Interlaboratory Study of a Test Method Measuring Total Volatile Organic Compound Content of Consumer Products

Abstract

Consumer products are potentially significant sources of volatile organic compounds (VOCs), which are precursors to the formation of ozone in photochemical smog. To address the problem of ozone formation in ambient air, the U.S. Environmental Protection Agency (EPA) has been involved in the development of test methods for measuring the VOC content of consumer products. This paper describes results of an interlaboratory study to estimate the repeatability (precision of analyses performed by a single laboratory) and reproducibility (precision of analyses performed by different laboratories) of the consumer products’ VOC measurement method based on EPA Method 24 (for VOCs in surface coatings).

The mean method repeatability was 2.7 wt % VOC, and the mean method reproducibility was 4.8 wt % VOC. Method repeatability ranged from 0.2 to 4.4 wt % VOC, and reproducibility ranged from 0.6 to 11.9 weight percent VOC. The precision of the VOC method for consumer

products is similar to the precision of EPA Method 24 for surface coatings.     

C1–C8 volatile organic compounds in the atmosphere of Hong Kong: Overview of atmospheric processing and source apportionment

We present measurements of C₁–C₈ volatile organic compounds (VOCs) at four sites ranging from urban to rural areas in Hong Kong from September 2002 to August 2003. A total of 248 ambient VOC samples were collected. As expected, the urban and sub-urban sites generally gave relatively high VOC levels. In contrast, the average VOC levels were the lowest in the rural area. In general, higher mixing ratios were observed during winter/spring and lower levels during summer/fall because of seasonal variations of meteorological conditions. A variation of the air mass composition from urban to rural sites was observed. High ratios of ethyne/CO (5.6 pptv/ppbv) and propane/ethane (0.50 pptv/pptv) at the rural site suggested that the air masses over the territory were relatively fresh as compared to other remote regions. The principal component analysis (PCA) with absolute principal component scores (APCS) technique was applied to the VOC data in order to identify and quantify pollution sources at different sites. These results indicated that vehicular emissions made a significant contribution to ambient non-methane VOCs (NMVOCs) levels in urban areas (65±36%) and in sub-urban areas (50±28% and 53±41%). Other sources such as petrol evaporation, industrial emissions and solvent usage also played important roles in the VOC emissions. At the rural site, almost half of the measured total NMVOCs were due to combustion sources (vehicular and/or biomass/biofuel burning). Petrol evaporation, solvent usage, industrial and biogenic emissions also contributed to the atmospheric NMVOCs. The source apportionment results revealed a strong impact of anthropogenic VOCs to the atmosphere of Hong Kong in both urban/sub-urban and rural areas.     

Application of passive sorbent tube and canister samplers for volatile organic compounds at refinery fenceline locations in Whiting,Indiana

Select volatile organic compounds (VOCs) in ambient air were measured at four fenceline sites at a petroleum refinery in Whiting, IN, using modified EPA Method 325 A/B with passive tubes and EPA Compendium Method TO-15 with canister samplers. One-week, time-integrated samplers were deployed for 8 weeks with tubes and canister samplers deployed in duplicate. Good precision was obtained from the duplicate tubes (<7%) and duplicate canisters (≤10%) for BTEX, perchloroethylene, and styrene. The tubes yielded statistically significantly higher concentrations than canisters for benzene, toluene, ethylbenzene, and m,p-xylene. However, all differences were estimated to be <0.1 ppbv. No concentration differences among the four Whiting sites were found for any of the VOCs.

Implications: Recently enacted EPA Methods 325A/B use passive-diffusive tube samplers to measure benzene at refinery fenceline locations. This pilot study presents VOC data applying a modified version of EPA Method 325 A/B and its comparison to EPA Compendium Method TO-15 canister samplers at four refinery fenceline sites. The findings from this study provide additional confidence in application of the tube method at refineries to ascertain VOC source influence since tube and canister samplers were comparable and good precision was obtained from duplicate sampling for both methods. No overall difference in these reported VOC concentrations was found between Whiting sites for tubes or canisters.     

Vertical and diurnal characterization of volatile organic compounds in ambient air in urban areas

More than half of the world's population lives in cities, and their populations are rapidly increasing. Information on vertical and diurnal characterizations of volatile organic compounds (VOCs) in urban areas with heavy ambient air pollution can help further understand the impact of ambient VOCs on the local urban environment. This study characterized vertical and diurnal variations in VOCs at 2, 13, 32, 58, and 111 m during four daily time periods (7:00 to 9:00 a.m., 12:00 to 2:00 p.m., 5:00 to 7:00 p.m., and 11:00 p.m. to 1:00 a.m.) at the upwind of a high-rise building in downtown, Kaohsiung City, Taiwan. The study used gas chromatography-mass spectrometry to analyze air samples collected by silica-coated canisters. The vertical distributions of ambient VOC profiles showed that VOCs tended to decrease at greater heights. However, VOC levels were found to be higher at 13 m than at ground level at midnight from 11:00 p.m. to 1:00 a.m. and higher at 32 than 13 m between 7:00 and 9:00 a.m. These observations suggest that vertical dispersion and dilution of airborne pollutants could be jointly affected by local meteorological conditions and the proximity of pollution sources. The maximum concentration of VOCs was recorded during the morning rush hours from 7:00 to 9:00 a.m., followed by rush hours from 5:00 to 7:00 p.m., hours from 12:00 to 2:00 p.m., and hours from 11:00 p.m. to 1:00 a.m., indicating that the most VOC compounds in urban air originate from traffic and transportation emissions. The benzene-toluene-ethyl benzene-xylene (BTEX) source analysis shows that BTEX at all heights were mostly associated with vehicle transportation activities on the ground.     

Comparison of receptor models for source apportionment of volatile organic compounds in Beijing, China

Identifying the sources of volatile organic compounds (VOCs) is key to reducing ground-level ozone and secondary organic aerosols (SOAs). Several receptor models have been developed to apportion sources, but an intercomparison of these models had not been performed for VOCs in China. In the present study, we compared VOC sources based on chemical mass balance (CMB), UNMIX, and positive matrix factorization (PMF) models. Gasoline-related sources, petrochemical production, and liquefied petroleum gas (LPG) were identified by all three models as the major contributors, with UNMIX and PMF producing quite similar results. The contributions of gasoline-related sources and LPG estimated by the CMB model were higher, and petrochemical emissions were lower than in the UNMIX and PMF results, possibly because the VOC profiles used in the CMB model were for fresh emissions and the profiles extracted from ambient measurements by the two-factor analysis models were "aged".     

Qualitative analysis of volatile organic compounds on biochar

Qualitative identification of sorbed volatile organic compounds (VOCs) on biochar was conducted by headspace thermal desorption coupled to capillary gas chromatographic-mass spectrometry. VOCs may have a mechanistic role influencing plant and microbial responses to biochar amendments, since VOCs can directly inhibit/stimulate microbial and plant processes. Over 70 biochars encompassing a variety of parent feedstocks and manufacturing processes were evaluated and were observed to possess diverse sorbed VOC composition. There were over 140 individual chemical compounds thermally desorbed from some biochars, with hydrothermal carbonization (HTC) and fast pyrolysis biochars typically possessing the greatest number of sorbed volatiles. In contrast, gasification, thermal or chemical processed biochars, soil kiln mound, and open pit biochars possessed low to non-detectable levels of VOCs. Slow pyrolysis biochars were highly variable in terms of their sorbed VOC content. There were no clear feedstock dependencies to the sorbed VOC composition, suggesting a stronger linkage with biochar production conditions coupled to post-production handling and processing. Lower pyrolytic temperatures (?350 °C) produced biochars with sorbed VOCs consisting of short carbon chain aldehydes, furans and ketones; elevated temperature biochars (>350 °C) typically were dominated by sorbed aromatic compounds and longer carbon chain hydrocarbons. The presence of oxygen during pyrolysis also reduced sorbed VOCs. These compositional results suggest that sorbed VOCs are highly variable and that their chemical dissimilarity could play a role in the wide variety of plant and soil microbial responses to biochar soil amendment noted in the literature. This variability in VOC composition may argue for VOC characterization before land application to predict possible agroecosystem effects.     

Assessment of spatial variation of ambient volatile organic compound levels at a power station in Kuwait

Twenty-four-hour integrated ambient air samples were collected in canisters at 10 locations within Kuwait’s major power station: Doha West Power Station to assess the spatial distribution of volatile organic compounds (VOCs) within the perimeter of the station. A total of 30 samples, i.e., three samples per location, were collected during February and March. The samples were analyzed using a gas chromatography with flame ionization detection (GC-FID) system and following the U.S. EPA Method TO-14A with modification. The results reflected the emission activities on the site and the meteorological conditions during sampling. Generally speaking, there was a negative correlation between the ambient temperature and the VOC concentrations, which indicates the sources were local. The halogenated compounds formed the highest proportion (i.e. 50–75 %) of the total VOC concentrations at the ten locations. 1,2,4-Trichlorobenzene and Vinyl Chloride concentrations were the highest amongst the other halogenated compounds. The aromatic compounds formed the least proportion (i.e. 1–4%) of the total VOC levels at all locations with Toluene having the highest concentrations amongst the aromatic compounds at seven locations. Propene, which is a major constituent of the fuel used, was the highest amongst the aliphatic compounds. The findings of this study and other relevant work suggests the measured VOC levels were the highest over the year, nevertheless, further work is required to assess the precisely temporal variation of VOC due to change in meteorological conditions and the emission rates.

Implications: Assessment of VOC concentrations around a power plant in Kuwait during the peak season showed halogenated compounds to be the dominant group. The calculated indoor concentrations were lower than those reported in a residential area about 12 km away.     

Characterization of ambient volatile organic compounds at a landfill site in Guangzhou,South China

Ambient air monitoring was conducted at Datianshan landfill, Guangzhou, South China in 1998 to investigate the seasonal and horizontal variations of trace volatile organic compounds (VOCs). Twelve sampling points over the Datianshan landfill were selected and samples were collected simultaneously using Carbontrap(TM) adsorption tubes. Thirty eight VOCs were detected in the winter, whereas 60 were detected in the summer. The VOC levels measured in summer were alkanes, 0.5-6.5 microg/m(3); aromatics, 2.3-1667 microg/m(3); chlorinated species, 0.2-31 microg/m(3); terpines, 0.1-34 microg/m(3); carbonyl species, 0.3-5.6 microg/m(3) and naphthalene and its derivatives, 0.4-27 microg/m(3). Compared to the summer samples the VOC levels in winter were much lower (mostly 1-2 orders of magnitude lower). The aromatics are dominant VOCs in landfill air both in winter and summer. High levels of alkylbenzene and terpines such as methyl-isopropylbenzene (max 1667 microg/m(3)) and limonene (max 162 microg/m(3)) cause undesirable odor. The similar correlation coefficients of BTEX in summer and winter suggest VOCs emissions were from landfill site sources. The variation of BTEX ratio at landfill site is different from that in the urban area of Guangzhou. It shows that the ambient VOCs at landfill site were different from the urban areas.     

Using a source–receptor approach to characterize the volatile organic compounds from control device exhaust in a science park

The science parks have helped shape Taiwan as a high-tech island with a good reputation worldwide. But some complaints on air pollution from the science parks have recently risen. To better understand the environmental effects of volatile organic compounds (VOCs) emitted from various high-tech factories in a science park, this study uses a source–receptor approach to characterize the environmental effects of VOCs from control device exhaust in Taichung Science Park. The chemical mass balance model (CMB8.2) of field measurements of 30 stacks and ambient air at nine sites was used to identify the source and relative contribution of ambient VOCs. The exhaust gas of various pollution control devices was also sampled by drawing a stream of the gases from the exhaust duct at its sampling port. The VOC source profile of each control device exhaust was determined using a database of noncharacteristic compounds. Monthly ambient concentrations of 167 VOCs were divided into monsoon datasets to investigate the effect of monsoon conditions on the emission of VOCs in the science park. This study also suggests a method for determining the optimum source profile in source–receptor modeling, and identifies and analyzes the sources of ambient VOCs at nine sites during southwest and northeast monsoons. Results show a direct relationship between the relative contribution of each source and its control device efficiency. The proposed source–receptor approach can characterize the environmental effect of air pollutants from various factories and successfully assess the efficiency of various control devices.     

Effect of outside air ventilation rate on volatile organic compound concentrations in a call center

A study of the relationship between outside air ventilation rate and concentrations of volatile organic compounds (VOCs) generated indoors was conducted in a call center office building. The building, with two floors and a total floor area of 4600 m², is located in the San Francisco Bay Area, CA. Ventilation rates were manipulated with the building's four air handling units (AHUs). VOC and CO₂ concentrations in the AHU returns were measured on 7 days during a 13-week period. VOC emission factors were determined for individual zones on days when they were operating at near steady-state conditions. The emission factor data were subjected to principal component (PC) analysis to identify groups of co-varying compounds. Potential sources of the PC vectors were ascribed based on information from the literature. The per occupant CO₂ generation rates were 0.0068–0.0092 l s⁻¹. The per occupant isoprene generation rates of 0.2–0.3 mg h⁻¹ were consistent with the value predicted by mass balance from breath concentration and exhalation rate. The relationships between indoor minus outdoor VOC concentrations and ventilation rate were qualitatively examined for eight VOCs. Of these, acetaldehyde and hexanal, which likely were associated with material sources, and decamethylcyclopentasiloxane, associated with personal care products, exhibited general trends of higher concentrations at lower ventilation rates. For other compounds, a clear inverse relationship between VOC concentrations and ventilation was not observed. The net concentration of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate isomers, examples of low-volatility compounds, changed very little with ventilation likely due to sorption and re-emission effects. These results illustrate that the efficacy of ventilation for controlling VOC concentrations can vary considerably depending upon the operation of the building, the pollutant sources and the physical and chemical processes affecting the pollutants. Thus, source control measures, in addition to adequate ventilation, are required to limit concentrations of VOCs in office buildings.     

Validation of in-situ measurements of volatile organic compounds through flask sampling and gas chromatography/mass spectrometry analysis

Continuous monitoring of ambient non-methane hydrocarbons (NMHCs) by automated gas chromatographs equipped with flame ionization detection (termed in-situ GC/FID) with hourly data resolution was instated in ozone non-attainment areas throughout Taiwan. Performance of these on-site in-situ GCs was validated by manual flask sampling, as well as by in-lab gas chromatography/mass spectrometry (GC/MS) analysis. More than 50 VOCs from C₂ to C₁₁ were analyzed by both methods. Ninety flask samples were collected in series near an in-situ GC monitoring station in order to closely compare with the in-situ measurements. Both time-series and scatter plots from the two methods are displayed and discussed. It was found that over-simplified, un-humidified single-point calibration leading to surface loss was responsible for the bias in the in-situ method, resulting in greater error in accuracy as VOC volatility decreased. Although this over-estimate of the concentrations was found across all target VOCs, both methods were able to consistently capture the variability of ambient VOCs, with R² values greater than 0.9 for most of the major VOCs.     

Determination of volatile organic profiles and photochemical potentials from chemical manufacture process vents

The main objective of this study was to monitor the volatile organic compounds (VOCs) in the stack gas released from organic chemical industrial plants to determine emission factors. Samples from 52 stacks, with or without air pollution control devices (APCDs), from seven industrial processes were taken and VOCs measured using U.S. Environmental Protection Agency (EPA) Method 18. These 7 processes, including 26 plants, were the manufacturers of acrylonitrile-butadiene-styrene (ABS), polyvinyl chloride (PVC), polystyrene (PS), acrylic resin (ACR), vinyl chloride (VC), para-terephthalic acid (PTA), and synthetic fiber (SYF). The results clearly indicate significant variations of emission factors among the various industrial processes, particularly emission factors for those without APCDs. As expected, those with APCDs yield much less emission factors. Regardless of those with or without APCDs, the order of manufacturing processes with regard to VOC emission factors is SYF > ABS > PS >ACR > PTA > PVC > VC. The emission factors for some processes also differ from those in EPA-42 data file. The VOC profiles further indicate that some VOCs are not listed in the U.S. VOC/Particulate Matter Speciation Data System (SPECIATE). The potential O3 formation is determined from the total amount of VOC emitted for each of seven processes. The resultant O3 yield varied from 0.22 (ACR) to 2.33 g O3 g(-1) VOC (PTA). The significance of this O3 yield is discussed.     

A new method for the rapid determination of volatile organic compound breakthrough times for a sorbent at concentrations relevant to indoor air quality

The use of sorbents has been proposed to remove volatile organic compounds (VOCs) present in ambient air at concentrations in the parts-per-billion (ppb) range, which is typical of indoor air quality applications. Sorbent materials, such as granular activated carbon and molecular sieves, are used to remove VOCs from gas streams in industrial applications, where VOC concentrations are typically in the parts-per-million range. A method for evaluating the VOC removal performance of sorbent materials using toluene concentrations in the ppb range is described. Breakthrough times for toluene at concentrations from 2 to 7500 ppb are presented for a hydrophobic molecular sieve at 25%) relative humidity. By increasing the ratio of challenge gas flow rate to the mass of the sorbent bed and decreasing both the mass of sorbent in the bed and the sorbent particle size, this method reduces the required experimental times by a factor of up to several hundred compared with the proposed American Society of Heating, Refrigerating, and Air-Conditioning Engineers method, ASHRAE 145P, making sorbent performance evaluation for ppb-range VOC removal more convenient. The method can be applied to screen sorbent materials for application in the removal of VOCs from indoor air.     

Investigating the capacity of an activated sludge process to reduce volatile organic compounds and odor emissions.

The effects of hydrogen sulfide (H2S) diffusion into activated sludge (AS) on odor and volatile organic compound (VOC) concentrations in offgas were studied over an 8-week period. Most VOCs detected in the offgas of both aeration tanks were aromatic hydrocarbons. The VOC concentrations generally decreased when H2S was introduced to the AS compared with the control, indicating a negative effect of H2S on VOC removal. Two volatile organic sulfur compounds present in the test AS offgas showed an increase followed by a decrease during H2S peak loads. Six VOCs and odor concentration increased during the introduction of an H2S peak; however no correlation was observed between H2S and odor concentration. The increase in odor concentration resulted from the increase in the concentration of six aromatic VOCs, which had their removal slowed down during a 100-ppmv H2S peak. Activated sludge diffusion provides effective H2S removal with minimal affect on odor emissions.     

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, 14.0microg/m3) was the most abundant VOC, followed by acetaldehyde (4.76microg/m3), and formaldehyde (2.58microg/m3). 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 land use regression model for predicting ambient volatile organic compound concentrations in Toronto,Canada

More than 25 studies have employed land use regression (LUR) models to estimate nitrogen oxides and to a lesser extent particulate matter indicators, but these methods have been less commonly applied to ambient concentrations of volatile organic compounds (VOCs). Some VOCs have high plausibility as sources of health effects and others are specific indicators of motor vehicle exhaust. We used LUR models to estimate spatial variability of VOCs in Toronto, Canada. Benzene, n-hexane and total hydrocarbons (THC) were measured from July 25 to August 9, 2006 at 50 locations using the TraceAir organic vapor monitors. Nitrogen dioxide (NO₂) was also sampled to assess its spatial pattern agreement with VOC exposures. Buffers for land use, population density, traffic density, physical geography, and remote sensing measures of greenness and surface brightness were also tested. The remote sensing measures have the highest correlations with VOCs and NO₂ levels (i.e., explains >36% of the variance). Our regression models explain 66–68% of the variance in the spatial distribution of VOCs, compared to 81% for the NO₂ model. The ranks of agreement between various VOCs range from 48 to 63% and increases substantially – up to 75% – for the top and bottom quartile groups. Agreements between NO₂ and VOCs are much smaller with an average rank of 36%. Future epidemiologic studies may therefore benefit from using VOCs as potential toxic agents for traffic-related pollutants.     

A study on dynamic volatile organic compound emission characterization of water-based paints

Volatile organic compounds (VOCs) emitted from surface coatings have caused growing public concern for air quality. Even the low-emitted VOC impact from water-based paints on indoor air quality in urban areas has caused concern. This paper presents experimental data using a mathematical model to simulate dynamic VOC emissions from water-based paints that is based on mass transfer and molecular diffusion theories. A series of field-analogous experiments were carried out to continuously measure the VOCs emitted from two typical water-based paints using a gas chromatography-flame-ionization detector monitor in an artificial wind tunnel system. In the study cases, the mass flux of VOCs emitted from the water-based paints was up to 50 microg/m2sec. It was found that the time needed to completely emit VOCs from water-based paints is just hundreds of seconds. However, the order of magnitude of the VOC emission rate from water-based paints is not lower than that from some dry building materials and solvent-based paints. The experimental data were used to produce a useful semiempirical correlation to estimate the VOC emission rates for water-based paints. This correlation is valid under appropriate conditions as suggested by this work with a statistical deviation of +/- 7.6%. With this correlation, it seems feasible to predict the dynamic emission rates for VOCs during a painting process. This correlation is applicable for assessing the hazardous air pollutant impact on indoor air quality or for environmental risk assessment. Associated with the dynamic VOC emission characterization, the air-exchange rate effect on the VOC emission rates is also discussed.     

Estimate of initial isoprene contribution to ozone formation potential in Beijing, China

Volatile organic compounds (VOCs) are important precursors of tropospheric ozone formation. Isoprene contributions to ozone formation by using ambient mixing ratios are generally underestimated because of rapid chemical losses. In this study, ambient mixing ratios of major VOC species were continuously measured at Peking university (PKU) and YUFA, urban and sub-urban sites in Beijing, the city that will host 2008 Olympic Games. The observed mixing ratios of methyl vinyl ketone (MVK), methacrolein (MACR) and isoprene were used to derive the mixing ratios of initial isoprene, which means the ambient isoprene level before it undergoes any photochemical reaction with OH radicals. The average mixing ratios of initial isoprene were 3.3±1.6 and 2.9±1.5 ppbv at PKU and YUFA sites, respectively. The percentages of initial isoprene in total initial VOCs were 10.8% at PKU site and 11.4% at YUFA site, in reasonable agreement with the isoprene contribution in total VOC emissions as derived from source inventories. Maximum increment reactivity (MIR) was used to evaluate the ozone formation potential (OFP) for major VOC species. The OFP for initial isoprene accounted for 23% of the total OFPs for all measured species, compared to 11% using ambient mixing ratios of isoprene at PKU site. Similarly, at YUFA site, the ambient measured isoprene and initial isoprene contributed 10% and 22%, respectively, to the OFPs for total measured VOCs. It seems that isoprene has similar contribution to ozone formation at both sites in Beijing city.     

室内环境中挥发性有机物释放过程的数学模型

根据组成结构,将室内环境中释放挥发性有机物(VOCs)的建筑装饰材料划分为单层干材料、单层湿材料、多层组合材料等类型,总结了这三种材料的VOCs释放特征、传输过程和数学模型研究现状,分析了模型的特点和适用范围,指出了模型研究发展的趋势,对应用中模型的选择提出了指导性建议.     

Evaluation of non-enteric sources of non-methane volatile organic compound (NMVOC) emissions from dairies

Dairies are believed to be a major source of volatile organic compounds (VOC) in Central California, but few studies have characterized VOC emissions from these facilities. In this work, samples were collected from six sources of VOCs (Silage, Total Mixed Rations, Lagoons, Flushing Lanes, Open Lots and Bedding) at six dairies in Central California during 2006–2007 using emission isolation flux chambers and polished stainless steel canisters. Samples were analyzed by gas chromatography/mass spectrometry and gas chromatography/flame ionization detection. Forty-eight VOCs were identified and quantified in the samples, including alcohols, carbonyls, alkanes and aromatics. Silage and Total Mixed Rations are the dominant sources of VOCs tested, with ethanol as the major VOC present. Emissions from the remaining sources are two to three orders of magnitude smaller, with carbonyls and aromatics as the main components. The data suggest that animal feed rather than animal waste are the main source of non-enteric VOC emissions from dairies.