LNAPL Retention in Sandy Soil by David W. Ostendorf", Robin J. Richards’, and Frank P. Beck? Abstract ‘The vertical distribution of free and residual aviation gasoline, alight nonaqueous phase liquid (LNAPL), through the capillary fringe of a uniform, medium sand is measured and used to calibrate an existing model. The total saturation profile is governed by a classical moisture retention characteristic, with the matric pressure head scaled by LNAPL air surface tension inthe presence of free LNAPL and water/air surface tension the absence of free LNAPL. The residual LNAPL is described by an empirical equation reflecting hysteretical trapping due to a fluctuating water table. The existing theory is calibrated with new and published field data at an aviation gasoline spill site in Traverse City, Michigan, Introduction ‘The vertical distribution of free and residual aviation gasoline through the capillary fringe ofa uniform, medium sand is measured and modeled in this investigation. The gasoline is a light nonaqueous phase liquid (LNAPL) immiscible with and less dense than water, so that infiltat- ing product from a surface source will spread out over the ‘water table subject to retention in the overlying capillary fringe under the action of surface tension (Schwille, 1967; Pinder and Abriola, 1986). The initial spreading of immisei- ble contaminants through the subsurface as a continuous phase is considered in numerous mathematical models (Abriola and Pinder, 1985; Corapeioglu and Baehr, 1987; Sleep and Sykes, 1989) and laboratory investigations Schwille, 1988; Reibe et a., 1990) These dynamic models describe the motion of water and contamination, and are complemented by constitutive relations describing static capillary pressure-saturation curves for continuous LNAPL air/water systems. Substantial advances have been achieved in the prediction (Lenhard and Parker, 1987; 1990) and laboratory measurement (Lenhard and Parker, 1988) of these latter continuous phase constitutive relations. The occurrence and distribution of a discontinuous residual “Civil Engineering Department, University of Massachu- setts, Amberst, Massachusetts 01003. Robert. Kerr Enviconmental Research Laboratory, US Environmental Protection Agency, Ada, Oklahoma 74820, Received May 1992, revised September 1992, accepted Sep- tember 1992 Discussion open until September 1, 1993, Vol, 31, No. 2 ROUND WATER March-April 1993 nonaqueous phase liquid has received a degree of theoretical (Parker and Lenhard, 1987) and laboratory study (Wilson and Conrad, 1984; Hoag and Marley, 1986; Kia and Abdul, 1990; Conrad et al., 1992) comparable to its continuous counterpart This impressive literature is augmented by a detailed field data base in the present investigation, The US Envi- ronmental Protection Agency has addressed the fate and horizontal transport of LNAPL at its research site at the US Coast Guard Air Station in Traverse City, Michigan, The site is distinguished by a 23 year old separate phase aviation ‘gasoline plume 80 m wide, which currently extends some 260 m downgradient from its original source location (Ostendorf et al,, 1989; Ostendorf, 1990). The horizontal extent is documented with depth averaged separate phase core samples, The depth averaging was necessary because of the large (0.2 m) and in some cases discontinuous depth intervals used in the study of the horizontal LNAPL distr- bution at the Traverse City site. The soil is uniform, with mean diameter of 3.8 X 10 m in the vicinity of the water table, which is located 5 to 6 m below the ground surface. ‘The mean grain size corresponds to a USDA classified medium sand (Hillel, 1982). Figure 1 shows the site area. The depth averaged samples used to document the horizontal trajectory of separate phase contamination have been complemented by a vertically resolved separate phase core sampling program atthe sit, discussed by Ostendorf et al. (1991). Continuous vertical profiles with a finer (0.05 m) resolution are presented for two sampling stations in the latter paper, along with a detailed description of the core barrel extrusion protocol, methylene chloride extraction, and gas chromatographic analysis of the LNAPL retained 285by the soil. We add three more profiles tothe data base in the present work, and substitute the expanded observations into an existing vertical LNAPL distribution model for free (Lenhard and Parker, 1990) and residual (Parker and Lenhard, 1987) product. Free Liquid Retention ‘We must describe the vertical distribution of water (W subscript) and LNAPL (L. subscript) in free and trapped residual states above the water table, located a depth bw below the ground surface (Figure 2). The free (F subscript) and residual (R subscript) liquids are quantified by appro- priately defined volumetric contents volume water = otal volume 2 — Yolume LNAPL _ vol volume Oy = bun + Ove as) 6. = faa + bux ua Following Parker and Lenhard (1987), the volumetric con- tents in turn can be cast in terms of effective saturations, based on the usual wetting progression of water/LNAPL/ air in initially water wet soil. The free liquid saturations are related to capillary pressure by well-established constitutive equations. Since the capillary pressure is proportional to the elevation above the water table, the constitutive equations lead directly to the desired vertical profiles of free LNAPL and free water. — Interdiction 7 Well Line _ / \ Fiowf | » Direction | / ° / ; °50BT Smith ‘500M Hall i plume Building ji 606, ‘sops soci? sock Boundary Tanke, Hangar ‘Administration Building f OX Spill Origin Air Station, Traverse City, Ae Water Trapped LNAPL, Volumetric Liga Content Monitoring id retention in the capillary ‘Water fills all the smallest pores toa residual volumet- rie water content since the soils initially water wet. The free water, which is assumed to exist over the entire spatial domain, traps residual LNAPL droplets due toa fluctuating water table. Since the free water includes the residual LNAPL volume, we define an apparent effective saturation Sw in accordance with Owe (2a) volume voids. oo total volume with porosity n. Parker and Lenard (1987) originated the concept, and the inferred profiles of free and trapped water and LNAPL. are shown in Figure 2. The free water (and ‘occluded LNAPL) is bound by free, continuous LNAPL over a depth ranging from by to the water table bw. The total effective saturation S includes the LNAPL content, free and residual Ou + Our + Bun — Bo = Set Bn SOT oon 3a n— Own a Sur =S Sw (3b) The effective LNAPL saturation Si-follows from equations (2a) and (3a); note that the subtraction of Sw from S auto- ‘matically excludes the residual LNAPL from Sir in equa- tion (3b). Figure 2 indicates that the total saturation profile features an upper region with an outer water) LNAPL inter face and a lower region with outer LNAPL/air and inner water/LNAPL interfaces.‘The surface tension and capillary pressure differential across these interfaces determine their radii of curvature, hhence pore size. All pores smaller than the interfacial radius of curvature are full of the wetting fluid, while larger pores contain the hydrophobic fluid. Consider a given depth on the vertical axis of Figure 2, The total saturation corre- sponds to the liquid content at the LNAPL/air interface, whose surface tension o. and capillary pressure p,estab- lish a large radius of curvature ry. All pores larger than r, contain air. The interface between water and LNAPL at the same depth features a capillary pressure difference between the LNAPL px and the water pw pressures and a surface tension ow:. These parameters determine an interfacial radius rw that is smaller than r,; pores of intermediate size contain free LNAPL, while pores smaller than rw are full of water (and trapped LNAPL). Thus, the water/LNAPL interface controls the water saturation from the shallowest depth of free LNAPL occurrence byto the LNAPL table at depth b., sketched on Figure 2, This LNAPL table marks the appearance of product in a monitoring well and deepest penetration of air into the soil. The free product persists down to the water table, The total saturation is governed by the LNAPL/air interfacial tension where free LNAPL. is present S=U+[Belbe — bYIU"! (bo. > b> bu) (4a) s=1 (b> by) (40) with depth b below the ground surface, The derivation of this form of Lenhard and Parker's (1990) model iscontained in the Appendix; a Van Genuchten (1980) distribution is, adopted for the pore size distribution. The exponent appearing in equation (4) varies directly with the uniformity of the pore sizes. Nonuniform silts and clays engender uni formity exponents approaching I in size, while sands are characterized by a values in excess of 2. The Appendix demonstrates that the LNAPL scaling factor Bis related to ‘the mean pore radius by the capillary equation (Streeter ‘and Wylie, 1979) for presumedly circular pores and a stall contact angle post 2ous 3 © with aviation gasoline density pr, and gravitational accelera- tion g. Equation (5) relates the empirically determined scal- ing factor to physically based parameters, whose value can be checked against fluid property and grain size data for plausible behavior. ‘The apparent effective water saturation is scaled by the LNAPL water surface tension ow, in the presence of free LNAPL, with @ capillary pressure differential across the interface of the two fluids Sw= (1+ [Bw(bw — by}! Sw= (bw > b> bu) (6a) (b> bw) (6b) ‘The distance to the water table by delineates the lower boundary of free LNAPL and extent (bw— bx) of product in «2 monitoring well. The scaling factor uw is given by the Appendix as Bw = Bo a ‘The free LNAPL has the depth by as an upper limit. This variable is determined by setting Sw and S equal in equa- tions (4a) and (6a) with the result _ Bub = Bubw BL Bw ‘The total saturation and water saturation are coinci- dent above by, and are governed by the water/air tension ‘ows and the water capillary pressure pw. The apparent effective water saturation in the shallower region follows from the Appendix derivation sw=(1 + {Ace bu @) ayia [bu — bw + _ (ov — )}") (ow >b) Equations (6a) and (9) match at by by virtue of equations (7) and (8), ensuring @ continuous water saturation profile as well Equations 3), (4), (6), and (9) specify the free liquid profile inthe yadose zone. These profile share the common form of Van Genuchten (1980), with scaling determined by appropriate interfacial surface tensions and eapillary pres- sures, a originally derived by Lenhard and Parker (1990) The free water and free LNAPL profiles reflect the postions of the LNAPL and water tables at the time of sampling, in contrast to the residual LNAPL, which is a function of historial fluctuations ofthese parameters. LNAPL Entrapment ‘The residual LNAPL is thought to be the result of hysteretical trapping of gasoline a it falls and rises through ‘the water wet soil over a fluctuating water table, As the water table changes position, the capillary pressure of both liquids changes too, creating different interfacial radii and different saturations at a given location. Free LNAPL in contact with, ‘water will form a progressively smaller interfacial radius as the water drops and the capillary pressuresrrise, After attain- nga maximum depth, the rising water table creates increas- ing radii that reflect decreasing pressures. Some of the LNAPL is trapped as the free liquids fill the soil, The effective residual LNAPL saturation Sex reflects the frac- tion of the drainable pore space that is filed by these resid- ual masses of aviation gasoline trapped by the process fr n= On Parker and Lenhard (1987) suggest that the distribution of residual produetin th soils governed by the behavior of the LNAPLwater interface, which also dictates the water saturation, Sux (19) 287LNAPLiWater Head ‘Saturation WT Ground Surtace Doan A.C (Summer) "L. (weer) iagram of hystetetical trapping of LNAPI... ‘The situation is shown conceptually in Figure 3. Avail- able sites at a given depth b drain as the water table drops. during the fall months along path AB to its maximum depth Dwwax in the winter at Traverse City. The minimum water saturation Swat this reversal point (Parkerand Lenhard, 1987) is specified by equation (11a), since free LNAPL. is present Swan = £1 + [Bw (bvstax ~ BI (ila) Swmax = (0+ [Bw(bwan — bY! (Ub) bwwax = boa + 4 (ite) Some of the free LNAPL is trapped during spring imbibi- tion asthe water table rises along adrier moisture character~ istic (path BC) towards a summer minimum depth busin, defined by the fluctuation amplitude A, The minimum water-table depth yields a maximum effective water satura tion Swnax {equation (I1b)] atthe given b value. This satura- tion includes trapped LNAPL, numerically equal to AC on Figure 3 The hysteretical wetting process yields a maximum ‘rapped LNAPL saturation Saya if the water table rises past the depth b under consideration, as described by Parker and Lenhard (1987) «ay Strata = 288 The hysteretical trapping factor» is geometrically defined bythe primary drainage and imbibition curves ofthe soil. In the absence of detailed field data describing the primary moisture characteristics, is calibrated in this study from observed maximum residual saturation data at the site Figure 3 indicates the occurrence of Stavax at the water- table condition of zero capillary pressure head. ‘Those elevations higher than the minimum water-table depth attained during trapping will experience occluded masses less than the maximum, sketched at line AC on Figure 3, Parker and Lenhard (1987) propose an empirical relationship for this residual saturation Sux = Sunmiax (1 — (uray > b) (Ba) Sin =Sunaax ——(Duarax > b> busts) (13) Sux=0 (b> bwsiand (130) Six=0 (bwax— €> d) to) Equation (13) reflects the concern with LNAPL, which floats on the heavier water, and so will not be present below the water table, Free LNAPL must have existed at a given location in order for trapping to occur, so that occluded product cannot exist above the historical minimum free product depth bwsiax — ¢. Practically speaking, ¢ is the observed thickness of residual LNAPL in the sol ‘The total LNAPL saturation S1 is comprised of the free and residual partitions, as described by equations (3b) and (13), respectively SL= Sin + Six i) Model Calibration ‘The saturation model is calibrated with five ses of total and LNAPL saturation data, with common parameter values cited in Table I. The cores are located downgradient ofthe LNAPL spill origi, asindicated by Figure I. Staions SOBS and SOBT are published data bases (Ostendor et al. 1991), while Stations SOCE, SOCL, and SOCM are new. Intact core sleeve segments are averaged with barrel extruded Mason jar data forthe firsttwo cores, while barrel exiruded (6 pint) Mason jar data solely characterize the latter Stations. The porosiy and LNAPI. density values of Table | are taken from earlier research at the site (Ostendorf etal, 1989), while iterature values for surface tensions are adopted. In the latter regard, the water air surface tension is assumed equal 10 the sum of the water/LNAPL. and LNAPL jie surface tensions (Lenhard and Parker, 199). Station SOCI. is the cleanest of the five Stations, with LNAPL contamination spread rather uniformly about a ‘maximum saturation of0.025 over a0.8 m interval, which is setequalto-. This uniform, low strength profile character- istic of residual LNAPL, so that free LNAPL is presumed to be absent atthe Station, The maximum observed residual saturation i used to estimate 7 through a simplification of equation (12)Table 1. Common Calibration Parameters Symbol Parameter Value ‘Source . Porosity om (Ostendorf etal. (1989) a LNAPL density 707 kgm? Ostendorf etal. (1989) ows ‘Water air surface tension 0.074 Nim. Streeter and Wylie (1979) os LNAPL jar surface tension 0.023 Nim. Lenhard and Parker (1990) ow Water) LNAPL surface tension 0.051 Nim Lenhard and Parker (1990) ‘ Residual LNAPL thickness 0.80 m SOCL Calibration y Trapping coefficient 40 S0CL Calibration a Hysteretical amplitude 035m NOAA (1992) a Uniformity exponent 30 S0CE Calibration Bi Scaling coefficient 82m! S0CE Calibration bux Irreducible moisture 0.039 S0CE Calibration We used an approximate peak concentration matching, Stamax, GD (15) relation to enforce a relation between the Van Genuchten y ‘Thus, the hysteretical trapping factor is equal to 40, The cited value for the fluctuation amplitude A is based upon historical records of the water level of Lake Michigan, as ‘measured ata gaging station in Holland, Michigan (NOAA, 1992). The difference between the maximum and minimum, monthly average lake level observed at the gage in @ given Year is taken as a measure of the annual water-able flue- tuation at the Air Station, due to its proximity to Lake Michigan (within 1300 m of Grand Traverse Bay). The figure of 0.35 m cited in Table 1 is the average of 22 such amplitudes, taken from 1970-1991 records. The three resid- ual LNAPL parameter values («, 7, A) are adopted for the five Stations, since the residual LNAPL. is emplaced by a fluctuating water table that is common to all contaminated locations. Equations (3)-(14) suggest that the presence of free LNAPL also influences the total saturation, so that Sand Si must be jointly calibrated, A series of nested Fibonacei searches was run through both $ and Si. data sets (Beveridge and Schechter, 1970), to establish minimal statistics of the saturation error. The error mean Bs and standard deviation (are defined by (Benjamin and Cornell, 1970) 1 B= 5 3 [s (observed) — S (predicted) + Si (observed) ~ S1.(predicted) Stax (observed) a 1 os= CG x {Is (observed) — § (predicted)]? + Su (observed) ~ Sx (predicted) [ ‘Simax (observed) Y }nt ) (J samples) (16b) The use of the maximum observed LNAPL. saturation Stax to normalize the LNAPL error places equal weight on the total and LNAPL saturation in determining theerror statistics, since S has a maximum value of unity (1980) pore size parameters (a, f) and the oil- and water- table depths (b., bw) for the free LNAPL profiles, The ‘maximum observed free LNAPL saturation S.rsax and its depth biseax are assumed known, The matching relations stem from equations (3b), (4a), and (6a), which specify the free LNAPL saturation between by and by, where the ‘maximum value resides Sur = (1 + [B.(b, — by} {1+ [Bw (bw — BH" (bu > b> bu) (17a) Sur = [1 = (ep {CB (bw ~ by] = (Bu. (b. — BIT") (076) Equation (7b) is a Taylor expansion of (17a), valid for saturations near unity. Approximate equations forthe loce- tion of Sax follow by setting the derivative of (17b) with respect to b equal to zero at depth brssax bw={ i a pu! + bawax ae Grey . + (18a) bi = (bw — bumax) (BoB) + buseax (186) Equation (18) is imposed on Station SOCE in a nested Fibonacci search for a, wx, A, and Bwsans With the results summarized in Tables | and 2 and Figures 4 and 5, The uniformity parameter and scaling coefficient from the SOCE. Station % 508 16 S0BT ia SOCE a S0CL 23 50CM Is2 i ay i oo ee | Bean ad 4 i 4 Boo a uy ee b> ba) 21) ‘The hydrocarbon liquid is in tension above the LNAPL table, so that pi, is negative in this region. The surface tension between air and LNAPL establishes a radius of curvature of the liquid/air imerface r,, and this radius is equal to largest wet pore size at the given depth b. The corresponding saturation is given by Van Genuchten’s (1980) distribution s=[r4(Ly TP edeay cam 2orn PL ‘The scaling factor fi, appearing in equations (4a) and (5) follows from equations (21) and (22). ‘The LNAPL/water interface and capillary pressure differential govern the largest water wet pore size rw in the presence of free LNAPL. This pore size is smaller than r., and determines Sw, which is smaller than S se [ET ex 20) (226) = (bw > b> by) (236) PL Pw ‘The water pressure pw is equal to p..g(bw— br at the water table, in view of the static conditions in the monitoring well displayed in Figure 2. Its value at higher elevations may be deduced by subtracting a hydrostatic column of water with, the result Bw = pig(bw — br) — pg(bw — b) (24a) PL ~ pw =(p~ pr)g(bw ~ b) (240) Equation (7) follows directly from equations (5), (6) (23). and (246), The total and effective water saturations coincide above the free LNAPL profile, and are specified by the wwater/air surface tension and the water pressure of equa: tions (23a) and (24a) 2own Pw (bu > b) 5) 21Equations (5), (24a), and (25) yiel _ surf fb. ~ bw + (p/p) expression for 7/tw bd) 26) Equation (9) is a consequence of equations (23a) and (26) Acknowledgments This research is supported as US Environmental Pro- tection Agency Contract CR 816821 with the University of Massachusetts at Amherst, administered through the Robert S. Kerr Environmental Research Laboratory of ‘Ada, Oklahoma. The paper has not been subjected to EPA review, however, and accordingly does not necessarily reflect the views of the Agency, so that no official endorse ‘ment should be inferred. Robin J. Richards is a National Science Foundation Graduate Fellow, and the authors acknowledge the NSF support with gratitude. We appre- ciate the continuing field support provided by the US Coast Guard and thank the Ocean and Lake Levels Division of NOAA for water-level data at Lake Michigan, References Abriola, LM. and G. F, Pinder, 1985, A multiphase approach to the modeling of porous media contamination by organic compounds, I. Equation development, Water Resour RES v.21, pp. lB, Benjamin, j. R_and C. A. Cornell. 1970. Probability, Statistics, and Decision for Civil Engineers. McGraw-Hill, New York, NY. Beveridge, G-S.G. and RS, Schechter. 970, Optimization: The ‘ory and Practice, McGraw-Hill, New York, NY. Conrad, $. H.,J.L. Wilson, W. R. Mason, and W. J. Peplinsk 1992. 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