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.     

Biogenic volatile organic compound emissions from a lowland tropical wet forest in Costa Rica

Twenty common plant species were screened for emissions of biogenic volatile organic compounds (BVOCs) at a lowland tropical wet forest site in Costa Rica. Ten of the species examined emitted substantial quantities of isoprene. These species accounted for 35–50% of the total basal area of old-growth forest on the major edaphic site types, indicating that a high proportion of the canopy leaf area is a source of isoprene. A limited number of canopy-level BVOC flux measurements were also collected by relaxed eddy accumulation (REA). These measurements verify that the forest canopy in this region is indeed a significant source of isoprene. In addition, REA fluxes of methanol and especially acetone were also significant, exceeding model estimates and warranting future investigation at this site. Leaf monoterpene emissions were non-detectable or very low from the species surveyed, and ambient concentrations and REA fluxes likewise were very low. Although the isoprene emission rates reported here are largely consistent with phylogenetic relations found in other studies (at the family, genus, and species levels), two species in the family Mimosaceae, a group previously found to consist largely of non-isoprene emitters, emitted significant quantities of isoprene. One of these, Pentaclethra macroloba (Willd.) Kuntze, is by far the most abundant canopy tree species in the forests of this area, composing 30–40% of the total basal area. The other, Zygia longifolia (Humb. & Bonpl.) Britton & Rose is a common riparian species. Our results suggest that the source strength of BVOCs is important not only to tropical atmospheric chemistry, but also may be important in determining net ecosystem carbon exchange.     

Volatile organic compound emissions from Siberian larch

We determined hourly emissions of isoprene, monoterpenes and sesquiterpenes from Siberian larch, one of the major tree species in Siberian forests. Summer volatile organic compounds (VOCs) emission from Siberian larch consisted mainly of monoterpenes (about 90%). The monoterpene emission spectrum remained constant during the measurement period, almost half was sabinene and other major monoterpenes were Δ³-carene, β- and α-pinene. During spring and summer, about 10% of the VOCs were sesquiterpenes, mainly α-farnesene. The sesquiterpene emissions declined to 3% in the fall. Isoprene, 2-methyl-3-buten-2-ol (MBO) and 1,8-cineole contributed to less than 3% of the VOC emission during the whole period. The diurnal variation of the emissions could be explained using a temperature-dependent parameterization. Emission potentials normalized to 30 °C were 5.2–21 μg g_dw⁻¹ h⁻¹ (using β-value of 0.09 °C⁻¹) for monoterpenes and 0.4–1.8 μg g_dw⁻¹ h⁻¹ (using β-value of 0.143 °C⁻¹, mean of determined values) for sesquiterpenes. Normalized monoterpene emission potentials were highest in late summer and elevated again in late fall. Sesquiterpene emission potentials were also highest in late summer, but decreased towards fall.     

A combined approach for the evaluation of a volatile organic compound emissions inventory

Emissions inventories significantly affect photochemical air quality model performance and the development of effective control strategies. However, there have been very few studies to evaluate their accuracy. Here, to evaluate a volatile organic compound (VOC) emissions inventory, we implemented a combined approach: comparing the ratios of carbon bond (CB)-IV VOC groups to nitrogen oxides (NOx) or carbon monoxide (CO) using an emission preprocessing model, comparing the ratios of VOC source contributions from a source apportionment technique to NOx or CO, and comparing ratios of CB-IV VOC groups to NOx or CO and the absolute concentrations of CB-IV VOC groups using an air quality model, with the corresponding ratios and concentrations observed at three sites (Maryland, Washington, DC, and New Jersey). The comparisons of the ethene/NOx ratio, the xylene group (XYL)/NOx ratio, and ethene and XYL concentrations between estimates and measurements showed some differences, depending on the comparison approach, at the Maryland and Washington, DC sites. On the other hand, consistent results at the New Jersey site were observed, implying a possible overestimation of vehicle exhaust. However, in the case of the toluene group (TOL), which is emitted mainly from surface coating and printing sources in the solvent utilization category, the ratios of TOL/ NOx or CO, as well as the absolute concentrations revealed an overestimate of these solvent sources by a factor of 1.5 to 3 at all three sites. In addition, the overestimate of these solvent sources agreed with the comparisons of surface coating and printing source contributions relative to NOx from a source apportionment technique to the corresponding value of estimates at the Maryland site. Other studies have also suggested an overestimate of solvent sources, implying a possibility of inaccurate emission factors in estimating VOC emissions from surface coating and printing sources. We tested the impact of these overestimates with a chemical transport model and found little change in ozone but substantial changes in calculated secondary organic aerosol concentrations.     

室内空气总挥发性有机物检测的热解吸参数优化

总挥发性有机物(TVOC)是评价室内空气质量最重要的指标。为了提高TVOC检测的准确度,选取解吸气流量、热解吸温度、进样时间和热解吸时间四项因素设计正交实验,以热解吸率作为指标,对TVOC的热解吸过程进行了优化。并讨论在优化后参数的控制下,TVOC各组分的检测准确度。实验结果表明,优化的热解吸条件下各参数指标分别为解吸气流量40 mL/min、热解吸温度280℃、进样时间120 s、热解吸时间30 s。检测准确度的结果表明,在优化热解吸参数的控制下,各组分的回收率在90.3%～97.3%之间,满足TVOC的实际检测需求。     

Biofilter treatment of volatile organic compound emissions from reformulated paint: complex mixtures, intermittent operation, and startup

Two biofilters were operated to treat a waste gas stream intended to simulate off-gases generated during the manufacture of reformulated paint. The model waste gas stream consisted of a five-component solvent mixture containing acetone (450 ppm(v)), methyl ethyl ketone (12 ppm(v)), toluene (29 ppm(v)), ethylbenzene (10 ppm(v)), and p-xylene (10 ppm(v)). The two biofilters, identical in construction and packed with a polyurethane foam support medium, were inoculated with an enrichment culture derived from compost and then subjected to different loading conditions during the startup phase of operation. One biofilter was subjected to intermittent loading conditions with contaminants supplied only 8 hr/day to simulate loading conditions expected at facilities where manufacturing operations are discontinuous. The other biofilter was subjected to continuous contaminant loading during the initial start period, and then was switched to intermittent loading conditions. Experimental results demonstrate that both startup strategies can ultimately achieve high contaminant removal efficiency (>99%) at a target contaminant mass loading rate of 80.3 g m(-3) hr(-1) and an empty bed residence time of 59 sec. The biofilter subjected to intermittent loading conditions at startup, however, took considerably longer to reach high performance. In both biofilters, ketone components (acetone and methyl ethyl ketone) were, more rapidly degraded than aromatic hydrocarbons (toluene, ethylbenzene, and p-xylene). Scanning electron microscopy and plate count data revealed that fungi, as well as bacteria, populated the biofilters.     

Assessment of control strategies for reducing volatile organic compound emissions from the polyvinyl chloride wallpaper production industry in Taiwan

This study attempts to assess the effectiveness of control strategies for reducing volatile organic compound (VOC) emission from the polyvinyl chloride (PVC) wallpaper production industry. In Taiwan, methyl ethyl ketone, TOL, and cyclohexanone have comprised the major content of solvents, accounting for approximately 113,000 t/yr to avoid excessive viscosity of plasticizer dioctyl phthalate (DOP) and to increase facility in working. Emissions of these VOCs from solvents have caused serious odor and worse air quality problems. In this study, 80 stacks in five factories were tested to evaluate emission characteristics at each VOC source. After examining the VOC concentrations in the flue gases and contents, the VOC emission rate before treatment and from fugitive sources was 93,000 and 800 t/yr, respectively. In this study, the semiwet electrostatic precipitator is recommended for use as cost-effective control equipment.     

Volatile organic compound emissions from dry mill fuel ethanol production

Ethanol fuel production is growing rapidly in the rural Midwest, and this growth presents potential environmental impacts. In 2002, the U.S. Environmental Protection Agency (EPA) and the Minnesota Pollution Control Agency (MPCA) entered into enforcement actions with 12 fuel ethanol plants in Minnesota. The enforcement actions uncovered underreported emissions and resulted in consent decrees that required pollution control equipment be installed. A key component of the consent decrees was a requirement to conduct emissions tests for volatile organic compounds (VOCs) with the goal of improving the characterization and control of emissions. The conventional VOC stack test method was thought to underquantify total VOC emissions from ethanol plants. A hybrid test method was also developed that involved quantification of individual VOC species. The resulting database of total and speciated VOC emissions from 10 fuel ethanol plants is relatively small, but it is the most extensive to date and has been used to develop and gauge compliance with permit limits and to estimate health risks in Minnesota. Emissions were highly variable among facilities and emissions units. In addition to the variability, the small number of samples and the presence of many values below detection limits complicate the analysis of the data. To account for these issues, a nested bootstrap procedure on the Kaplan-Meier method was used to calculate means and upper confidence limits. In general, the fermentation scrubbers and fluid bed coolers emitted the largest mass of VOC emissions. Across most facilities and emissions units ethanol was the pollutant emitted at the highest rate. Acetaldehyde, acetic acid, and ethyl acetate were also important emissions from some units. Emissions of total VOCs, ethanol, and some other species appeared to be a function of the beer feed rate, although the relationship was not reliable enough to develop a production rate-based emissions factor.     

Biofiltration of a mixture of volatile organic emissions

Air biofiltration is now under active consideration for the removal of the volatile organic compounds (VOCs) from polluted airstreams. To optimize this emerging environmental technology and to understand compound removal mechanisms, a biofilter packed with peat was developed to treat a complex mixture of VOCs: oxygenated, aromatic, and chlorinated compounds. The removal efficiency of this process was high. The maximum elimination capacity (ECmax) obtained was approximately 120 g VOCs/m3 peat/hr. Referring to each of the mixture's components, the ECmax showed the limits in terms of biodegradability of VOCs, especially for the halogenated compounds and xylene. A stratification of biodegradation was observed in the reactor. The oxygenated compounds were metabolized before the aromatic and halogenated ones. Two assumptions are suggested. There was a competition between bacterial communities. Different communities colonized the peat-based biofilter, one specialized for the elimination of oxygenated compounds, the others more specialized for elimination of aromatic and halogenated compounds. There was also substrate competition. Bacterial communities were the same over the height of the column, but the more easily biodegradable compounds were used first for the microorganism metabolism when they were present in the gaseous effluent.     

Biogenic volatile organic compound emissions (BVOCs). I. Identifications from three continental sites in the U.S

Vegetation composition and biomass were surveyed for three specific sites in Atlanta, GA; near Rhinelander, WI; and near Hayden, CO. At each research site emissions of biogenic volatile organic compounds (BVOCs) from the dominant vegetation species were sampled by enclosing branches in bag enclosure systems and sampling the equilibrium head space onto multi-stage solid adsorbent cartridges. Analysis was performed using a thermal desorption technique with gas chromatography (GC) separation and mass spectrometry (MS) detection. Identification of BVOCs covering the GC retention index range (stationary phase DB-1) from approximately 400 to 1400 was achieved (volatilities C4-C14).     

Interlaboratory exercises for volatile organic compound determination

The results of a European level intercomparison involving measurements of 26 hydrocarbons (from C2 to C9) at ambient air concentration level are discussed. On-line sampling with cryo-GC-FID analysis was the most commonly used methodology among the 20 participating laboratories. The stability of the gas samples in the canisters; the calibration methodology, the separation of peaks and the low level of concentrations were identified as the most important factors, which contributed to the increase in the uncertainty of the measurement. Uncertainty values associated with the common method used for the quantification of each compound and exercise were also determined.     

Microwave process for volatile organic compound abatement

The CHA Corporation has completed the U.S. Air Force Phase II Small Business Innovation Research program to investigate the feasibility of using a novel microwave-based process for the removal and destruction of volatile organic compounds (VOCs) in effluents from noncombustion sources, such as paint booth ventilation streams. Removal of solvents by adsorption, followed by the regeneration of saturated granular activated carbon (GAC) by microwave energy, was achieved in a single fixed-bed reactor. Microwave regeneration of the fixed-bed-saturated carbon restored the original GAC adsorption capacity. After 20 adsorption/regeneration cycles, the adsorption capacity dropped from 13.5 g methyl ethyl ketone (MEK)/100 g GAC to 12.5 g MEK/100 g GAC. During microwave regeneration of the GAC fixed bed, the concentrated desorbed paint solvent was oxidized by passing the solvent mixture through a fixed bed of an oxidation catalyst mixed with silicon carbide in a microwave reactor. A 98% oxidation efficiency was consistently achieved from the oxidation of VOCs in the microwave catalytic reactor.     

Source location and characterization of volatile organic compound emissions at a petrochemical plant in Kaohsiung, Taiwan

This paper elucidated a novel approach to locating volatile organic compound (VOC) emission sources and characterizing their VOCs by database and contour plotting. The target of this survey was a petrochemical plant in Linyan, Kaohsiung County, Taiwan. Samples were taken with canisters from 25 sites inside this plant, twice per season, and analyzed by gas chromatography-mass spectrometry. The survey covered 1 whole year. By consolidated into a database, the data could be readily retrieved, statistically analyzed, and clearly presented in both table and graph forms. It followed from the cross-analysis of the database that the abundant types of VOCs were alkanes, alkenes/dienes, and aromatics, all of which accounted for 99% of total VOCs. By contour plotting, the emission sources for alkanes, aromatics, and alkenes/ dienes were successfully located. Through statistical analysis, the database could provide the range and 90% confidence interval of each species from each emission source. Both alkanes and alkene/dienes came from tank farm and naphtha cracking units and were mainly composed of C3-C5 members. Regarding aromatics, benzene, toluene, and xylenes were the primary species; they were emitted from tank farm, aromatic units, and xylene units.     

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.     

Effect of vegetation removal and water table drawdown on the non-methane biogenic volatile organic compound emissions in boreal peatland microcosms

Biogenic volatile organic compound (BVOC) emissions are important in the global atmospheric chemistry and their feedbacks to global warming are uncertain. Global warming is expected to trigger vegetation changes and water table drawdown in boreal peatlands, such changes have only been investigated on isoprene emission but never on other BVOCs. We aimed at distinguishing the BVOCs released from vascular plants, mosses and peat in hummocks (dry microsites) and hollows (wet microsites) of boreal peatland microcosms maintained in growth chambers. We also assessed the effect of water table drawdown (?20 cm) on the BVOC emissions in hollow microcosms. BVOC emissions were measured from peat samples underneath the moss surface after the 7-week-long experiment to investigate whether the potential effects of vegetation and water table drawdown were shown. BVOCs were sampled using a conventional chamber method, collected on adsorbent and analyzed with GC–MS. In hummock microcosms, vascular plants increased the monoterpene emissions compared with the treatment where all above-ground vegetation was removed while no effect was detected on the sesquiterpenes, other reactive VOCs (ORVOCs) and other VOCs. Peat layer from underneath the surface with intact vegetation had the highest sesquiterpene emissions. In hollow microcosms, intact vegetation had the highest sesquiterpene emissions. Water table drawdown decreased monoterpene and other VOC emissions. Specific compounds could be closely associated to the natural/lowered water tables. Peat layer from underneath the surface of hollows with intact vegetation had the highest emissions of monoterpenes, sesquiterpenes and ORVOCs whereas water table drawdown decreased those emissions. The results suggest that global warming would change the BVOC emission mixtures from boreal peatlands following changes in vegetation composition and water table drawdown.     

Biogenic volatile organic compound emissions (BVOCs). II. Landscape flux potentials from three continental sites in the U.S

Landscape flux potentials for biogenic volatile organic compounds (BVOCs) were derived for three ecosystems in the continental U.S. (Fernbank Forest, Atlanta, GA; Willow Creek, Rhinelander, WI; Temple Ridge, CO). Analytical data from branch enclosure measurements were combined with ecological survey data for plant species composition and biomass. Other quantitative flux measurements at the leaf and landscape level were incorporated to scale the results from the enclosure measurements to the landscape level. Flux estimates were derived by using a one week ambient temperature and light record (30 min time resolution) and adjusting all emission rates to these conditions with temperature and light correction algorithms.     

Modeling the influence of biogenic volatile organic compound emissions on ozone concentration during summer season in the Kinki region of Japan

Tropospheric ozone adversely affects human health and vegetation, and biogenic volatile organic compound (BVOC) emission has potential to influence ozone concentration in summer season. In this research, the standard emissions of isoprene and monoterpene from the vegetation of the Kinki region of Japan, estimated from growth chamber experiments, were converted into hourly emissions for July 2002 using the temperature and light intensity data obtained from results of MM5 meteorological model. To investigate the effect of BVOC emissions on ozone production, two ozone simulations for one-month period of July 2002 were carried out. In one simulation, hourly BVOC emissions were included (BIO), while in the other one, BVOC emissions were not considered (NOBIO). The quantitative analyses of the ozone results clearly indicate that the use of spatio-temporally varying BVOC emission improves the prediction of ozone concentration. The hourly differences of monthly-averaged ozone concentrations between BIO and NOBIO had the maximum value of 6 ppb at 1400 JST. The explicit difference appeared in urban area, though the place where the maximum difference occurred changed with time. Overall, BVOC emissions from the forest vegetation strongly affected the ozone generation in the urban area.     

A study of volatile organic sulfur emissions causing urban odors

Levels of hydrogen sulfide and sulfur containing organic compounds were studied in the air at the deltas of the polluted creeks in the city of Izmir, Turkey in summer 2001. High concentrations of these malodorous compounds were measured in the air samples. Presence of these compounds in the air was connected with the dark appearance and rising gas bubbles in the studied segments of the creeks. These creeks were like open sewers carrying wastewaters from the industry and residential areas into the inner Izmir Bay until September 2001.Within the scope of this study organic sulfur compounds such as methane thiol, ethane thiol, 2-propane thiol, 2-butane thiol, dimethylsulfide, dimethyldisulfide, thiophene, diphenylsulfide and hydrogen sulfide were studied in the air at selected urban sites where odor nuisance was recognized. Flux measurements from polluted surfaces were preferred rather than direct ambient air measurements. Organic sulfur emission fluxes from the creek surfaces were found above the values reported in the literature. Their concentrations and fluxes were higher in June field program. A limited number of measurements of reduced sulfur compound emission concentrations from the wastewater treatment plant equalization tank and the sludge drying beds as well as the landfill soil surface were also included in the study.Concentrations of total organic sulfur compounds and certain individual components such as dimethylsulfide and hydrogen sulfide in emitted gases from river surfaces were correlated with ambient SO(2) concentrations.     

Near surface soil vapor clusters for monitoring emissions of volatile organic compounds from soils

The overall objective of this research was to develop and test a method of determining emission rates of volatile organic compounds (VOCs) and other gases from soil surfaces. Soil vapor clusters (SVCs) were designed as a low dead volume, robust sampling system to obtain vertically resolved profiles of soil gas contaminant concentrations in the near surface zone. The concentration profiles, when combined with a mathematical model of porous media mass transport, were used to calculate the contaminant flux from the soil surface. Initial experiments were conducted using a mesoscale soil remediation system under a range of experimental conditions. Helium was used as a tracer and trichloroethene was used as a model VOC. Flux estimations using the SVCs were within 25% of independent surface flux estimates and were comparable to measurements made using a surface isolation flux chamber (SIFC). In addition, method detection limits for the SVC were an order of magnitude lower than detection limits with the SIFC. Field trials, conducted with the SVCs at a bioventing site, indicated that the SVC method could be easily used in the field to estimate fugitive VOC emission rates. Major advantages of the SVC method were its low detection limits, lack of required auxiliary equipment, and ability to obtain real-time estimates of fugitive VOC emission rates.     

Design and laboratory testing of a chamber device to measure total flux of volatile organic compounds from the unsaturated zone under natural conditions

To determine if an aquifer contaminated with volatile organic compounds (VOCs) has potential for natural remediation, all natural processes affecting the fate and transport of VOCs in the subsurface must be identified and quantified. This research addresses the quantification of air-phase volatile organic compounds (VOCs) leaving the unsaturated zone soil gas and entering the atmosphere-including the additional flux provided by advective soil-gas movement induced by barometric pumping. A simple and easy-to-use device for measuring VOC flux under natural conditions is presented. The vertical flux chamber (VFC) was designed using numerical simulations and evaluated in the laboratory. Mass-balance numerical simulations based on continuously stirred tank reactor equations (CSTR) provided information on flux measurement performance of several sampling configurations with the final chamber configuration measuring greater than 96% of model-simulated fluxes. A laboratory device was constructed to evaluate the flux chamber under both diffusion-only and advection-plus-diffusion transport conditions. The flux chamber measured an average of 82% of 15 diffusion-only fluxes and an average of 95% of 15 additional advection-plus-diffusion flux experiments. The vertical flux chamber has the capability of providing reliable measurement of VOC flux from the unsaturated zone under both diffusion and advection transport conditions.