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

Abstract

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.     

Evaluating sources of indoor air pollution

Evaluation of indoor air pollution problems requires an understanding of the relationship between sources, air movement, and outdoor air exchange. Research is underway to investigate these relationships. A three-phase program is being implemented: 1) Environmental chambers are used to provide source emission factors for specific indoor pollutants; 2) An IAQ (Indoor Air Quality) model has been developed to calculate indoor pollutant concentrations based on chamber emissions data and the air exchange and air movement within the indoor environment; and 3) An IAQ test house is used to conduct experiments to evaluate the model results. Examples are provided to show how this coordinated approach can be used to evaluate specific sources of indoor air pollution. Two sources are examined: 1) para-dichlorobenzene emissions from solid moth repellant; and 2) particle emissions from unvented kerosene heaters. The evaluation process for both sources followed the three-phase approach discussed above. Para-dichlorobenzene emission factors were determined by small chamber testing at EPA's Air and Energy Engineering Research Laboratory. Particle emission factors for the kerosene heaters were developed in large chambers at the J. B. Pierce Foundation Laboratory. Both sources were subsequently evaluated in EPA's IAQ test house. The IAQ model predictions showed good agreement with the test house measurements when appropriate values were provided for source emissions, outside air exchange, in-house air movement, and deposition on "sink" surfaces.     

Evaluating Sources of Indoor Air Pollution

Evaluation of Indoor air pollution problems requires an understanding of the relationship between sources, air movement, and outdoor air exchange. Research is underway to investigate these relationships. A three-phase program is being implemented: 1) Environmental chambers are used to provide source emission factors for specific indoor pollutants; 2) An IAQ (Indoor Air Quality) model has been developed to calculate indoor pollutant concentrations based on chamber emissions data and the air exchange and air movement within the indoor environment; and 3) An IAQ test house is used to conduct experiments to evaluate the model results. Examples are provided to show how this coordinated approach can be used to evaluate specific sources of indoor air pollution. Two sources are examined: 1) para-dichlorobenzene emissions from solid moth repellant; and 2) particle emissions from unvented kerosene heaters.

The evaluation process for both sources followed the three-phase approach discussed above. Para-dichlorobenzene emission factors were determined by small chamber testing at EPA’s Air and Energy Engineering Research Laboratory. Particle emission factors for the kerosene heaters were developed In large chambers at the J. B. Pierce Foundation Laboratory. Both sources were subsequently evaluated in EPA’s IAQ test house. The IAQ model predictions showed good agreement with the test house measurements when appropriate values were provided for source emissions, outside air exchange, in-house air movement, and deposition on “sink” surfaces.     

Lead and cadmium in indoor air and the urban environment

The present study was conducted to find potential terrestrial biomonitors for heavy metals in indoor air in an urban environment. TSP, PM(10), and PM(2.5) were collected in three retirement facilities in the urban area of Vienna. In addition, particulate matter and soil, vegetation, and isopods (Porcellio scaber L.) were collected in the adjacent garden areas. Aerosols were sampled with a low-volume air sampler. The sampled materials were wet ashed and total lead and cadmium contents were determined. Water-soluble heavy metal concentrations were measured in aqueous extracts from air exposed filters, soil, and vegetation. Lead and cadmium were analyzed by graphite furnace AAS. Lead contents in the vegetation were inferred from water-soluble lead in soils. Lead in isopods generally reflected the contents in vegetation. Cadmium in plants probably derived from soil solutions as well as from atmospheric input. Isopods reflected the total cadmium contents in soils. Particulate matter was dominated by PM(2.5), both with respect to mass concentrations and to heavy metal contents. The indoor aerosol was found to be influenced by human activity, indoor sources, and outdoor particles. Relationships between indoor airborne heavy metals and the contents in vegetation (lead and cadmium: positive) and isopods (lead: negative) were identified to have the potential for biomonitoring indoor air quality.     

The Use of Indoor Air Measurements To Evaluate Intrusion of Subsurface VOC Vapors into Buildings

ABSTRACT

The implementation of a risk-based corrective action approach often requires consideration of soil vapor migration into buildings and potential inhalation exposure and risk to human health. Due to the uncertainty associated with models for this pathway, there may be a desire to analyze indoor air samples to validate model predictions, and this approach is followed on a somewhat frequent basis at sites where risks are considered potentially significant. Indoor air testing can be problematic for a number of reasons. Soil vapor intrusion into buildings is complex, highly dependent on site-specific conditions, and may vary over time, complicating the interpretation of indoor air measurements when the goal is to deduce the subsurface-derived component. An extensive survey of indoor air quality data sets highlights the variability in indoor volatile organic compound (VOC) concentrations and numerous sources that can lead to elevated VOC levels. The contribution from soil vapor is likely to be small relative to VOCs from other sources for most sites. In light of these challenges, we discuss how studies that use indoor air testing to assess subsurface risks could be improved. To provide added perspective, we conclude by comparing indoor air concentrations and risks arising from subsurface VOCs, predicted using standard model equations for soil vapor fate and intrusion into buildings, to those associated with indoor sources.     

Sequential box models for indoor air quality: Application to airliner cabin air quality

In this paper we present the development and application of a model for indoor air quality. The model represents a departure from the standard box models typically used for indoor environments which has applicability in residences and office buildings. The model has been developed for a physical system consisting of sequential compartments which communicate only with adjacent compartments. Each compartment may contain various source and sink terms for a pollutant as well as leakage, and air transfer from adjacent compartments. The mathematical derivation affords rapid calculation of equilibrium concentrations in an essentially unlimited number of compartments. The model has been applied to air quality in the passenger cabin of three commercial aircraft. Simulations have been performed for environmental tobacco smoke (ETS) under two scenarios, CO₂ and water vapor. Additionally, concentrations in one aircraft have been simulated under conditions different from the standard configuration. Results of the simulations suggest the potential for elevated concentrations of ETS in smoking sections of non-air-recirculating aircraft and throughout the aircraft when air is recirculated. Concentrations of CO₂ and water vapor are consistent with expected results. We conclude that this model may be a useful tool in understanding indoor air quality in general and on aircraft in particular.     

Air quality modeling in the South Coast Air Basin of California: what do the numbers really mean?

This study evaluates air quality model sensitivity to input and to model components. Simulations are performed using the California Institute of Technology (CIT) airshed model. Results show the impacts on ozone (O3) concentration in the South Coast Air Basin (SCAB) of California because of changes in: (1) input data, including meteorological conditions (temperature, UV radiation, mixing height, and wind speed), boundary conditions, and initial conditions (ICs); and (2) model components, including advection solver and chemical mechanism. O3 concentrations are strongly affected by meteorological conditions and, in particular, by temperature. ICs also affect O3 concentrations, especially in the first 2 days of simulation. On the other hand, boundary conditions do not significantly affect the absolute peak O3 concentration, although they do affect concentrations near the inflow boundaries. Moreover, predicted O3 concentrations are impacted considerably by the chemical mechanism. In addition, dispersion of pollutants is affected by the advection routine used to calculate its transport. Comparison among CIT, California Photochemical Grid Model (CALGRID), and Urban Airshed Model air quality models suggests that differences in O3 predictions are mainly caused by the different chemical mechanisms used. Additionally, advection solvers contribute to the differences observed among model predictions. Uncertainty in predicted peak O3 concentration suggests that air quality evaluation should not be based solely on this single value but also on trends predicted by air quality models using a number of chemical mechanisms and with an advection solver that is mass conservative.     

The use of indoor air measurements to evaluate intrusion of subsurface VOC vapors into buildings

The implementation of a risk-based corrective action approach often requires consideration of soil vapor migration into buildings and potential inhalation exposure and risk to human health. Due to the uncertainty associated with models for this pathway, there may be a desire to analyze indoor air samples to validate model predictions, and this approach is followed on a somewhat frequent basis at sites where risks are considered potentially significant. Indoor air testing can be problematic for a number of reasons. Soil vapor intrusion into buildings is complex, highly dependent on site-specific conditions, and may vary over time, complicating the interpretation of indoor air measurements when the goal is to deduce the subsurface-derived component. An extensive survey of indoor air quality data sets highlights the variability in indoor volatile organic compound (VOC) concentrations and numerous sources that can lead to elevated VOC levels. The contribution from soil vapor is likely to be small relative to VOCs from other sources for most sites. In light of these challenges, we discuss how studies that use indoor air testing to assess subsurface risks could be improved. To provide added perspective, we conclude by comparing indoor air concentrations and risks arising from subsurface VOCs, predicted using standard model equations for soil vapor fate and intrusion into buildings, to those associated with indoor sources.     

A pesticide emission model (PEM) Part II: model evaluation

In the first part of the paper, the development of a numerical pesticide emission model (PEM) is described for predicting the volatilization of pesticides applied to agricultural soils and crops through soil incorporation, surface spraying, or in the furrow at the time of planting. In this paper the results of three steps toward the evaluation of PEM are reported. The evaluation involves: (i) verifying the numerical algorithms and computer code through comparison of PEM simulations with an available analytical solution of the advection/diffusion equation for semi-volatile solutes in soil; (ii) comparing hourly heat, moisture and emission fluxes of trifluralin and triallate modeled by PEM with fluxes measured using the relaxed eddy-accumulation technique; and (iii) comparison of the PEM predictions of persistence half-life for 29 pesticides with the ranges of persistence found in the literature. The overall conclusion from this limited evaluation study is that PEM is a useful model for estimating the volatilization rates of pesticides from agricultural soils and crops. The lack of reliable estimates of chemical and photochemical degradation rates of pesticide on foliage, however, introduces large uncertainties in the estimates from any model of the volatilization of pesticide that impacts the canopy.     

Analytical solutions to compartmental indoor air quality models with application to environmental tobacco smoke concentrations measured in a house

This paper derives the analytical solutions to multi-compartment indoor air quality models for predicting indoor air pollutant concentrations in the home and evaluates the solutions using experimental measurements in the rooms of a single-story residence. The model uses Laplace transform methods to solve the mass balance equations for two interconnected compartments, obtaining analytical solutions that can be applied without a computer. Environmental tobacco smoke (ETS) sources such as the cigarette typically emit pollutants for relatively short times (7-11 min) and are represented mathematically by a "rectangular" source emission time function, or approximated by a short-duration source called an "impulse" time function. Other time-varying indoor sources also can be represented by Laplace transforms. The two-compartment model is more complicated than the single-compartment model and has more parameters, including the cigarette or combustion source emission rate as a function of time, room volumes, compartmental air change rates, and interzonal air flow factors expressed as dimensionless ratios. This paper provides analytical solutions for the impulse, step (Heaviside), and rectangular source emission time functions. It evaluates the indoor model in an unoccupied two-bedroom home using cigars and cigarettes as sources with continuous measurements of carbon monoxide (CO), respirable suspended particles (RSP), and particulate polycyclic aromatic hydrocarbons (PPAH). Fine particle mass concentrations (RSP or PM3.5) are measured using real-time monitors. In our experiments, simultaneous measurements of concentrations at three heights in a bedroom confirm an important assumption of the model-spatial uniformity of mixing. The parameter values of the two-compartment model were obtained using a "grid search" optimization method, and the predicted solutions agreed well with the measured concentration time series in the rooms of the home. The door and window positions in each room had considerable effect on the pollutant concentrations observed in the home. Because of the small volumes and low air change rates of most homes, indoor pollutant concentrations from smoking activity in a home can be very high and can persist at measurable levels indoors for many hours.     

Source apportionment of indoor air pollution

An understanding of the relative contributions from important pollutant sources to human exposures is necessary for the design and implementation of effective control strategies. In the past, societal efforts to control air pollution have focused almost exclusively on the outdoor (ambient) environment. As a result, substantial amounts of time and money have been spent to limit airborne discharges from mobile and stationary sources. Yet it is now recognized that exposures to elevated pollutant concentrations often occur as a result of indoor, rather than outdoor, emissions. While the major indoor sources have been identified, their relative impacts on indoor air quality have not been well defined. Application of existing source apportionment models to nonindustrial indoor environments is only just beginning. It is possible that these models might be used to distinguish between indoor and outdoor emissions, as well as to distinguish among indoor sources themselves. However, before the feasibility and suitability of source-apportionment methods for indoor applications can be assessed adequately, it is necessary to take account of model assumptions and associated data requirements. This paper examines the issue of indoor source apportionment and reviews the need for emission characterization studies to support such source-apportionment efforts.     

Mass balance modelling of contaminants in river basins: a flexible matrix approach

A novel and flexible approach is described for simulating the behaviour of chemicals in river basins. A number (n) of river reaches are defined and their connectivity is described by entries in an n x n matrix. Changes in segmentation can be readily accommodated by altering the matrix entries, without the need for model revision. Two models are described. The simpler QMX-R model only considers advection and an overall loss due to the combined processes of volatilization, net transfer to sediment and degradation. The rate constant for the overall loss is derived from fugacity calculations for a single segment system. The more rigorous QMX-F model performs fugacity calculations for each segment and explicitly includes the processes of advection, evaporation, water-sediment exchange and degradation in both water and sediment. In this way chemical exposure in all compartments (including equilibrium concentrations in biota) can be estimated. Both models are designed to serve as intermediate-complexity exposure assessment tools for river basins with relatively low data requirements. By considering the spatially explicit nature of emission sources and the changes in concentration which occur with transport in the channel system, the approach offers significant advantages over simple one-segment simulations while being more readily applicable than more sophisticated, highly segmented, GIS-based models.     

Effect of a cationic surfactant on the volatilization of PAHs from soil

Purpose

Cationic surfactants are common in soils because of their use in daily cosmetic and cleaning products, and their use as a soil amendment for the mitigation and remediation of organic contaminated soils has been proposed. Such surfactant may affect the transfer and fate of organic contaminants in the environment. This study investigated the effect of a cationic surfactant, dodecylpyridinium bromide (DDPB), on the volatilization of polycyclic aromatic hydrocarbons (PAHs) from a paddy soil.

Materials and methods

The volatilization of PAHs from moist soil amended with different concentrations of DDPB was tested in an open system. The specific effects of DDPB on the liquid?Cvapor and solid?Cvapor equilibriums of PAHs were separately investigated in closed systems by headspace analysis.

Results and discussion

DDPB affects both liquid?Cvapor and solid?Cvapor processes of PAHs in soil. At DDPB concentrations below the critical micelle concentration (CMC), movement of PAHs from the bulk solution to the gas?Cliquid interface appeared to be facilitated by interaction between PAHs and the surfactant monomers adsorbed at the gas?Cliquid interface, promoting the volatilization of PAHs from solution. However, when DDPB was greater than the CMC, volatilization was inhibited due to the solubilization of PAHs by micelles. On the other hand, the formation of sorbed surfactant significantly inhibited the solid?Cvapor volatilization of PAHs.

Conclusions

The overall effect of the two simultaneous effects of DDPB on liquid?Cvapor and solid?Cvapor processes was a decreased volatilization loss of PAHs from soil. Inhibition of PAH volatilization was more significant for the soil with a lower moisture content.     

Air Quality Modeling in the South Coast Air Basin of California: What Do the Numbers Really Mean?

Abstract

This study evaluates air quality model sensitivity to input and to model components. Simulations are performed using the California Institute of Technology (CIT) airshed model. Results show the impacts on ozone (O₃) concentration in the South Coast Air Basin (SCAB) of California because of changes in: (1) input data, including meteorological conditions (temperature, UV radiation, mixing height, and wind speed), boundary conditions, and initial conditions (ICs); and (2) model components, including advection solver and chemical mechanism. O₃ concentrations are strongly affected by meteorological conditions and, in particular, by temperature. ICs also affect O₃ concentrations, especially in the first 2 days of simulation. On the other hand, boundary conditions do not significantly affect the absolute peak O₃ concentration, although they do affect concentrations near the inflow boundaries. Moreover, predicted O₃ concentrations are impacted considerably by the chemical mechanism. In addition, dispersion of pollutants is affected by the advection routine used to calculate its transport. Comparison among CIT, California Photochemical Grid Model (CALGRID), and Urban Airshed Model air quality models suggests that differences in O₃ predictions are mainly caused by the different chemical mechanisms used. Additionally, advection solvers contribute to the differences observed among model predictions. Uncertainty in predicted peak O₃ concentration suggests that air quality evaluation should not be based solely on this single value but also on trends predicted by air quality models using a number of chemical mechanisms and with an advection solver that is mass conservative.     

A mass transfer model for simulating VOC sorption on building materials

The sorption of volatile organic compounds (VOCs) by different building materials can significantly affect VOC concentrations in indoor environments. In this paper, a new model has been developed for simulating VOC sorption and desorption rates of homogeneous building materials with constant diffusion coefficients and material–air partition coefficients. The model analytically solves the VOC sorption rate at the material–air interface. It can be used as a “wall function” in combination with more complex gas-phase models that account for non-uniform mixing to predict sorption process. It can also be used in conjunction with broader indoor air quality studies to simulate VOC exposure in buildings.     

The effects of ozone/limonene reactions on indoor secondary organic aerosols

An indoor air quality model was used to predict dynamic particle mass concentrations based on homogeneous chemical mechanisms and partitioning of semi-volatile products to particles. The ozone–limonene reaction mechanism was combined with gas-phase chemistry of common atmospheric organic and inorganic compounds and incorporated into the indoor air quality model. Experiments were conducted in an environmental chamber to investigate secondary particle formation resulting from ozone/limonene reactions. Experimental results indicate that significant fine particle growth occurs due to the interaction of ozone and limonene and subsequent intermediate by-products. Secondary particle mass concentrations were estimated from the measured particle size distribution. Predicted particle mass concentrations were in good agreement with experimental results—generally within ∼25% at steady-state conditions. Both experimental and predicted results suggest that air exchange rate plays a significant role in determining secondary fine particle levels in indoor environments. Secondary particle mass concentrations are predicted to increase substantially with lower air exchange rates, an interesting result given a continuing trend toward more energy efficient buildings. Lower air exchange rates also shifted the particle size distribution toward larger particle diameters. Secondary particle mass concentrations are also predicted to increase with higher outdoor ozone concentrations, higher outdoor particle concentrations, higher indoor limonene emission rates, and lower indoor temperatures.     

Personal exposure levels and microenvironmental concentrations of formaldehyde and acetaldehyde in the Helsinki metropolitan area, Finland

Personal 48-hr exposures to formaldehyde and acetaldehyde of 15 randomly selected participants were measured during the summer/autumn of 1997 using Sep-Pak DNPH-Silica cartridges as a part of the EXPOLIS study in Helsinki, Finland. In addition to personal exposures, simultaneous measurements of microenvironmental concentrations were conducted at each participant's residence (indoor and outdoor) and workplace. Mean personal exposure levels were 21.4 ppb for formaldehyde and 7.9 ppb for acetaldehyde. Personal exposures were systematically lower than indoor residential concentrations for both compounds, and ambient air concentrations were lower than both indoor residential concentrations and personal exposure levels. Mean workplace concentrations of both compounds were lower than mean indoor residential concentrations. Correlation between personal exposures and indoor residential concentrations was statistically significant for both compounds. This indicated that indoor residential concentrations of formaldehyde and acetaldehyde are a better estimate of personal exposures than are concentrations in ambient air. In addition, a time-weighted exposure model did not improve the estimation of personal exposures above that obtained using indoor residential concentrations as a surrogate for personal exposures. Correlation between formaldehyde and acetaldehyde was statistically significant in outdoor microenvironments, suggesting that both compounds have similar sources and sinks in ambient urban air.     

Concentrations of particulate matter,carbon dioxide,VOCs and risk assessment inside Korean taxis and ships

The objective of this study was to investigate the concentration distribution of indoor air pollutants in taxis and ships (passengers) which are frequently used for public transportation and recreational activities in South Korea. In addition, it aimed to assess air quality factors to establish and evaluate the health risks of exposure to polluted indoor air. Particulate matter (PM₁₀) concentrations were not affected by the number of passengers, time of day, and driving characteristics because there were only a few passengers (2 to 4 people) and the space was confined. In the ships, indoor air pollutants responded more sensitively to the operation characteristics depending on the time of sailing (i.e., anchoring and departure, movement of vehicles on the ship, movement of passengers, combustion in the shop, and ventilation) than to the number of people boarding and alighting. The carbon dioxide concentrations in different ship rooms did not vary according to season and degree of congestion; however, there were differences between different ships. These differences may result from the size, type, and operating characteristics of the ships. Volatile organic compounds (VOCs) and aldehydes in new taxis exceeded the standard levels during summer. VOC concentrations in ships were particularly high during summer when the outdoor temperature was high. Similar observations were made for other means of transportation. The risk assessment depended on the means of transportation and demonstrated that mortality risks due to PM₁₀ and excess carcinogenic and non-carcinogenic risks from VOCs and aldehydes were within safety levels.

     

Characteristics of indoor aerosols in residential homes in urban locations: a case study in Singapore

As part of a major study to investigate the indoor air quality in residential houses in Singapore, intensive aerosol measurements were made in an apartment in a multistory building for several consecutive days in 2004. The purpose of this work was to identify the major indoor sources of fine airborne particles and to assess their impact on indoor air quality for a typical residential home in an urban area in a densely populated country. Particle number and mass concentrations were measured in three rooms of the home using a real-time particle counter and a low-volume particulate sampler, respectively. Particle number concentrations were found to be elevated on several occasions during the measurements. All of the events of elevated particle concentrations were linked to indoor activities based on house occupant log entries. This enabled identification of the indoor sources that contributed to indoor particle concentrations. Activities such as cooking elevated particle number concentrations < or =2.05 x 10(5) particles/cm3. The fine particles collected on Teflon filter substrates were analyzed for selected ions, trace elements, and metals, as well as elemental and organic carbon (OC) contents. To compare the quality of air between the indoors of the home and the outdoors, measurements were also made outside the home to obtain outdoor samples. The chemical composition of both outdoor and indoor particles was determined. Indoor/outdoor (I/O) ratios suggest that certain chemical constituents of indoor particles, such as chloride, sodium, aluminum, cobalt, copper, iron, manganese, titanium, vanadium, zinc, and elemental carbon, were derived through migration of outdoor particles (I/O <1 or - 1), whereas the levels of others, such as nitrite, nitrate, sulfate, ammonium, cadmium, chromium, nickel, lead, and OC, were largely influenced by the presence of indoor sources (I/O >1).     

Validation of Models for Predicting Formaldehyde Concentrations in Residences due to Pressed-Wood Products

This paper describes a laboratory project to assess the accuracy of emission and indoor air quality models to be used in predicting formaldehyde (HCHO) concentrations in residences due to pressed-wood products made with urea-formaldehyde bonding resins. The products tested were partlcleboard underlayment, hardwood- plywood paneling and medium-density fiberboard (mdf). The products were initially characterized in chambers by measuring their formaldehyde surface emission rates over a range of formaldehyde concentrations, air exchange rates and two combinations of temperature and relative humidity (23° C and 5 0% RH; 26°C and 60% RH). They were then installed in a two-room prototype house in three different combinations (underlayment flooring only; underlayment flooring and paneling; and underlayment flooring, paneling, and mdf). The equilibrium formaldehyde concentrations were monitored as a function of air exchange rate. Particleboard underlayment and mdf, but not paneling, behaved as the emission model predicted over a large concentration range, under both sets of temperature and relative humidity. Good agreement was also obtained between measured formaldehyde concentrations and those predicted by a mass-balance indoor air quality model.