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Journal of Environmental Quality 31:1774-1781 (2002)
© 2002 American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America

TECHNICAL REPORTS
Atmospheric Pollutants and Trace Gases

Design and Performance of a Dynamic Gas Flux Chamber

Rivka Reichman*,a and Dennis E. Rolstonb

a Environmental Physics Dep., Israel Institute for Biological Research, P.O. Box 19, Ness-Ziona 74100, Israel
b Land, Air and Water Resources, University of California, One Shields Ave., Davis, CA 95616

* Corresponding author (raichman{at}iibr.gov.il)

Received for publication September 24, 2001.

    ABSTRACT
 TOP
 ABSTRACT
 INTRODUCTION
 THEORY
 MATERIALS AND METHODS
 RESULTS AND DISCUSSION
 CONCLUSIONS
 REFERENCES
 
Chambers are commonly used to measure the emission of many trace gases and chemicals from soil. An aerodynamic (flow through) chamber was designed and fabricated to accurately measure the surface flux of trace gases. Flow through the chamber was controlled with a small vacuum at the outlet. Due to the design using fans, a partition plate, and aerodynamic ends, air is forced to sweep parallel and uniform over the entire soil surface. A fraction of the air flowing inside the chamber is sampled in the outlet. The air velocity inside the chamber is controlled by fan speed and outlet suction flow rate. The chamber design resulted in a uniform distribution of air velocity at the soil surface. Steady state flux was attained within 5 min when the outlet air suction rate was 20 L/min or higher. For expected flux rates, the presence of the chamber did not affect the measured fluxes at outlet suction rates of around 20 L/min, except that the chamber caused some cooling of the surface in field experiments. Sensitive measurements of the pressure deficit across the soil layer in conjunction with measured fluxes in the source box and chamber outlet show that the outflow rate must be controlled carefully to minimize errors in the flux measurements. Both over- and underestimation of the fluxes are possible if the outlet flow rate is not controlled carefully. For this design, the chamber accurately measured steady flux at outlet air suction rates of approximately 20 L/min when the pressure deficit within the chamber with respect to the ambient atmosphere ranged between 0.46 and 0.79 Pa.


    INTRODUCTION
 TOP
 ABSTRACT
 INTRODUCTION
 THEORY
 MATERIALS AND METHODS
 RESULTS AND DISCUSSION
 CONCLUSIONS
 REFERENCES
 
VOLATILIZATION OF soil-applied organic chemicals (e.g., pesticides) from soil to the atmosphere and their vapor transport in air are the principal processes leading to their widespread dispersion in the environment (Glotfelty et al., 1984; Taylor and Spencer, 1990). There are growing concerns over the potential risks from exposure to airborne pesticides and other hazardous materials that have immediate and/or long-term human and ecological health impacts. Accurate measurement of soil trace gases emission to the atmosphere is essential for estimating amounts of hazardous materials emitted into the atmosphere, and thus for assessing the effects of such emissions upon the environment.

A variety of techniques has been developed and used to measure emission in the field (de Mello and Hines, 1994; Denmand and Raupach, 1993; Lenschow, 1995; Hutchinson and Livingston, 1993, 2002; Livingston and Hutchinson, 1995; Majewski et al., 1990, 1995; Rolston, 1986, 1994; Weseley et al., 1989; Yates et al., 1997). Various micrometeorological methods (e.g., aerodynamic method) (Lenschow, 1995; Majewski et al., 1990, 1995; Yates et al., 1997) and enclosure-based methods (e.g., flux chambers) (de Mello and Hines, 1994; Denmand and Raupach, 1993; Hutchinson and Livingston, 1993, 2002; Livingston and Hutchinson, 1995; Rolston, 1986, 1994; Weseley et al., 1989) are the most common. The micrometeorological-based measurements that are frequently used for measuring pesticide volatilization rates require extensive instrumentation and highly sensitive pesticide concentration measurements at different heights in the air (e.g., the gradient method). The treated area also needs to be large to achieve a reasonable fetch. Measuring emission with chamber methods is relatively simple and does not require a large surface area. These methods involve placing an open-bottom chamber over a small area of soil surface and measuring the gas emitted into the chamber. The trapping arrangement may be by passive (or closed) systems or active (or dynamic, flowing) systems. Various assumptions are applied to these chamber methods, and models based on these assumptions have been developed and used to calculate fluxes from the data obtained (de Mello and Hines, 1994; Denmand and Raupach, 1993; Gao and Yates, 1998b; Rolston, 1986, 1994, Livingston and Hutchinson, 1995; Hutchinson and Livingston, 2002). Although some of the assumptions associated with these methods may not be entirely valid under real-world situations, chambers have been used extensively for measuring emissions of a variety of gases due to their simplicity and ease in fabrication and operation. The variety of gases measured includes trace gases, such as CO2, N2O, NOx, CH4, and selenium (Se) (de Mello and Hines, 1994; Fukui and Doskey, 1996; Hutchinson and Mosier, 1981; Jury et al., 1982; Kanemasu et al., 1974; Valente et al., 1995; Lin et al., 1999; Dungan et al., 2000) and volatile organic compounds (VOCs), such as volatile pesticides (Gao et al., 1997; Gao and Yates, 1998a; Sanders et al., 1985; Yates et al., 1997; Yagi et al., 1993; Wang et al., 1997; Woodrow and Seiber, 1991), spilled volatile solvents, and volatile constituents from waste disposal sites (Balfour et al., 1987; Eklund, 1992). Experience gained from numerous applications of both types of flux chambers has shown that both methods have their own advantages and disadvantages. Summaries and comments on the advantages and disadvantages of these chamber methods can be found in the reviews of Hutchinson and Livingston (1993)( 2002), Livingston and Hutchinson (1995), Rolston (1986), Weseley et al. (1989), and Denmead and Raupach (1993).

Although the flux chamber method is probably one of the simplest tools for measuring volatile organic compound volatilization, it can have several disadvantages compared with micrometeorological-based measurements (Yates et al., 1997; Wang et al., 1997). First, when the chamber sampling area is a small fraction of total area for emission, the measured flux could be highly variable due to soil spatial heterogeneity. Next, the presence of the chamber can change the environmental properties (such as soil temperature and the wind profile near the soil surface) of the sampled area compared with the rest of the surface area. This effect on local environment is especially large for the static chambers but may be small for the dynamic chambers if designed and operated properly (Jury et al., 1982; Hutchinson et al., 2000; Wang et al., 1997). Yates et al. (1997) used four independent methods including flux chamber and micrometeorological (aerodynamic, theoretical profile shape [TPS], and integrated horizontal flux [IHF]) methods to estimate the total methyl bromide lost after application. They found a reasonable agreement between fluxes measured using the dynamic chamber and the aerodynamic method, which was better than the agreement between the aerodynamic and the other (theoretical profile shape and integrated horizontal flux) micrometeorological methods where lower rates were obtained.

One major disadvantage associated with dynamic chambers is that the air flowing through the chamber may change the pressure gradient between the soil-gas phase and the chamber interior (Gao et al., 1997; Gao and Yates, 1998a,b; Livingston and Hutchinson, 1995; Hutchinson and Livingston, 1993, 2002; Rolston, 1986). This pressure difference may create advective mass flow of the target gas that will result in an under- or overestimate of emissions, depending on design. In the case of pumping air into the chamber, an underestimation of the flux is most likely, while overestimation can be observed where the air is sucked out (Kanemasu et al., 1974). Another potential problem with the dynamic chamber is associated with the aerodynamic behavior or airflow pattern if not designed properly (Gao et al., 1997). Gao and Yates (1998b) analyzed flux chambers using diffusion theory and mass balance principles. Simulations using a mathematical model for the dynamic chamber showed that the proper measurement of flux depends on both chamber operation conditions and soil air permeability. A dynamic chamber may underestimate the actual flux when operating on low permeability soils. On soils with high air permeability, a dynamic chamber may give an underestimate of the actual flux when operating at low airflow rate but an overestimate when the airflow rate is high. The latter predictions were confirmed in a laboratory study where emission of methylene chloride from a constant source was measured (Gao and Yates, 1998a).

In this paper, we describe a dynamic flux chamber that was designed and fabricated to minimize the bias of underestimation or overestimation of the actual flux. Results from laboratory and field tests are presented and discussed.


    THEORY
 TOP
 ABSTRACT
 INTRODUCTION
 THEORY
 MATERIALS AND METHODS
 RESULTS AND DISCUSSION
 CONCLUSIONS
 REFERENCES
 
In general, a flow-through chamber can be analyzed with the principle of mass balance, that is, the mass change of the target gas within the chamber headspace (dM) is due to the mass input and output, which can be expressed as (Gao and Yates, 1998b):

[1]
where V is the volume of the chamber headspace, dCa is the change of the target gas concentration within the chamber headspace, A is the enclosed soil surface area, Jg is the flux of the target gas at the enclosed soil surface, Q is the airflow rate, and Cin(t) and Cout(t) are the target gas concentrations in the chamber for the incoming air and outgoing air, respectively.

A hidden assumption in Eq. [1] is that the airstream through the chamber sweeps over the entire covered soil surface with a uniform velocity, and its direction is parallel to the enclosed soil surface. If the chamber is operating under steady state, that is, the rate of airflow through the chamber is constant and not a function of time, we have:

[2]
which is a commonly used equation to calculate steady state fluxes for dynamic chambers (de Mello and Hines, 1994; Livingston and Hutchinson, 1995; Hutchinson and Livingston, 1993, 2002; Gao and Yates, 1998a,b; Rolston, 1986; Wang et al., 1997). However, this equation can be used only if the dynamic chamber design follows the above assumptions.


    MATERIALS AND METHODS
 TOP
 ABSTRACT
 INTRODUCTION
 THEORY
 MATERIALS AND METHODS
 RESULTS AND DISCUSSION
 CONCLUSIONS
 REFERENCES
 
Aerodynamic Chamber Design and Fabrication
The aerodynamic flux chamber was designed and fabricated to meet the following criteria.

1. The airflow in the chamber should sweep over the entire enclosed soil surface, eliminating any stagnant air zones in the chamber.

2. The direction of the airflow in the chamber should be parallel to the covered soil surface, and any components of airflow perpendicular to the soil surface should be eliminated.

3. The openings of the chamber's air inlet and outlet should be large enough to minimize pressure changes due to air introduction and to ensure a relatively uniform velocity of airstream in the chamber at the desired air flow rates.

4. Air velocity inside the chamber should be as close as possible to the ambient conditions, approximately 1 and 4.5 m/s for 2 cm and 2 m above the soil surface, respectively. These values were obtained with the logarithmic profile equation (Eq. [3]) that is commonly used to describe the vertical wind velocity distribution in the Ekman layer (turbulent boundary layer) (McIlveen, 1986) with u* = 0.3 m/s (a centered value of a wide range of measurements; McIlveen, 1986) and z0 = 0.5 cm (laminar boundary layer depth):

[3]
where v is the vertical wind velocity, u* is the friction velocity, k = 0.4 is von Karman constant, z is the vertical coordinate, and z0 is the aerodynamic roughness length.

5. The pattern of airflow in the chamber should be relatively uniform across the soil surface to simplify the analysis of such flow.

6. The outside surface of the chamber should reflect solar radiation so that radiant heating can be effectively reduced.

7. Material for chamber fabrication should be strong and rigid to avoid structural deformation under field conditions.

The flux chamber, schematically shown in Fig. 1 , consists of a large air inlet (2.5 cm), main body (40 x 40 cm) divided into two sections by a partition plate, five fans, aerodynamic edges, and air outlet. The entire chamber body was made with 20-gauge galvanized sheet metal. Due to the design using fans, a partition plate, and aerodynamic ends, air is forced to sweep parallel and uniform over the entire soil surface. A fraction of the air flowing inside the chamber is sampled in the outlet. The air velocity inside the chamber is controlled by fan speed and outlet suction flow rate (Q).



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Fig. 1. Schematic diagram of the flux chamber: (a) side view and (b) top view.

 
Laboratory Tests
Two sets of laboratory tests were conducted: (i) aerodynamic behavior, and (ii) constant source flux measurement in conjunction with pressure deficit measurement.

Aerodynamic Behavior
To study the aerodynamic behavior of the chamber and to evaluate whether it meets the design criteria, the air velocity distribution within the chamber was measured with a hotwire anemometer Model W-141-A (Weather Measure Corporation, Sacramento, CA). The air velocity inside the chamber was measured at 16 evenly distributed points, shown schematically in Fig. 1b, at the height of 1.3 to 2.3 cm above the soil surface. The velocity distribution was measured for different fan positions and outlet suction flow rates while the chamber was set up as shown in Fig. 2 .



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Fig. 2. Experimental setup.

 
Flux Measurement
A possible chamber effect on flux measurements was studied with a constant emission source of Freon 113. Over the course of the study, the chamber was tested for (i) its time response for steady flux measurement and (ii) the outlet air suction rate (Q) and the inside air velocity (v) effects on measured steady state flux.

These tests were performed with the experimental system shown in Fig. 2 that consisted of a constant source box, a layer of soil supported by a screen above the source, chamber, and air flow system. During the experiments, the apparatus was placed in a laboratory fume hood at 25°C ambient temperature.

Constant Source Box. The constant source was an open top box (75 x 75 x 21.5 cm) packed with 7.5 cm of fine sandy soil creating a 14-cm chamber for the vapor source. The chamber base (40 x 40 x 5 cm) covers only a part of the soil surface area leaving some soil area open to the atmosphere. Liquid Freon 113 was introduced through a burette connected to the input port into a Petri dish. A fan achieved mixing inside the chamber. The Freon was allowed to evaporate for 4 to 6 h to establish steady state flux conditions prior to chamber tests. Sampling and analyzing gaseous Freon at several points within the source box confirmed Freon uniformity and well-mixed conditions inside the box.

Soil Properties. The soil used in this study was Oso-flocco sand classified as fine sand. The bulk density was 1.57 g/cm3, and the air permeability was 2 x 10-11 m2.

Chemical Properties. Freon-113 (1,1,2-trichloro-1,2,2-trifluororthane), a volatile organic liquid, was the constant vapor source chemical in this study. Due to its boiling point (47.6°C), Freon 113 evaporates from its liquid phase under ambient temperature and can provide a vapor source of constant concentration. It also has low toxicity and low adsorption (Altevogt, 2001) to sand compared with other volatile organic solvents with the same volatility. The Freon-113 (Fisher Scientific Co., Fair Lawn, NJ) used in these experiments was of Optima grade purity. Other chemical–physical properties are summarized in Table 1.


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Table 1. Freon 113 properties.

 
The Freon concentration in the chamber outlet was sampled with a 50-µL syringe and analyzed by a SRI (Torrance, CA) 8610 gas chromatograph with flame ionization detection. High concentrations were diluted with 5-mL bottles prior to analysis.

Pressure Deficit
The pressure deficit between the soil surface inside the chamber and the outside open air and across the soil layer (P2–P1; Fig. 2) was measured with an Omega Engineering (Stamford, CT) Model PX2670 differential pressure transducer (range: ±25 Pa; sensitivity: 0.01 Pa). The pressure deficit was measured for different air velocities and outlet suction flow rates.

The pressure deficit influence on the measured soil emissions was studied by simultaneous measurement of fluxes in the source box, chamber outlet, and pressure deficits across the soil layer for three air velocities and three outflow suction rates. Emission rate from the source box was determined from the changing mass of the Freon source measured with a balance (Ohaus [Florham Park, NJ] Scout II Model SR2020) inserted into the source box.

Field Tests
Chamber effects on soil temperature were studied at a University of California-Davis experimental field during July 2000. The soil at the site is Yolo silt loam (22% sand, 56% silt, 22% clay and 1.9% organic matter) and is classified as fine-silty, mixed, superactive, nonacid, thermic Mollic Xerofluvent. Bulk density of the upper 2 cm was 1.2 g/cm3.

Soil temperature was measured at two depths (1 and 5 cm) with a Campbell Scientific (Logan, UT) 101 thermistor probe. The dependence of soil temperature deviation on the duration that the chamber was in place, time of day, and soil moisture was evaluated. The chamber effect on soil temperature was determined from the deviation of the measurement from that expected from the normal diurnal temperature curve.


    RESULTS AND DISCUSSION
 TOP
 ABSTRACT
 INTRODUCTION
 THEORY
 MATERIALS AND METHODS
 RESULTS AND DISCUSSION
 CONCLUSIONS
 REFERENCES
 
Aerodynamic Behavior
The results for air velocity distribution within the chamber as a function of three average flow velocities are summarized in Table 2 and shown in Fig. 3 . The average air velocity at 1.3 to 2.3 cm above the soil surface varied in the range of 1.06 to 1.26 m/s, a velocity consistent with the design criteria. The low coefficient of variation (6–8%) suggests a fairly uniform distribution of air velocity within the chamber. The outlet suction rate showed no effect on air velocity distribution.


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Table 2. The average and standard deviation of velocity inside the chamber.

 


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Fig. 3. Distribution of air velocity in the chamber.

 
Pressure Deficit and Flux Comparisons
Pressure deficits between the soil surface within the chamber (P1) and the open atmosphere (OA) ({Delta}POA-P1), and across the soil layer ({Delta}PP2-P1) as a function of outlet air suction for three different average air velocities within the chamber are summarized in Table 3. These two pressure deficits for the three different average air velocities are directly related and fit a 1:1 line (not shown). The results show that the pressure deficit increases with increasing outlet air suction and air velocity within the chamber. The pressure at the soil surface within the chamber (P1) was lower than the open atmosphere pressure (OA) and the pressure at the soil lower boundary (P2). Pressure deficit values measured across the soil layer were similar to pressure deficit values measured between the open atmosphere and the soil surface within the chamber except for v = 1.15 m/s, where they were higher (Table 3).


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Table 3. Pressure deficits measured between the open atmosphere (POA) and the soil surface inside the chamber ({Delta}POA-P1), and across the soil layer ({Delta}PP2-P1) as function of outlet suction rates for three different average velocities inside the chamber.

 
Fluxes measured in the chamber outlet vs. fluxes in the source box and the pressure deficit across the soil layer for three outlet air suction rates and three air flow velocities within the chamber are given in Fig. 4 through 6 . Results show that the steady state flux was attained within 5 min when the outlet air suction rate was 20 L/min or higher for the three air velocities. Data not shown demonstrate that two different source strengths did not have an influence on the time to attain steady flux. Comparison between emission rates measured in the source box and from the chamber outlet show a high accuracy when (i) outlet suction rate is 20 L/min for the three average velocities (Fig. 4b, 5b, and 6b) and (ii) outlet suction rate is 30 L/min and the average velocity is 1.05 m/s (Fig. 6a) and/or 1.15 m/s (Fig. 5a). For these cases, the pressure deficit across the soil layer and between the open atmosphere and the soil surface within the chamber varied in the range of 0.46 to 1 Pa and 0.43 to 0.79 Pa, respectively. Underestimation of the soil emission was observed with a suction rate of 10 L/min (Fig. 4c, 5c, and 6c). This underestimation of the flux occurred apparently because the outflow rate from the chamber was not sufficient to keep up with flux through the soil, although there was still a pressure deficit that ranged between 0.1 to 0.27 Pa. Overestimation of soil efflux was observed only when the air velocity was 1.26 m/s, and the suction rate was 30 L/min (Fig. 5a) with pressure deficits greater than 1 Pa (1.13–1.18 Pa).



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Fig. 4. Fluxes measured in the chamber outlet vs. fluxes measured in source box and pressure deficits across the soil layer for v = 1.26 m/s and (a) Q = 30 L/min, (b) Q = 20 L/min, and (c) Q = 10 L/min.

 


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Fig. 6. Fluxes measured in the chamber outlet vs. fluxes measured in source box and pressure deficit across the soil layer for v = 1.06 m/s and (a) Q = 30 L/min, (b) Q = 20 L/min, and (c) Q = 10 L/min.

 


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Fig. 5. Fluxes measured in the chamber outlet vs. fluxes measured in source box and pressure deficit across the soil layer for v = 1.15 m/s and (a) Q = 30 L/min, (b) Q = 20 L/min, and (c) Q = 10 L/min.

 
Results from the dynamic chamber tests, reported in Gao and Yates (1998a), indicate that the steady state flux may underestimate flux when the chamber is operating at low airflow rates and pressure deficit (within the chamber with respect to the ambient pressure) is less than 0.25 Pa, but overestimate the actual flux at high airflow rates when pressure deficit is higher than 1 Pa (Fig. 7 and 8 in Gao and Yates, 1998a). This effect was observed for both fine and coarse sands with air permeability of 3.2 x 10-6 and 3 x 10-5 cm2, respectively. These results, obtained under laboratory conditions with an experimental configuration similar to the configuration reported in the current study, with methylene chloride as the constant source chemical, support the present findings (e.g., Fig. 46). However, the pressure deficit influence on measured soil efflux can be larger in some field situations. For example, for forest soils with a high organic matter surface horizon, Lund et al. (1999) and Longdoz et al. (2000) found a change of 70 and 20%, respectively, in soil CO2 efflux due to a 0.5-Pa pressure deficit. The dependence of these results on soil air permeability and rate of CO2 gas production may explain the differences from our results. For moist soils, particularly of loamy or clayey texture, it would be expected that the air permeability would be at least one or two orders of magnitude smaller than for the sand used in this study. Thus, the advective flux due to a pressure deficit in the chamber would be expected to have a lesser effect on the measured flux.

Soil Temperature
Chamber effects on soil temperature at two soil depths for two soil surface moisture conditions (Fig. 7) show that the chamber depressed soil temperature. The extent of soil cooling depended on soil depth, soil moisture conditions, time of day, and time period that the chamber was in place. Chamber effects on soil temperature at 5 cm were negligible compared with 1 cm, especially under wet soil conditions. The decrease in temperature under dry soil conditions was three times higher (maximum 6–9°C) compared with wet soil conditions (maximum 2–3°C) for the same time of day. The maximum cooling was observed during the period between 1400 and 1600 h. Generally, the longer the chamber was in place, the greater the soil cooling. However, significant cooling was observed only during the afternoon hours (1400–1600 h), which is a small portion of the diurnal period of time (8%). On a daily basis, the average soil temperature perturbation was about 1.5°C, which is expected to cause only small errors in flux measurements. The main effect of this perturbation could be observed only on the diurnal pattern of flux measurement. We expect that during the midday and early afternoon hours, the observed volatilization rates will be lower due to the lowered soil temperature. As a result, higher pesticide concentrations will remain in the soil surface layer, enhancing the volatilization rates during the late afternoon hours. More field experiments and/or modeling will need to be done to fully understand this effect and test its magnitude.



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Fig. 7. Chamber effect on soil temperature at two depths for two soil surface water contents.

 

    CONCLUSIONS
 TOP
 ABSTRACT
 INTRODUCTION
 THEORY
 MATERIALS AND METHODS
 RESULTS AND DISCUSSION
 CONCLUSIONS
 REFERENCES
 
The chamber design described above provides a practical tool for accurate measurements of surface gas fluxes from soils. Performance test results show that (i) there was a uniform distribution of air velocity within the chamber at the soil surface, (ii) steady state flux was attained within 5 min when the outlet air suction was 20 L/min or higher, (iii) the presence of the chamber did not affect the measured flux for outlet suction rates of 20 L/min, except that the chamber caused some cooling of the surface soil that could have an effect on volatilization of chemicals, and (iv) the chamber measured soil efflux accurately when pressure deficit within the chamber with respect to ambient atmosphere ranges between 0.46 and 0.79 Pa. Pressure deficits larger than 1.2 Pa caused a 20% overestimation in measured steady state flux. Underestimation of measured steady state flux was observed for the outlet suction rate of 10 L/min, apparently due to a buildup of gas in the chamber, a decrease in the concentration gradient across the soil, and thus a decrease in the flux. The optimum outlet flow rate to use for a dynamic chamber will be dependent upon soil type and water content conditions (which influences the air permeability) and to some degree on gas production rates in the soil. The outlet flow rate must be large enough to not significantly affect the concentration gradient across the soil surface and not so large as to cause significant pressure deficits within the chamber. This paper provides some guidance in design, but we recommend that dynamic chambers be instrumented with sensitive pressure transducers to monitor and minimize the pressure deficit that will occur.


    ACKNOWLEDGMENTS
 
This research was supported by the NIEHS Superfund Basic Research Program (P42ESO4699) and the USEPA Center for Ecological Health Research (R819658, R825433) at the University of California-Davis. Although the information in this document has been funded in part by the USEPA, it may not necessarily reflect the views of the Agency and no official endorsement should be inferred. We thank Dianne Louie, Matt Quok, and Jakov and Edan Reichman for their assistance with some of the experiments.


    REFERENCES
 TOP
 ABSTRACT
 INTRODUCTION
 THEORY
 MATERIALS AND METHODS
 RESULTS AND DISCUSSION
 CONCLUSIONS
 REFERENCES
 




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