Volume Estimation of Light Nonaqueous Phase Liquids in Porous Media by A.M, Farr, R. J. Houghtalen”, and D. B. McWhorter® ABSTRACT An analytie method is deseribed for estimating the volume of mobile Light Nonaqueous Phase Liquids (LNAPL) in porous media from observed LNAPL. thick nesses in monitoring wells. Static (mechanical) equilibeium Of fluids in a homogeneous porous medium isthe key con: dition on which the method is based. Both the Brooks Corey and van Genuehten equations, with paramecers derived from laboratory column experiments reported in the literature, are used to relate fluid contents ro capillary pressures, The calculations show that LNAPL in the vadose zone does not distribute iself as a distinct layer floating on, the top of a capillary fringe, Rather, the traditional concept of a capillary fringe is not applicable when LNAPL. is present. Further, neither the LNAPLL level nor the water level in monizoring wels is equal to the water table eleva- tion. The water table, being the surface on which the water pressure is zero gage, is located above the LNAPL-water interface in the well, and LLNAPL. in the porous media will reside below the water table It is shown that finite volumes of LNAPL theoretically can exist in materials with positive entry pressures (eg Brooks-Corey porous media) without revealing their presence in the form of an LNAPL. layer in monitoring wells, However, LNAPL. in porous media with zero entey pressure will always appear in monitoring wells, rogardless| fof the volume of LNAPI. in the porous medium. In addi tion, the theory shows that the ratio of the volume of LNAPL per unit area in the vadose zone to the thickness of ENAPL in monitoring wells is strongly dependent upon the capillary properties of the porous medium. Only in porous ‘media with very uniform pore sizes is the volume of LNABL in the vadose zone approximately proportional to the thickness of LNAPL in monitoring wells. senior Geohydrologist, Kennedy /Jenks/Chilton, 303 Second St., San Francisco, California 94107. Associate Professor, Civil Engineering Department, Ruse-Hulmen Institute of Technology, Teere Haute, Indiana 47803, “professor, Agricultural and Chemical Engineering Department, Colorado State University, Fort Collins, Colorado 80523, Received November 1988, revised May 1989, accepted June 1989, Discussion open until July 1, 1990, 48 INTRODUCTION The use of organic chemicals such as hydro- carbon fuels and chlorinated solvents is common: place in all of industrialized society. It is hardly surprising that subsurface contamination by these substances has become a correspondingly wide: spread problem. Frequently, organic compounds center the subsurface as constituents of a nonaque- ‘ous phase liquid (NAPL). Liquids less dense than water are referred to as LNAPLs (cg., gasoline). Such liquids enter the subsurface from a spill or leak and then accumulate in the vadose zone. ‘Their presence is often manifested by the occurrence of the LNAPL in monitoring wells ‘The relationships between the vertical distribu- tions of water, LNAPL, and air in the porous medium and the corresponding distributions of, these fluids in monitoring wells is very complex in the general case of fluctuating water levels in heterogeneous materials. A first step toward under- standing these relationships is afforded by an analysis of three-phase distributions under mechanical equilibrium in homogeneous porous media, We present such an analysis in this paper. The condition of static equilibrium is key. ‘Together with observed fluid levels in monitoring wells, it permits calculation of the spatial distribu- tions of LNAPLe-water and air-LNAPL capillary pressures in the porous medium (Corey, 1986). Then prescribed functions relating fluid contents and capillary pressures can be translated directly to spatial distributions of fluid content. (Hysteresis in the functions relating fluid content to capillary pressures is not considered in this analysis.) Finally, vertical integration of the LNAPL content yields the volume of LNAPL in the porous medium per The above procedure results in volume esti mates that are dependent upon the densities and interfacial tensions of air, LNAPL, and water, The relevant porous medium properties are incorporated through the functions used to relate fluid contents, Vol. 28, No, 1 GROUND WATER January-February 1990eu © aren SESE TS] sect soe 8m 02,9 00 © Oo] Thonracant S00. goo 58 ——— 78 (oer LNA PL ane Air One-Pnote Zone 0888 wwe to capillary pressures (Brooks and Corey, 1966; Lenhard and Parker, 1988; van Genuchten, 1980). ‘These functions relate only to the continuous fluids; thus, any entrapped and/or residual LNAPL that may exist is not accounted for in the method presented here, The method applies in principle to both homogeneous and stratified porous media, For stratified media, relationships between fluid contents and capillary pressures for each stratum are required, and the analysis becomes more com- plex. Only homogeneous media are treated here, Following the development of the relevant equations for LNAPL volume, computations are presented for several porous media/fluid systems, In this way, the sensitivity of the calculated LNAPL volume to the properties of the fluids and porous media is explored, Both the Brooks-Corey Cy ( and van Genuchten equations are used to relate fluid contents to capillary pressures. Computations were performed by use of FORTRAN computer codes, EQUATIONS FOR VOLUME OF LNAPL Figure 1 is a conceptual illustration of one physically possible distribution of water, LNAPL, and air in a porous medium. In this figure, the Circles represent the continuous pore volume which is occupied by one of the three fluids. The space between the circles represents the porous medium, Residual LNAPL is assumed to be absent from the upper region of the porous medium in this repre sentation, For volatile LNAPLs, this upper region would be depleted by volatilization and upward transport to the ground surface. Any entrapped LNAPL is not shown in this figure Figure 2 (a) is a quantitative depiction of the static distribution of fluids that is qualitatively shown in Figure 1. The saturation, §, isa fraction of the pore volume. ‘The shaded area Vo represents the volume of nonresidual LNAPL in the porous medium. Throughout this paper, the focus is on LNAPL in excess of any residual immobile LNAPL that may exist. ‘The symbol D represents a depth measured from the ground surface. The subscript w on D denotes a depth measured in an observation well open for fluid entry over its entire length. The subscript a on D denotes a depth measured in the porous medium penetrated by the observation well. The superscripts w, o, and a refer to water, organic liquid (LNAPL), and air, respectively. The fe a To | (WATER) ° i |-rorous MEDIUM 4 Wei 2, Representative distributions of LNAPL in @ porous medi s———— | PoRGUS MEDLM —-f oeeeees eo evosius weowm —| \ WELL WELL und monitoring well 49depth Di° is the depth in the porous medium at which the air-onganie capillary pressure is the minimum required for continuous air and organic liquid to exist simultaneously within a representa- tive volume element. Similarly, the depth Dg is, the depth in the porous medium at which the organie-water capillary pressure is the minimum. required for continuous organic liquid and water to exist simultaneously. Corey (1986) refers to the minimum capillary pressure required for the coexistence of two con- tinuous fluids in a representative volume element as the entry pressure. The Brooks and Corey (1966) displacement pressure closely approximates the entry pressure (Corey, 1986), and in the remainder of this paper we will consider these terms synony- mous, Some researchers (eg, van Genuchten, 1980) take the entry pressures to be zero, The values of the entry pressures are usually devermined via laboratory measurement of the relation between capillary pressure and fluid saturation for small soil samples and the fluid pairs of interest ‘The water table, being the surface on which the water pressure is zero gage, is shown in Figure 2 to be above the water level in the well by an amount h. Equality of pressures between the water in the well and in the adjacent porous medium requires this to be the case and, further, that Po ow ney w where po = density of the organic liquid, pw = density of the water, and T= D2 ~ D& is, the thickness of the LNAPI, layer in the monitoring well. Thus, the level of neither LNAPL nor water in the monitoring well is equal to the water-table elevation, It is to be noted that the LNAPL does not form a distinct layer floating on top of a capillary fringe. Such a distribution would violate the fundamental equations that describe the fluid pressure distributions in the porous media and in the monitoring well under the condition of mechanical equilibrium. Pore-water pressure above the water table is negative relative to atmospheric pressure. Likewise, LNAPL. in the porous medium located above the air-LNAPL interface in the observation well exists at negative gage pressure ‘The values of D3? and D2 are readily calc lated from hydrostatics (Corcy, 1986) with knowledge of the relevant displacement pressures and the interface levels in an observation well. The following results are obtained: pe Dx = Dy - Q bok 50 pow ow 3 Oe Oe Fo) 7 new where Pi? = air-organic displacement pressure, 2” = organic-water displacement pressure, and = acceleration of gravity. Equation (3) can be writcen as, Pe pew = pa + 7-4 co (ow ~ bo) Because D2™ must always be greater than or equal 10 Di, itis concluded that equations (2) and (3) are applicable only for pow ‘ TS 6 (ow ~ WE ’ From a physical point-of-view, inequality (5) expresses the condition that if any of the LNAPI. in the porous medium exists at positive pressure i.c., Do” > Di), there will result an LNAPI. layer in the observation well that is at least PS" pw ~ bo) units thick, On the other hand, if the volume of LNAPL per unit area in the porous medium is less than a critical value, all LNAPL will exist at negative gage pressures, and equations (2) and (3) do not apply. In such a case the LNAPL zone in the porous medium is positioned above the fluid level in the well as shown in Figure 2(b). Note that the observation well does not reveal the presence of the LLNAPL in the subsurface in this case. The critical volume that must be exceeded to result in the presence of LLNAPL in the well is given explicitly at a later point in the analysis. It is, important to note that even a very small excess (theoretically infinitesimal) of the critical volume will cause T to jump from zero to PE ow ~ Pod 8. Porous media for which the displacement pressures are effectively zero will not result in the above discontinuous behavior of the relationship between LNAPI. volume in the porous medium and the thickness of LNAPL in the observation well. The distribution of fluids in porous media zero displacement pressure will be as shown in Figure 2(c), and the function Vo(T) will be con- tinuous for all T > 0 [where Vo(T) = volume of, LNAPL in the porous medium corresponding to a thickness T of LNAPL. in a well], The significance of Vo(0) = 0 is thar the presence of any nonresidual LNAPL in the porous medium, regardless of its volume, will be revealed by the presence of LNAPL, in the observation well. With reference to Figure 2(a), the volume ofnonresidual LNAPL in the porous medium is given by Vo=e{ f* (1~Sw)dz- byt J* I~ Gw +S0)] dz} ©) pe where Vo = volume of organic liquid (LNAPL) in porous medium per unit area [L.], ¢ = porosity of medium, Sw = saturation of water, Sq = saturation of organic liquid, z = vertical coordinate measured positive downward [L], and other symbols are as previously defined. The values for D3? and DE are determined from equations (2) and (3) respectively for porous materials with nonzero entry pressures (e.g., Brooks-Corey porous media) The displacement pressures in equations (2) and (3) are set equal to zero for porous media with zero entry pressures (eg., van Genuchten porous media). The symbol D0" denotes the depth to the top of the body of continuous LNAPL., While it is possible for continuous LNAPL to extend to the ground surface, such a situation requires either a large volume of LNAPL. in the porous medium and/or small depths to the water table. If con tinuous LNAPL does extend to the ground surface, the lower limit in the integrals of equation (6) ate zero. In all other cases, 3°" is calculated as the point at which the saturation of LNAPL is zero. The specific manner in which this is accom- plished is clarified in subsequent paragraphs. Evaluation of equation (6) requires that the relationships Sy(z) and Sp(z) be known. Brooks and Corey (1966) and van Genuchten (1980) present algebraic equations that express fluid contents as a function of capillary pressure in two- fluid systems. Lenhard and Parker (1987, 1988) used concepts first proposed by Leverett (1941) to extend two-phase relationships to predict three- phase relationships. In a fluid system comprised of ait, LNAPL, and water these concepts can be stated as: (1) the total liquid saturation is a function of the capillary pressure on air-LNAPL. interfaces, independent of the individual saturations of water and LNAPL; and (2) the water saturation isa function of the capillary pressure on LNAPL- water interfaces, Based on the above, the required fluid content relations can be expressed as Pe oy 20 5 pio $5w= (SENS, , PS PH (7a) Py So * Sw=1 » P< PHP (7b) +S, PONS PY” (Ba) Swot » P< Pe (Bb) using the Brooks-Corey (1966) equation, Alterna- tively, use of the van Genuchten (1980) equation gives So + Sy = (I= §) (JM 48, n> 1+ ayo PEP} (9 Sw = (1S) 45, n> 1 Te GoW PY (10) where S; = residual saturation of water, 2 = Brooks-Corey pore-size distribution index, van Genuchten fluid/soil parameter, and n= van Genuchten soil parameter. The final step is to relate equations (7) and (8) or equations (9) and (10) to equation (6) through PE = po g(Dyy ~ ipo 2) +P (11) and Pew = Apg(DYY ~ PYM /Apg- 2) +PY™ (12) where 49 = pw ~ po: Equations (11) and (12) follow from the condition of mechanical equilib- rium, The displacement pressures in equations (11) and (12) are simply set equal to zero for use in conjunction with equations (9) and (10). ‘The depth at which the saturation equations predict So = 0 is the depth to the top of the body of continuous LNAPL, DY Integration of equation (6) for Dio” > 0, using the Brooks-Corey relationships [equations (7) and (8)], together with (11) and (12), yields equation (13) after some algebraic manipulation. ve Ae (d+ (1- dC /D)= (DY), #1 (13a) Vo =¢(1-S)[1-D(4+InT)], A=1 (13b) where ad APE Mok . and T= De — D> PN /Aog When continuous LNAPL extends to the ground surface, D2" doesn’t exist, and integration of equation (6) using the Brooks-Corey equation results in the following: 5st, pogDee p= 0(1- 8) (CT—D)- — 2 — 1-2, Pod). Fo ia aogpet ot ER) net ty Apg(1-) Py” ee = Vo = 61-8) (T= D)- = in Dg +—* In DEE} 0B bok ,A=1 (14b) The results in equation (14) show Vo to be dependent upon the fluid levels in the well (relative to ground surface). This is in contrast to equation (13) in which Vo depends only upon the difference in fluid levels. As noted previously, equations (2) and (3) require that T be equal to or greater than PO"/apg for a Brooks-Corey porous medium with displacement pressure # 0. The critical volume, below which all the LNAPL is at negative gage pressure, follows from equations (13) upon setting T = PS"/Apg. Further, it is observed that equation (13) predicts the linear relation Vo = 6(1~ S) D(TID ~ 1) (as) for large A. Large ) are realized in porous materials, with very uniform pore sizes (Brooks and Corey, 1966). The unconsolidated sand used in the example of the next section is such a material. Finally, for sufficiently large T/D, equation (15) becomes Vo = 91 - ST (16) ‘The product 9(1 ~ SP), called the effective porosity by Brooks and Corey (1966), is usually in the range of 0.2 to 0.4 for soils ‘When using the van Genuchten equation, equation (6) cannot be integrated in closed form and must be evaluated numerically. Thus, conclu- sions concerning the dependence of Vo on various factors is not apparent from the form of the equation, but must be assessed through comparison of solutions for different porous media/fluid systems. These conclusions are addressed in following sections, EXAMPLE — ESTIMATE OF GASOLINE VOLUME IN AN UNCONSOLIDATED SAND Before proceeding to the computations involv- ing various fluid/porous media combinations, a simple example of gasoline in a sand is presented, Capillary pressure-saturation data were collected for an unconsolidated sand by Laliberte, Corey, and Brooks (1966) using air and Soltrol. These 52 data were fit to the Brooks-Corey and van Genuchten equations using a nonlinear least- square regression. The Brooks-Corey best-fit parameters were: S; = 0.0910, \ = 4.02, and Py = 5.210 cm H;0 (for Soltrol). The van Genuchten best-fit parameters were: Sp = 0,100, n = 8.00, and ago = 0.153 em? HO (for Soltrol). These two-phase saturation-pressure relationships can be extended to predict three- phase relationships as discussed by Lenhatd and Parker (1987). The interfacial tensions for the three fluid pairs of interest can be used to estimate the values of Pg (Brooks-Corey) or « (van Genuchten) for the other fluid pairs using eae an and a0 Fao = &wo Fwo = Saw Faw (18) where oj = surface tension between fluids i and j Following the assumption made by Parker et al (1987), S is considered as a porous media property, independent of fluid properties. The parameters \ and n are considered to be constant porous media properties as well. To extend the Soltrol/air capillary pressure-saturation data to air/water/gasoline, the following surface tension ‘measurements were utilized: Gao (dynes/em) dow (dynes/cm) Gasoline 20.2 12.2 (fresh) 22.5 9.8 (aged) Solirol 24.2 442 ‘The sources of these measurements are referenced in Table 2. Figure 3 illustrates the predicted volume of gasoline in the porous medium per unit area as a function of the thickness of the gasoline that would be observed in a monitoring well. ‘These calculations were made assuming that gasoline does not extend to the ground surface. This figure shows that the van Genuchten and Brooks-Corey-based equations arrive at approximately the same estimate of gasoline in the porous medium for volumes greater than 1,765 em?/em®. It also demonstrates that the volume of gasoline in the porous medium, expressed asa depth, is about 30 percent of the thickness, T, of gasoline in the monitoring well for sufficiently large '. This is in rough agreement with the one-to- four “rule-of-thumb” that has been used to estimate LNAPL volumes (CONCAWE, 1979). However, subsequent calculations will show this rule to be generally unreliable, Figure 3 also shows an important differencebetween the two predictions for small volumes. ‘The prediction based on the van Genuchten ‘equation is continuous, showing a single-valued volume for all thicknesses in the monitoring well ‘On the other hand, the calculations based on the Brooks-Corey equation predict that up to 1.765 cm®/em? of gasoline can exist in the porous medium without causing any gasoline to be present in the monitoring well. In other words, up to 1.765 cm°fem? of gasoline can be retained in the sand under negative gage pressure. A small quantity of gasoline (theoretically an infinitesimal quantity) in excess of 1.765 cm'/em? will cause gasoline to appear in the monitoring well at a thickness of 10.1 cm. This thickness is equal to the quantity Pi" /A0g [see inequality (5)]. Both the Brooks- Corey and the van Genuchten equations fit the ‘measured capillary pressure-saturation data quite well. However, the subtle difference in interpreta: tion of the data near Sy = 1, as implied by the differences in these equations, results in an impor- ® Fig. 3. Volume of gasoline in @ porous media for an uncon- solidated sand, van Genuchten vs. Brooks-Corey-based t i i Fig. 4. Volume of gasoline in an unconsolidated sand, ‘van Genuchten-bated equation, ble 1. Properties of Porous Medi Unconsolidatea soils Porous medium O %Sand Sit % Clay Fox Hill, sandstone’ 0.0863 — Dakora 4, sindstone! 0.149 - Lyons4,sandstone' 0.215. Toucher siltloam? 0.43032, 53S Columbia sandy loam? 0.428 $4351 Unconsolidated sand? 0.424 «9064 Sandy porousmedia? 0.415 925 3 White (1966) ? Laliberte, Corey, and Brooks (1968), * Lenhard and Parker (1987) tant difference in the predicted function Vo(T) for small volumes of LNAPL in the porous medium, Figure 4 shows the predicted volume of gasoline in the sand based on two different measurements of dow : (a) being a fresh sample prior to volatilization and (b) being the same sample after volatilization has been allowed to occur. The figure shows that as dow decreases and ogo increases, the volume of predicted LNAPI. in the porous medium will increase slightly. SENSITIVITY OF LNAPL VOLUME ESTIMATES TO SOIL TYPE AND LNAPL PROPERTIES To assess the sensitivity of the LNAPL, volume estimates to soil type and LNAPL properties, laboratory measured capillary-saturation data were selected representing porous media ranging from sandstones to silt loams. Five LNAPLs (Soltrol, benzene, o-xylene, p-cymene, and gasoline) were considered. The physical properties of these soils and fluids are summarized in Tables 1 and 2. The data for these examples were obtained from Parker et al, (1987), White (1968), and Laliberte, Corey, and Brooks (1966). In most of the experiments referenced above, Table 2. Fluid Propertios Fiuid _pgiem?) Oyo (dynesicm) _Ogy (dynes/em) Gasoline’ 074 20.2 12.2 (freshy*| 225 9.8 (aged) Soltro 0.785, 24.2 442 Benzene? 0.879 28.9 35.0 Oxylene? 0.8573 30,53 36.1 Peeymene? 0.88 28.09 364 ¥ Measured by J. M, Farr for 85 octane RON unleaded gasoline, CSU. * Lenhard and Parker (1988), 8 Lenhard and Parker (1987) * Firse measurement made on a “fresh sample,” second measurement made after the sample had been allowed to volasilize, with a 60% loss of the original gasoline volume, 53Table 3, Brooks-Corey Parameters Table 4. van Genuchten Parameters Porous medium SPE soe Fox Hil 1 A098 1.2528 38.506 0.04216 Dakota + 0.0921 1.8373 33.356 0.03910 Lyons 4 0.0242 1.2182 20.473, 0.04363 Touchet silt loam (0.3950 1.8320 73.450 0.00683, Columbia sandy loam 0.0379 1.2420 54.080 0.02870 Unconsolidated sand 0.0910 4.0200 $.210 0.07420 Sandy porous media? 0.075 0.5360 9.675 NA Tin em of water for 0 = Soltrl. 2 Converted from benzene data NA = Information not available capillary pressure-saturation data were measured for only two fluids, usually Soltrol and air, Where no data existed for the same soil with different fluids, the owo-phase saturation-pressure relation- ships were extended to predict three-phase relation- ships as discussed by Lenhard and Parker (1987). ‘The saturation-pressure data for all the porous media listed in Table 1 were fit by the Brooks-Corey and van Genuchten equations using a nonlinear least-square regression. The best-fit parameter values are summarized in Table 3 for the Brooks-Corey equation and in Table 4 for the van Genuchten equation. Comparing the sum of squares deviations [= 3 (prediction - observation)? } for the best fit of these two models, it is observed that the van Genuchten model provides a slightly better fit to the data, although both models provide relative ly good fits of the saturation-pressure curves. ‘The van Genuchten and Brooks-Corey equations describing the relationship between saturation and pressure were used in equation (6) for the seven porous media to estimate the volume of LNAPL asa function of T. Figures 5 and 6 show the estimated volume of gasoline and Soltrol in a fairly porous sandstone (Lyons 4) based on the Fig. 5. Volume of gasoline in a sandstone (Lyons 4), van Genuchten vs. Brooks-Corey-based estimation. 54 Porous medium Si, Tsk Fox Hill ‘04983 4.2575 0.01777 0.06997 Dakota + 0.1792 5.9763 0.02193 0.02554 Lyons + 0.1435 4.3438 0.03176 0.00617 Touchet sit loam 0.3130. 5.145 0.01000 0.00896 Columbia sandy loam 0.4939 8.478 0.01458 0.01126 Unconsolidated sand 0.1000 8.000 0.15300 0.010687 Sandy porous media? 0.075 1,962 0.0544 NA. Ta Wem of water for o = Soltrol. 2 Converted from benzene daca NA = Information not available van Genuchten and Brooks-Corey equations, These figures illustrate that there is litle difference in the prediction of a sufficiently large volume of LNAPI. in the porous medium regardless of whether a Brooks-Corey or van Gemuchten equation is used. However, the Brooks-Corey solution predicts that no LNAPL will be observed in a well unless a critical volume of LNAPI in the porous medium is exceeded, as discussed previously. For the soils considered, the theoretical minimum thickness in the well ranged from 10 em for an unconsolidated sand to 98 cm for a silt-loam for gasoline. This minimum thickness is thought to be unreasonably large, based on field observations of relatively smatl depths of LNAPL in wells. For this reason, the van Genuchten-based method might be preferable, especially when small volumes per unit area are of concern, However, situations in which significant volumes of LNAPL in the vadose zone are not manifest by the presence of LNAPL in monitoring wells may exist in materials exhibiting a finite entry pressure For the Lyons 4 sandstone, Figure 7 illustrates the importance of the fluid properties on the prediction of the estimated volume of LNAPL in Fig, 6, Volume of Soltrol ina sandstone (Lyons 4), van Genuchten vs. Brooks-Corey-based estimation4 i i i : : Fig. 7. Volume of LNAPL in a sandstone (Lyons 4), van Genuchten-based estimation. the porous medium, The van Genuchten equation was used for these calculations. As discussed previously, the volume of LNAPL predicted using the van Gemuchten equation is similar to that predicted by the Brooks Corey, except for small volumes. Therefore, using the Brooks-Corey-based estimation, it can be observed from equation (14) that as T/D increases, Vo increases. Therefore as the quantity D decreases, Vo in the porous medium, increases, for a given observed depth of LNAPL in a well, T. Since gasoline has the smallest value of D of the LNAPLs selected for analysis, the predicted volume of LNAPL is greatest for gasoline. Lastly, Figure 8 illustrates that the estimated LNAPL volume is also very sensitive to soil type. Both Figures 7 and 8 show that large LNAPL. thicknesses in wells can be associated with very small LNAPL volumes in the porous medium. It is concluded from examination of Figures 7 and 8 that the important parameters required to i i i i j 8. Volume of gatoline in porous media, van Genuchter ed estimation, estimate the volume of LNAPL in a porous medium by the procedures of this paper are: (1) the properties of the fluid, specifically 039, dows and p; and (2) the properties of the porous media, specifically n, agg, and aow, for a van Genuchten soil, and 2, PA°, and P§"* for a Brooks-Corey soil DISCUSSION AND CONCLUSIONS ‘The foregoing calculations of LNAPL in porous media as a function of LNAPL thickness in a monitoring well were made for the condition of static equilibrium in homogeneous porous media. Subject to these conditions, the following conclusions can be drawn: 1, For any porous medium exhibiting a posi- tive entry pressure, PQ”, the minimum nonzero thickness of LNAPL in a monitoring well is T= P)"/Aog. Up to a critical volume, the entire body of LNAPL in the porous medium will exist at negative gage pressure and will not manifest itself in monitoring wells. Exceeding the critical volume will cause T to be equal to or greater than P3"/Apg. Therefore, calculation of Vo(T) based on the Brooks-Corey equation is possible only for T> PO Mog. 2. The function Vo(T) calculated using the van Genuchten equation is smooth over all values of T because the entry pressure is regarded as being zero. It appears that the relation Vo(T) calculated with the van Genuchten equation is more nearly commensurate with field observation than is Vo(T) calculated with the Brooks-Corey equation. 3. The function Vo(T) is highly sensitive to two length parameters that arc dependent upon the interfacial tension between fluid pairs, the fluid densities, and a characteristic pore size. In the formulation that utilizes the Brooks-Corey equation, these two important length parameters are PQ/Apg and P{?/gog. Fluid/porous mei combinations that cause D in equation (13) to be large result in small Vo for a given thickness of LNAPL. In other words, even small volumes of LNAPL in a porous media are manifest by large LNAPL thicknesses in monitoring wells. In the formulation that utilizes the van Genuchten equation, the two important length parameters are APgHow ANd pogo. Because equation (6) cannot be integrated in closed form for this case, the importance of these two parameters is not revealed explicitly as in the Brooks-Corey case. Nevertheless, a comparison of Figures 5 and 6 clearly reveals the sensitivity. The dramatically different results observed in these two figures are caused by the different values of Apgdow and pogta0 arising from 35the different properties of gasoline and Soltrol, ‘Any combination of fluids and porous media that results in small values for these parameters results, in small Vo for a given TT. 4. The calculations in this paper show there is, no simple relation between Vo and T with general applicability. The ratio of Vp to TT is not, in general, 0.25 (the 4:1 “rule-of-thumb” ratio), nor is the ratio even constant. For the special case of very uniform pore size the relation V(T) is approxi= mately linear with a slope of 6(1 ~ S,). Values for (1 ~ S,) for soils will usually fall in the range of 0.2-04, 5, The estimation of LNAPL volumes in porous media by the method discussed in this paper does not include residual LNAPL in the porous media. We do not intend to imply by our analysis that the total volume of LNAPL. in the porous medium can be recovered by extraction of LNAPL floating in wells, Residual LNAPL. and. mobile LNAPL residing at negative gage pressures, will not flow into wells in which the floating product has been removed. Additional consequences of mechanical equilibrium in three fluid systems of the kind treated in this paper are: 1, Neither the LNAPL level nor the water level in an observation well with floating LNAPL is equal to the water-table elevation in the adjacent porous medium. 2. LNAPL does not distribute itself as a distinct layer floating on top of a capillary fringe. Rather, the traditional concept of a capillary fringe is not applicable when mobile LNAPL is present. 3. The interval of porous medium containing mobile LNAPL extends above the LNAPL. in the well and downward to a point below the water table, The LNAPL is variably distributed in this interval and does not resemble a layer with, constant LNAPL, saturation, ACKNOWLEDGMENTS ‘The authors wish to acknowledge the assis- tance of John M, Farr in performing laboratory ‘measurements on interfacial tensions of gasoline and for his general assistance and review of this work. The work reported in this paper is a contribu- tion to the Agricultural Experiment Station project COLO 0349 entitled “Maintenance and Protection of Water Quality for Agriculture.” The financial support provided R, Houghtalen through the USDA National Needs Fellowship program is gratefully acknowledged. REFERENCES Brooks, R. H. and A."T, Corey. 1966. Properties of porous media affecting fluid flow. J. Ire. Drain, Div., ASCE. ¥, 92, no. IR2, pp. 61-88. CONCAWE. 1979. de Pastrovieh, T. L., Y. Baradat, R. Barthel, A. Chiarelli, and D. R. Sussell. Protection. of groundwater from oil pollution, Den Haag. Water Pollution Special Task Force. no. 11,61 pp. Corey, A. T, 1986. Mechanics of Lmmiscible Fluids in Porous Medi. Water Resources Publications, Liteleton, CO. 253 pp. Laliberte, G. E), A. T. Corey, and R. H. Brooks. 1966. Properties of unsaturated porous media. Colorado State Univ., Fort Collins. Hydrology Papers no. 17, Lenhard, R. J. and J. C, Parker, 1987. Measurement and prediction of saturation pressure relationships in three-phase porous media systems, Journal of Contaminant Hydrology. v. 1, pp. 407-424 Lenhard, R. J. and J.C. Parker. 1988, Experimental valida- tion of the theory of extending two-phase saturation- pressure relations to three-fluid phase system for ‘monotonic drainage paths. Water Resources Research, v. 24, pp. 373-380. Leverett, M. C. 1941, Capillary behavior in porous solids ‘Transactions AIME, Petroleum Engineering Div v, 142, pp. 152-169. Parker, J. ., R. J, Lenbard, and T. Kuppusamy. 1987. A paramettic model for constitutive properties ‘governing multiphase flow in porous media. Water Resources Research. v.23, pp. 618624, van Genuchten, M, Th. 1980. A closed-form equation for predicting the hydraulie conductivity of unsaturated soil. Soil Sci. Soe. Am. J. v. 44, pp. 892-898. White, N. F, 1968, The desaturation of porous materials. Ph, D. dissertation, Colorado State Univ., Fort Collins Anne M. Farris a Senior Geobydrologist at Kennedy! Jenks/Cbilton Consulting Engineers and is completing ber Pb.D. at Colorado State University in the area of optimiza tion of ground-water monitoring networks uilizing sto chastic ground-water models. She previously worked for Kennedy /Jenks/Chilton Consulting Engineers focusing on bazardous waste site assessments and as a hydrologist with the USGS-WRD. Robert J. Houghtalen is an Associate Professor of Civil Engineering at Rose-Hulman Institute of Technology. He recently completed his Pb. D. im Water Supply and ‘Systems Engineering Analysis at Colorado State University ‘asa U.S.D.A. National Needs Fellow. David B, McWhorter is Professor of Agricultural and Chemical Engineering at Colorado State University. He teaches courses and conducts research in ground-water bydvology and muttifiuid flow in porous media, Editor's Note: This paper deals with the identical subject as the paper by R. J. Lenbard and J. C. Parker inthis issue. The ‘work was dane by the two groups of researchers simultaneously but witb no knowledge of the other group's work, The papers were submitted within twa weeks of each other in tbe latter part of 1988. After significant review and revision, both original pieces of work were deemed appropriate for publication inasmuch as the subject is of significant importance in ground-water hydrology, and the duplicate effort clearly enbances the validity of the work as well as its future impact. 56