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).     

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.     

Evaluation of total volatile organic compound emissions from adhesives based on chamber tests

In 1997, Homeswest in western Australia and Murdoch University developed a project to construct low-allergen houses (LAHs) in a newly developed suburb. Before the construction of LAHs, all potential volatile organic compound (VOC) emission materials used in LAHs are required to be measured to ensure that they are low total VOC (TVOC) emission materials. This program was developed based on this purpose. In recent times, the number of complaints about indoor air pollution caused by VOCs has increased. A number of surveys of indoor VOCs have indicated that many indoor materials contribute to indoor air pollution. Although some studies have been conducted on the characteristics of VOC emissions from adhesives, most of them were focused on VOC emissions from floor adhesives. Few measurements of VOC emissions from adhesives used for wood, fabrics, and leather are available. Furthermore, most research on VOC emissions from adhesives has been done in countries with cool climates, where ventilation rates in the indoor environment are lower than those in Mediterranean climates, due to energy conservation. VOCs emitted from adhesives have not been sufficiently researched to prepare an emission inventory to predict indoor air quality and to determine both exposure levels for the Australian population and the most appropriate strategies to reduce exposure. An environmental test chamber with controlled temperature, relative humidity, and airflow rate was used to evaluate emissions of TVOCs from three adhesives used frequently in Australia. The quantity of TVOC emissions was measured by a gas chromatography/flame ionization detector. The primary VOCs emitted from each adhesive were detected by gas chromatography/mass spectrometry. The temporal change of TVOC concentrations emitted from each adhesive was tested. A double-exponential equation was then developed to evaluate the characteristics of TVOC emissions from these three adhesives. With this double-exponential model, the physical processes of TVOC emissions can be explained, and a variety of emission parameters can be calculated. These emission parameters could be used to estimate real indoor TVOC concentrations in Mediterranean climates.     

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.     

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.     

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.     

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.     

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.     

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.     

Perspectives on secondary forest management in tropical humid lowland America

Secondary forests regrowing on abandoned agricultural land constitute an important, albeit widely overlooked, component in the landscape matrix of tropical lowland America. These 'new' forest resources on private land-holdings derive either from unsustainable cattle-ranching practices of better-off farmers or are part of the crop/fallow system of resource-poor farmers. If previous land use was light, secondary forest management may offer an interesting use option to better-off farmers, providing that subsidies for stand improvement are given. Improved fallow systems using partly the successional vegetation may be a way to establish sustainable small-scale agriculture for resource-poor farmers. Given some technical and financial input, land-use systems based on secondary vegetation could play a vital role both in sustainable landscape management and biodiversity conservation.     

Biogenic volatile organic compounds as a potential stimulator for organic contaminant degradation by soil microorganisms

The effects of monoterpenes on the degradation of ¹⁴C-2,4-dichlorophenol (DCP) were investigated in soils collected from areas surrounding monoterpene and non-monoterpene-emitting vegetation. Indigenous microorganisms degraded ¹⁴C-2,4-DCP to ¹⁴CO₂, after 1 d contact time. Degradation was enhanced by prior exposure of the soils to 2,4-DCP for 32 d, increasing extents of mineralisation up to 60%. Monoterpene amendments further enhanced 2,4-DCP degradation, but only following pre-exposure to both 2,4-DCP and monoterpene, with total 2,4-DCP mineralisation extents of up to 71%. Degradation was greatest at the higher monoterpene concentrations (≥1 μg kg⁻¹). Total mineralisation extents were similar between concentrations, but higher than the control and the 0.1 μg kg⁻¹ amendment, indicating that increases in monoterpene concentration has a diminishing enhancing effect. We suggest that monoterpenes can stimulate the biodegradation of 2,4-DCP by indigenous soil microorganisms and that monoterpene amendment in soils is an effective strategy for removing organic contaminants.     

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.     

Variations in the emissions of volatile organic compounds from the toner for a specific photocopier

A laboratory thermal desorption apparatus was used to measure emissions from a number of nominally identical photocopier toners--manufactured to meet the specifications of one specific model copier--when these toners were heated to fuser temperature (180-200 degrees C). The objective was to assess how potential volatile organic compound (VOC) emissions from the toner for a given copier can vary, depending upon the production run and the supplier. Tests were performed on a series of toner (and associated raw polymer feedstock) samples obtained directly from a toner manufacturer, representing two production runs using a nonvented extrusion process, and on toner cartridges purchased from two local retailers, representing three different production lots (histories unknown). The results showed that the retailer toners consistently had up to 350% higher emissions of some major compounds (expressed as microgram of compound emitted/g of toner), and up to 100% lower emissions of others, relative to the manufacturer toners (p < or = 0.01). The manufacturer toners from one production run had emissions of certain compounds, and of total VOCs, that were modestly higher (13-18%) than those from the other run (p < or = 0.01). The emission differences between the retailer and manufacturer toners are probably due to differences in the manufacturing processes and/or feedstocks used to produce the toners from these different sources.     

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.     

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.     

Development of a database for chemical mechanism assignments for volatile organic emissions

The development of a database for making model species assignments when preparing total organic gas (TOG) emissions input for atmospheric models is described. This database currently has assignments of model species for 12 different gas-phase chemical mechanisms for over 1700 chemical compounds and covers over 3000 chemical categories used in five different anthropogenic TOG profile databases or output by two different biogenic emissions models. This involved developing a unified chemical classification system, assigning compounds to mixtures, assigning model species for the mechanisms to the compounds, and making assignments for unknown, unassigned, and nonvolatile mass. The comprehensiveness of the assignments, the contributions of various types of speciation categories to current profile and total emissions data, inconsistencies with existing undocumented model species assignments, and remaining speciation issues and areas of needed work are also discussed. The use of the system to prepare input for SMOKE, the Speciation Tool, and for biogenic models is described in the supplementary materials. The database, associated programs and files, and a users manual are available online at http://www.cert.ucr.edu/~carter/emitdb.

Implications: Assigning air quality model species to the hundreds of emitted chemicals is a necessary link between emissions data and modeling effects of emissions on air quality. This is not easy and makes it difficult to implement new and more chemically detailed mechanisms in models. If done incorrectly, it is similar to errors in emissions speciation or the chemical mechanism used. Nevertheless, making such assignments is often an afterthought in chemical mechanism development and emissions processing, and existing assignments are usually undocumented and have errors and inconsistencies. This work is designed to address some of these problems.     

Emission of volatile organic compounds (VOC) from tropical plant species in India

Foliar emission of volatile organic compounds (VOC) from common Indian plant species was measured. Dynamic flow enclosure technique was used and the gas samples were collected onto Tenax-GC/Carboseive cartridges. The Tenax-GC/Carboseive cartridges were attached to the thermal disorber sample injection system and the gas sample was analysed using gas chromatography (GC) with flame ionisation detection (FID). Fifty-one local plant species were screened, out of which 36 species were found to emit VOC (4 high emitter; 28 moderate emitter; and 4 low-emitter), while in the remaining 15 species no VOC emission was detected or the levels of emission were below detection limit (BDL). VOC emission was found to vary from one species to another. There was a marked seasonal and diurnal variation in VOC emission. The minimum and maximum VOC emission values were < 0.1 and 87 microgg(-1) dry leaf h(-1) in Ficus infectoria and Lantana camara respectively. Out of the 51 plant species studied, 13 species are reported here for the first time. Among the nine tree species (which were selected for detailed study), the highest average hourly emission (9.69+/-8.39 microgg(-1) dry leaf) was observed in Eucalyptus species and the minimum in Syzygium jambolanum (1.89+/-2.48 microgg(-1) dry leaf). An attempt has been made to compare VOC emission from different plant species between present study and the literature (tropical and other regions).     

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.     

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.     

Monoterpene emissions from soil in a Sitka spruce forest

A dynamic soil enclosure was used to characterise monoterpene emissions from 3 soil depths within a Picea sitchensis (Sitka spruce) forest. In addition, a dynamic branch enclosure was used to provide comparative emissions data from foliage. In all cases, limonene and α-pinene dominated monoterpene soil emissions, whilst camphene, β-pinene and myrcene were also present in significant quantities. α-Phellandrene, 3-carene and α-terpinene were occasionally emitted in quantifiable amounts whilst cymene and cineole, although tentatively identified, were always non-quantifiable. Total daily mean monoterpene emission rates, normalised to 30°C, varied considerably between soil depths from 33.6 μg m⁻² h⁻¹ (range 28.3–38.4) for undisturbed soil, to 13.0 μg m⁻² h⁻¹ (8.97–16.4) with uppermost layer removed, to 199 μg m⁻² h⁻¹ (157–216) with partially decayed layer removed, suggesting that the surface needle litter was the most likely source of soil emissions to the atmosphere. Relative monoterpene ratios did not vary significantly between layers. Foliar monoterpenes exhibited a similar emission profile to soils with the exceptions of camphene and 3-carene whose contributions decreased and increased, respectively. Emission rates from foliage, normalised to 30°C were found to have a daily mean of 625 ng g⁻¹ dw h⁻¹ (299–1360). On a land area basis however, total soil emissions were demonstrated to be relatively insignificant to total emissions from the forest ecosystem.