil samples had only a slight effect on desorption peak areas for samples stored at 5 degrees C up to two weeks, but after six months of storing, differences were observed between dry sand and moistened garden soil. In both cases, peak areas were diminished. On average, 46% of compounds could be desorbed from the aged sand and 86% from the aged garden soil. The modified vapor fortification method was used in preparing standard soil samples, which were analyzed by static headspace gas chromatography (HSGC) and PAM-MS. Some authentic soil samples were also analyzed using both of these techniques. Many of the vapor fortification samples and the authentic samples were also analyzed in another laboratory by HSGC. The agreement between the methods and the laboratories was generally good.

Environmental Monitoring↗
PubMed2001

Mass transfer in VOC adsorption on zeolite: experimental and theoretical breakthrough curves.

From experimental results of adsorption of volatile organic compounds (VOCs) on zeolite, we propose simulations of the breakthrough curves based on the Linear Driving Force model. Experiments were run on fixed beds of hydrophobic commercial zeolites. Pollutants chosen are from several chemical classes with different polarities. A good agreement between experimental and numerical results is found when an adjustable value of the internal mass-transfer coefficient is used. A constant value of effective diffusivity is found independent of the nature and the amount of VOCs adsorbed. A relation linking intrapellet mass-transfer coefficient and equilibrium constant is proposed, including the average effective diffusivity, to make predictions of breakthrough curves for any kind of volatile organic pollutant in gaseous effluents.

Adsorption↗
PubMed2004

Novel aqueous foams for suppressing VOC emission.

Reducing volatile organic compound (VOC) emissions from crude oil/gasoline distribution and storage facilities is important in controlling environmental pollution and enhancing workplace safety. Stable aqueous foam formulations are developed to provide a mass transfer barrier to the emission of VOCs during loading of gasoline. Experiments are carried out in a bench-scale foam cell using liquid hexane as oil. The foam columns of 32 cm in height were able to suppress the plateau concentration of hexane vapors in the effluent by 87% under experimental conditions tested. Vapor suppression increased with foam height but was almost insensitive to liquid viscosity. These experiments are then upscaled from bench-scale to a vessel having an exposed surface area of roughly 2 orders of magnitude higher. Gasoline is used as oil in the upscaled experiments, and the concentrations of volatile hydrocarbons in the effluent are measured during oil loading. A 40-cm-thick foam column is found to reduce the emissions by 96% for foams prepared with deionized water and by 93.8% for foams prepared with 3.5 wt % NaCl brine for 10 h of oil loading.

Air Pollutants↗
PubMed2004

Framework for evaluating the "greenness" of chemical processes: case studies for a novel VOC recovery technology.

A system of metrics is proposed for a rough-guide evaluation of the greenness of new and existing chemical technologies as well as for the analysis of flow sheets of new processes. The proposed methodology is based on a hierarchical approach. The main feature of the proposed system is the reflection of the stakeholder relevance of various aspects of green chemistry at different levels of the hierarchy and the corresponding system boundaries. Therefore, the developed methodology provides a basis for the multiobjective comparison of alternative technologies in terms of their greenness. A novel technology for recovery of volatile organic chemicals (VOCs) using monolithic adsorbents has been evaluated in terms of its environmental efficiency using a small set of indicators assembled into a hierarchical metric. A comparison between incineration and recovery of VOCs via adsorption has been performed using the proposed methodology. The comparison highlights considerable environmental advantages of the recovery technology. Flow sheet analysis points out which stages of the adsorption process could be further improved. Indicators have been evaluated within defined system boundaries.

Adsorption↗
PubMed2005

Combustion of chlorinated VOC on nanostructured chromia aerogel as catalyst and catalyst support.

The chromia-based catalysts have been reported to combine the high activity and resistance to deactivation in oxidative removal of chlorinated VOC. However, their activity is limited by the low amount of chromia that can be deposited on supports maintaining the optimal state of surface species and high surface area. The pure nanostructured chromia was used as a catalytically active support for noble metals and transition-metal oxide oxidation catalysts. High efficiency of Pt-promoted CrOOH aerogel with surface area of 500 m2*g(-1) was demonstrated in full combustion of 1,2-dichloroethane (DCE) and chlorobenzene (CB). At gas hour space velocity (GHSV) of 46 000 h(-1), the total conversion to CO2/H2O/HCl was achieved at 330 degrees C (DCE) and 380 degrees C (CB). The combustion rate constants measured at standard conditions with 0.5% Pt/CrOOH catalyst were 1 or 2 orders of magnitude higher than measured with 15%Cr2O3/Al2O3 or 0.5%Pt/Al2O3, respectively. The effects of Pt, Au, Mn, and Ce additives on the performance of CrOOH aerogel in combustion of chlorinated VOC were analyzed related to the materials structure.

Aluminum Oxide↗
PubMed2000

Introduction of a sink-diffusion model to describe the interaction between volatile organic compounds (VOCs) and material surfaces.

A sink-diffusion model to describe the interaction between material surfaces and volatile organic compounds (VOCs) in indoor air has been introduced. The model is based on adsorption/desorption on the material surfaces and diffusion into the materials. Test chamber experiments with exposure of nylon carpet and polyvinyl chloride (PVC) covering against alpha-pinene and toluene were used to validate the model and to make comparisons with a sink model based on the Langmuir adsorption isotherm. The results showed that the sink-diffusion model gave a better description of the desorption curve than the Langmuir model. The model predictions improved with increasing sorption effect. The Langmuir model gave good predictions of relative weak sorption effects, whereas the sink-diffusion model improved the predictions for stronger sorption effects. In this case, nylon carpet showed substantial stronger sorption than PVC covering and alpha-pinene showed stronger sorption than toluene. Controlled field experiments with combinations of building materials and a mixture of VOCs, encountered in real indoor environments, are needed to further validate the sink-diffusion model.

Adsorption↗
PubMed2001

A coupled airflow and source/sink model for simulating indoor VOC exposures.

In this paper, a numerical model is presented to study the indoor air quality (IAQ) in a room with different emission sources, sinks, and ventilation methods. A computer program, ACCESS-IAQ, is developed to simulate the airflow pattern, the time history of the contaminant concentrations in the occupied zone, and the inhalation exposures. The program developed may be useful for IAQ professional to design healthy and comfortable indoor environments. A numerical study has been carried out to predict the effectiveness of a displacement ventilation and a mixing ventilation on volatile organic compound (VOC) removal in a model office. Results from the numerical predictions show that when a "wet" emission source (a freshly painted wood stain) is distributed uniformly across the floor area with sinks (gypsum board) from the four vertical walls, displacement ventilation has consistently lower exposure at the breathing level of the occupant in the room. Such an effect is mainly due to the higher ventilation efficiency of displacement ventilation compared to the mixing ventilation. The simulation results also show that the walls adsorb significant amounts of VOCs during the first hour and act as secondary sources thereafter.

Absorption↗
PubMed2003

A two-column method for long-term monitoring of non-methane hydrocarbons (NMHCs) and oxygenated volatile organic compounds (o-VOCs).

A method has been developed for concurrent analysis of C2-C7 hydrocarbons and C2-C5 oxygenated volatile organic compounds (o-VOCs) including alcohols, aldehydes, ketones and ethers. A multi-bed, Peltier-cooled adsorbent trap, consisting of Carboxen 1000 and Carbopack B, was used to acquire one sample per hour. Upon injection the sample was split in an approximately 50:50 ratio between a 50 m aluminium oxide (Al2O3) porous layer open tubular (PLOT) column and a 10 m LOWOX column. Eluents from each column were then analysed using flame ionisation detection (FID). Regular calibration of the system was performed using a standard cylinder mixture at the parts per billion by volume (ppbV) level for non-methane hydrocarbons (NMHCs) and a permeation tube method for the oxygenated species. The system is fully automated with NMHC detection limits between 1 and 10 parts per trillion by volume (pptV) and o-VOC detection limits between 10 and 40 pptV.

Absorption↗
PubMed2002

Ambient level volatile organic compound (VOC) monitoring using solid adsorbents--recent US EPA studies.

Ambient air spiked with 1-10 ppbv concentrations of 41 toxic volatile organic compounds (VOCs) listed in US Environmental Protection Agency (EPA) Compendium Method TO-14A was monitored using solid sorbents for sample collection and a Varian Saturn 2000 ion trap mass spectrometer for analysis. The adsorbent was a combination of graphitic carbon and a Carboxen-type carbon molecular sieve. The method detection limits (MDLs) for 11 samples were typically 0.5 parts per billion by volume (ppbv) and lower except for bromomethane and chloromethane, both of which exhibited breakthrough. Thirty-day sample storage on the sorbents resulted in less than a 20% change for most compounds, and water management was required for humid samples to avoid major anomalous decreases in response during analyses. The adsorbent-based system, a system using canister-based monitoring, and a semi-continuous automated GC/MS (autoGC) monitoring system with a Tenax GR/Carbotrap B/Carbosieve S-III adsorbent preconcentrator were compared using spiked ozone concentrations as a variable. In this comparison, the target compounds included a number of n-aldehydes as well as those listed in TO-14A. The effects of ozone on the TO-14A compounds were relatively minor with the exception of negative artifacts noted for styrene and 1,1,2,2-tetrachloroethane. However, a small, systematic decrease in response was evident for a number of aromatic VOCs and 1,1,2,2-tetrachloroethane when ozone was increased from 50 to 300 ppbv. Method averages for multiple runs under the same conditions were typically within +0.25 ppbv of their mean for most compounds. For n-aldehydes, strong positive artifacts using the autoGC preconcentrator and strong negative artifacts for the canister-based and carbon sorbent approaches caused major disagreement among methods. These artifacts were mostly eliminated by using MnO2 ozone scrubbers, although loss of the n-aldehydes for all methods occurred after a single sample collection of 1 h duration, apparently due to the interaction of the n-aldehydes and products of the O3, MnO2 reaction on the scrubber.

Adsorption↗
PubMed2005

24 h diffusive sampling of toxic VOCs in air onto Carbopack X solid adsorbent followed by thermal desorption/GC/MS analysis-laboratory studies.

Diffusive sampling of a mixture of 42 volatile organic compounds (VOCs) in humidified, purified air onto the solid adsorbent Carbopack X was evaluated under controlled laboratory conditions. The evaluation included variations in sample air temperature, relative humidity and ozone concentration. Linearity of samples with loading was examined both for a constant concentration with time varied up to 24 h and for different concentrations over 24 h. Reverse diffusion and its increase with accumulation of sample were determined for all compounds. Tubes were examined for blank levels, change of blanks with storage time, and variability of blanks. Method detection limits were determined based on seven replicate samples. Based on this evaluation, 27 VOCs were selected for quantitative monitoring in the concentration range from approximately 0.1 to 4 ppbv. Comparison results of active and diffusive samples taken over 24 h and under the same simulated ambient conditions at a constant 2 ppbv were interpreted to estimate the effective diffusive sampling rates (ml min(-1)) and their uncertainties and to calculate the corresponding diffusive uptake rates (ng ppmv(-1) min(-1)).

Adsorption↗
PubMed2006

Simultaneous measurement of ventilation using tracer gas techniques and VOC concentrations in homes, garages and vehicles.

Air exchange rates and interzonal flows are critical ventilation parameters that affect thermal comfort, air migration, and contaminant exposure in buildings and other environments. This paper presents the development of an updated approach to measure these parameters using perfluorocarbon tracer (PFT) gases, the constant injection rate method, and adsorbent-based sampling of PFT concentrations. The design of miniature PFT sources using hexafluorotoluene and octafluorobenzene tracers, and the development and validation of an analytical GC/MS method for these tracers are described. We show that simultaneous deployment of sources and passive samplers, which is logistically advantageous, will not cause significant errors over multiday measurement periods in building, or over shorter periods in rapidly ventilated spaces like vehicle cabins. Measurement of the tracers over periods of hours to a week may be accomplished using active or passive samplers, and low method detection limits (<0.025 microg m(-3)) and high precisions (<10%) are easily achieved. The method obtains the effective air exchange rate (AER), which is relevant to characterizing long-term exposures, especially when ventilation rates are time-varying. In addition to measuring the PFT tracers, concentrations of other volatile organic compounds (VOCs) are simultaneously determined. Pilot tests in three environments (residence, garage, and vehicle cabin) demonstrate the utility of the method. The 4 day effective AER in the house was 0.20 h(-1), the 4 day AER in the attached garage was 0.80 h(-1), and 16% of the ventilation in the house migrated from the garage. The 5 h AER in a vehicle traveling at 100 km h(-1) under a low-to-medium vent condition was 92 h(-1), and this represents the highest speed test found in the literature. The method is attractive in that it simultaneously determines AERs, interzonal flows, and VOC concentrations over long and representative test periods. These measurements are practical, cost-effective, and helpful in indoor air quality and other investigations.

Air Movements↗
PubMed2000

Modeling effects of moisture content and advection on odor causing VOCs volatilization from stored swine manure.

Two models for evaluating the contents and advection of manure moisture on odor causing volatile organic compounds (VOC-odor) volatilization from stored swine manure were studied for their ability to predict the volatilization rate (indoor air concentration) and cumulative exposure dose: a MJ-I model and a MJ-II model. Both models simulating depletion of source contaminant via volatilization and degradation based on an analytical model adapted from the behavior assessment model of Jury et al. In the MJ-I model, manure moisture movement was negligible, whereas in the MJ-II model, time-dependent indoor air concentrations was a function of constant manure moisture contents and steady-state moisture advection. Predicted indoor air concentrations and inhaled doses for the study VOC-odors of p-cresol, toluene, and p-xylene varied by up to two to three orders of magnitude depending on the manure moisture conditions. The sensitivity analysis of both models suggests that when manure moisture movement exists, simply MJ-I model is inherently not sufficient to represent a more generally volatilization process, which can even become stringent as moisture content increases. The conclusion illustrates how one needs to include a wide variety of manure moisture values in order to fully assess the complex volatilization mechanisms that are present in a real situation.

Air Pollution, Indoor↗