Journal of Contaminant Hydrology 105 (2009) 28–37

Contents lists available at ScienceDirect

Journal of Contaminant Hydrology

j o u r n a l h o m e p a g e : w w w. e l s e v i e r. c o m / l o c a t e / j c o n h y d

Unsaturated zone leaching models for assessing risk to groundwater of

contaminated sites
Mads Troldborg a,⁎, Philip J. Binning a, Signe Nielsen a,b, Peter Kjeldsen a, Anders G. Christensen c
a
Department of Environmental Engineering, Technical University of Denmark, Miljøvej, Building 113, 2800 Kgs. Lyngby, Denmark
b
Now at Orbicon A/S, Ringstedvej 20, 4000 Roskilde, Denmark
c
NIRAS A/S, Sortemosevej 2, 3450 Allerød, Denmark

a r t i c l e i n f o a b s t r a c t

Article history: Risk assessments of sites contaminated with organic contaminants are typically conducted
Received 5 February 2008 using models that ignore gas phase transport in the unsaturated zone. Here a general approach
Received in revised form 12 September 2008 to developing analytical solutions to multiphase transport is presented. The approach is based
Accepted 4 November 2008
on a combined gas and aqueous phase contaminant transport equation. The equation has the
Available online 12 November 2008
same general form as the standard advection–diffusion equation for which many analytical
solutions have been derived. Four new analytical solutions are developed using this approach: a
Keywords:
three-dimensional solution accounting for infiltration, lateral gas diffusion, sorption and
Unsaturated zone
Contaminant transport degradation; a simple one-dimensional screening model, and two one-dimensional radial gas
Risk assessment diffusion models for use in simulating volatile organic contaminant diffusion in unsaturated
Analytical models soils with an impermeable cover. The models show that both degradation and diffusion are
important mechanisms for attenuation of contaminant concentrations at the water table.
Finally, model results are compared with field data to illustrate the applicability of the solutions
in risk assessment.
© 2008 Elsevier B.V. All rights reserved.

1. Introduction coupled phases (air and water) under influence of different

Most point source contamination originates from releases
at or near the land surface and must therefore pass through
the vadose zone before reaching an underlying aquifer. In
many cases attenuation processes in the unsaturated zone
are critical determinants for the risk to groundwater. It is
therefore important to account for these processes when
assessing the risk of groundwater contamination from point
sources. However, in most screening tools for risk assessment,
the transport through the unsaturated zone is very simplified.
In general these models only consider transport of dissolved
contaminants in infiltrating water. However, transport pro-
cesses in the unsaturated zone are much more complicated,
because the solute contaminants are transported in two
⁎ Corresponding author. Tel.: +45 4525 1596; fax: +45 4593 2850.
E-mail address: mat@env.dtu.dk (M. Troldborg).
reaction processes.
To describe the transport through the unsaturated zone
more adequately, it is essential to include the most important
fate and transport processes. The processes that should be
included depend on the chemical properties of the contami-
nant and the soil properties of the vadose zone. For example,
highly soluble compounds are easily transported to ground-
water in infiltrating rain water.
However, many studies have shown that gas phase transport
in the unsaturated zone can be a dominant transport mechan-
ism, especially for volatile organic compounds (VOCs) like
chlorinated solvents and BTEXs. Diffusion has often been found
to be the most significant transport process in the gas phase
(Conant et al., 1996; Pasteris et al., 2002; Christophersen et al.,
2005) and contributes significantly to the spreading of
contamination over a larger area at the water table, which
results in lower concentrations infiltrating to groundwater. The
transport of volatile organic compounds may also be affected by
gas phase advection due to e.g. barometric pressure variations,

0169-7722/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.jconhyd.2008.11.002
 M. Troldborg et al. / Journal of Contaminant Hydrology 105 (2009) 28–37
gas density gradients, temperature changes and fluctuating
groundwater table (Falta et al., 1989; Mendoza and Frind, 1990;
Auer et al., 1996; Parker, 2003). Advective gas phase transport is
often considered to be less significant than diffusion and
degradation (Conant et al., 1996; Pasteris et al., 2002; Choi and
Smith, 2005). Recent experience has also shown that aerobic
microbial degradation is an important attenuation process in
the unsaturated zone for a wide variety of oil components
(Lahvis et al., 1999; DeVaull et al., 2002; Hohener et al., 2006),
and this may reduce the impact to groundwater considerably.
Neither gas transport nor biodegradation is accounted for in
most screening tools for risk assessment.
There are many analytical solutions available for simulat-
ing contaminant transport in the unsaturated zone. However,
few of these consider combined gas and water phase transport
and none are available in higher dimensions. For example,
Jury et al. (1983) presented a one-dimensional solution
considering advection, diffusion, soil sorption and degrada-
tion in the aqueous and gas phases. Shan and Stephens
(1995) extended Jury et al.'s solution to include dispersion.
Other notable solutions include the aqueous phase transport
solution of Unlu et al. (1992), which forms the basis for the risk
assessment tool RISC Workbench (Spence, 2001). Leij et al.
(1993) presented three-dimensional analytical solutions for
vertical transport through the unsaturated zone that do
not take gas phase transport into account. These solutions
can be used for modelling non-equilibrium solute transport
in media, where the liquid phase consists of a mobile and
an immobile region and incorporate advection, dispersion
and first-order decay. Karapanagioti et al. (2003) examined
several public domain models capable of unsaturated zone
modelling and also found that the majority of the codes
describe the fate and transport of contaminants only in the
aqueous phase.
A general applicable unsaturated zone leaching model
for assessing the risk to groundwater of contaminated
sites should be able to deal with many different types of
contaminants and should therefore ideally include as many
processes as possible. At the same time the available data in
risk assessments are often limited and the model should
therefore not be too data demanding. Finding the right balance
between data requirements and the processes descriptions is
therefore crucial.
We aim to develop a general approach for deriving water
and gas phase analytical solutions that describe the down-
Fig. 1. Conceptual sketch of the problem simulated by models 1 and 2 (left), 3 and 4 (right).
29
ward vertical contaminant transport through the unsaturated
zone from a surface-near source to an underlying aquifer.
The approach is applied to develop a set of four analytical
solutions for assessing the risk posed by sites contaminated
by volatile contaminants. These analytical solutions can be
used to simulate transport through homogeneous saturated
and unsaturated soils and includes advection and dispersion
in the water phase, diffusion in the gas phase, sorption and
first-order degradation. The solutions are expected to cover
typical cases of contamination that involve unsaturated zone
and to be useful in practical risk assessment.
The new analytical models for risk assessment have been
tested at a range of contaminated sites to evaluate applic-
ability. In each case the concentration of water reaching the
water table from a contaminant source in the unsaturated
zone was modelled and results compared with measured
data. Results from two of these case studies are presented
here.
2. Mathematical models
Four mathematical models are presented. The first
describes the 3-dimensional vertical transport and horizontal
spreading of contaminant in the air and water phases from an
immobile patch source of constant concentration at the
ground surface. The second is a steady-state one-dimensional
analogue of the three-dimensional solution. The third solves
the steady-state transport equations for radial spreading of a
contaminant partitioning between the air and water phases
between the water table and an impermeable surface cover
and the fourth considers transient radial transport without
reactions. A sketch of the scenarios modelled is shown in Fig. 1.
The models are based on the following set of assump-
tions: (i) homogeneous soil properties consisting of a
constant water content, bulk density, porosity and organic
carbon fraction, (ii) linear reversible and instantaneous
equilibrium partitioning between phases, (iii) soil sorption
occurs only from the water phase, (iv) advection in the gas
phase is neglected, (v) advection in the water phase only
occurs in the vertical direction and is constant, (vi) degrada-
tion can be described as a first-order process and only occurs
in the water phase, (vii) the source concentration is constant,
(viii) contaminant transport is only considered for a single
component, and (ix) separate liquid phase transport is not
considered.
30 M. Troldborg et al. / Journal of Contaminant Hydrology 105 (2009) 28–37

2.1. Governing equations volumetric air content multiplies the pore diffusion coefficient
in Eqs. (8) and (9), and so the exponent of θa in Eq. (10) is 1.5.
By summing the transport equations for water and air and Moldrup et al. (2001) do not separate the air content in this way
employing the phase partitioning expression Ca = KHCw, the in their paper, and so there the exponent is 2.5.
following equation is obtained:
2.2. Model 1 — vertical transport and spreading of contaminant
AðRθw + KH θa ÞCw ACw in three dimensions
= jðθw Dw + KH θa Da ÞjCw −qw −θw λCw
At Az
ð1Þ The above equations can be solved with boundary and
−3 initial conditions describing a patch source of contamination
where Cw (M L ) is the solute concentration in the water
perpendicular to the flow direction and a zero concentration
phase, R (−) is the retardation coefficient, KH (−) is the dimen-
initial condition.
sionless Henrys constant, θw (−) is the water content, θa (−) is
the air content, Dw (L2 T − 1) is the dispersion tensor in water, Cw ðz; x; y; 0Þ = 0 0 < z < ∞ −∞ < x < ∞ −∞ < y < ∞ ð12Þ
Da (L2 T − 1) is the diffusion coefficient in air, qw (L T − 1) is the
(
water infiltration rate, and λ (T− 1) is the first-order degrada- X X Y Y
Cw ð0; x; y; t Þ = C0 − < x < ;− < y < ð13Þ
tion rate. Because partitioning is assumed linear, the retarda- 2 2 2 2
tion coefficient R can be determined from: 0 otherwise

ρb ρ where X (L) and Y (L) are the width and length of the patch
R=1+ K = 1 + b Koc foc ð2Þ
θw d θw source, respectively, and C0 is the constant source concentration
in the water phase. An analytical solution to Eq. (3) is presented
where ρb (M L− 3) is the bulk density, foc (−) is the fraction of by Sagar (1982) and Wexler (1992) and has the following form:
organic carbon, and Koc (−) is the partition coefficient between
τ=t
the contaminant and natural organic matter (Bedient et al.,
1997; Fetter, 1999). Eq. (1) is a mass balance statement for the Cw ðz; x; y; t Þ =
C0
8 τ=0
∫
f Vz ðz; τÞf Vx ðx; τ Þf yVð y; τÞdτ
contaminant including the solid, aqueous and gas phases. Under
the assumptions described above, this equation can be written: where
  " ! #
ACw ACw z v Vz ðvVÞ2 z2
+ vV −jD′jCw + λ VCw = 0 ð3Þ f Vz ðz; τÞ = pffiffiffiffiffiffiffiffiffi exp  exp −τ + λV −  τ−3=2
At Az πD zV 2D Vz 4D zV 4D Vz τ
where 8 2 3 2 39
> X X >
< x+ x− =
v V= qw =RV ð4Þ 6 7 6 2 ffi7
2 ffi5−erf 4 pffiffiffiffiffiffiffiffi
f Vx ðx; τÞ = erf 4 pffiffiffiffiffiffiffiffi 5
>
: 2 D xVτ 2 D xVτ > ;
0 1
DxV 0 0 8 2 3 2 39
> Y Y >
D′ = @ 0 Dy 0 A
V
ð5Þ < y+ y− =
6 pffiffiffiffiffiffiffiffi 7 6 2 ffi7
2 ffi5−erf 4 pffiffiffiffiffiffiffiffi
0 0 DzV f yVð y; τÞ = erf 4 5 :
>
: 2 D Vy τ 2 DV yτ > ;
λ V= θw λ=RV ð6Þ
The solution has been evaluated using MAPLE (Maplesoft,
RV= Rθw + KH θa : ð7Þ 2007).

The dispersion coefficients in Eq. (5) are written: 2.3. Model 2 — 1D vertical transport
 e e

x = DyV = θw Dw + θw α T vw + θa KH Da =RV
DV ð8Þ
A one-dimensional steady-state solution of Eq. (3) with an
  infinite source area at the land surface can be derived and is
z=
DV θw Dew e
+ θw α L vw + θa KH Da =RV ð9Þ
based on the work of Unlu et al. (1992):
where α L (L) and α T (L) are the longitudinal and transverse  
ðvw −uÞz
dispersivities in the water phase respectively and vw (L T − 1) is Cw ðzÞ = C0 exp
2Dz
the seepage velocity. It should be noted that longitudinal here is
along the vertical axis z and that transverse means horizontal in where
the x and y directions. The pore diffusion coefficients in air and
water phase are given by (Moldrup et al., 2001):  
4λDz 1=2
u = vw 1 + 2
vw
θ1:5
Dea = D0aa
ð10Þ
n  
  0 θw Dew + θw α L vw + θa KH Dea
Dew = 1:1θw θw −0:039SA0:52 ð11Þ Dz = :
vol Dw θw

where Dα0 (L2 T − 1) is the free diffusion coefficient in phase α and A transient version of this model can also be developed
SAvol is the surface area of the porous medium. Note that the based on Eq. (3) and the solution of Unlu et al. (1992).
 M. Troldborg et al. / Journal of Contaminant Hydrology 105 (2009) 28–37 31

2.4. Model 3 — steady-state radial transport of contaminant the Bessel function of second kind and order 0. μn are the
with reactions roots of:

The first two models simulate transport through the J0 ðμ ÞY0 ðmμ Þ−J0 ðmμ ÞY0 ðμ Þ = 0: ð16Þ
unsaturated zone in cases where infiltration occurs. When
there is an impermeable land cover such as saturated clays Table 1 shows the first 10 values of μn, where m =R2 /R1 = 100
or paved areas, infiltration is zero. In these cases the main (i.e., the source has a radial dimension of R1 = 1 m, and the
mechanism of contaminant transport is gaseous diffusion. Here concentration is zero at a distance R2 = 100 m from the source).
a radial diffusion model with partitioning between phases is
developed to describe this case. 3. Application of models
If the infiltration rate is zero the transport equation for
volatile, reactive contaminant (Eq. (1)) formulated in radial 3.1. Risk of groundwater contamination from a fuel release near
coordinates becomes: land surface — application of model 1 and model 2
 
AðRθw + KH θa ÞCw   A2 Cw 1 ACw Models 1 and 2 are used to assess the risk posed by a site
= θw Dew + θa KH Dea + −θw λCw
At Ar 2 r Ar contaminated by leakage from a fuel oil tank. The description
ð14Þ of the site and the data used in the calculations are based on
unpublished site characterisation reports prepared by an
where r is the radial distance from the centre of the source. environmental consulting agency (NIRAS, 2006).
Eq. (14) is the modified Bessel equation. With boundary Free phase fuel oil has leaked from a pipe leading to a fuel oil
conditions Cw(0 < r < R1) = C0 and Cw(r → ∞) = 0, the steady- tank for an unknown period. The pipe is 0.5 m below ground
state solution is given by (Spiegel, 1968): surface and the contaminant source is estimated to have an
area of 5 ×5 m2, with residual phase contamination extending
C0
Cw ðr Þ = K0 ðrωÞ to a depth of 3 m below ground surface. The source zone is
K0 ðR1 ωÞ considered to be immobile. The average concentration in the
area is estimated to be 3000 mg/kg dry soil, and the contaminant
where K0 is the modified Bessel function of the second kind
source therefore contains approximately 320 kg fuel oil. Analyses
and order 0, R1 is the radial extent of the source and ω is:
of soil samples from the source zone have shown that the fuel
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi oil contains approximately 0.1% BTEX. It is expected that the
θw λ
ω= : lightest and most mobile components will be transported from
θw Dew + θa KH Dea
the source zone dissolved in either the gas or the water phase.
This is supported by pore gas samples from and below the
2.5. Model 4 — transient radial transport of contaminant source zone, where only the most volatile components are
without reactions observed. The mass fraction of BTEX in the pore gas samples has
been estimated to around 1–3%, and the average source zone
A transient solution to Eq. (14) without degradation can be concentration in the gas phase is estimated to 11.25 mg/m3
derived using the boundary conditions Cw(0 < r < R1) = C0 and corresponding to a water phase concentration of 75 μg/l.
Cw(r = R2) = 0, and is given by (Luikov and Hartnett, 1968): Model 1 is used to assess the concentration of contaminant
  leaching to the groundwater table 18 m below land surface,
C0 R2
Cw ðr; t Þ = ln i.e. a transport of 15 m in the vertical direction through an
lnðmÞ r
unsaturated zone consisting of well sorted fine sand with
∞  
a porosity of 0.45 (estimated on the basis of the grain size)
 
+π ∑ J0 ðμ n mÞV0 ðμ n r=R1 Þ
J0 ðμ n Þ + J0 ðμ n mÞ
exp −μ 2n F0
C0 J0 ðμ n mÞ
J0 ðμ n Þ−J0 ðμ n mÞ and a water content of 0.15 (estimated to be a typical field
n=1
capacity of fine sand). The net infiltration rate is estimated to
where be 200 mm/yr.
The choice of model parameter values is highly uncertain
V0 ðμ n r=R1 Þ = J0 ðμ n r=R1 ÞY0 ðμ n Þ−J0 ðμ n ÞY0 ðμ n r=R1 Þ ð15Þ because there is limited data available at the site. Data
limitations are common in risk assessment contexts where
 
θa KH Dea + θw Dew t thousands of sites must be assessed. Given that the aim of the
F0 = model application is such a risk assessment, parameters are
ðθa KH + Rθw Þ R21
chosen so as to ensure that contaminant concentrations at the
m = R2 =R1 , C0 is the water phase concentration of the source, receptor are as high as possible. This means that parameters
R2 is a radial distance at which the concentration is zero, J0(x) are set to extreme ends of the range plausible for the problem.
is the Bessel function of the first kind and order 0, and Y0(x) is For example, degradation rates are set at the low end of the

Table 1
The roots μn of the characteristic Eq. (15) for m = 100

m μ1 μ2 μ3 μ4 μ5 μ6 μ7 μ8 μ9 μ 10
100 0.028 0.060 0.092 0.124 0.156 0.188 0.220 0.252 0.284 0.315
32 M. Troldborg et al. / Journal of Contaminant Hydrology 105 (2009) 28–37

range of values presented in the literature and contaminant

properties are chosen to be those of the most mobile of the
toxic components in fuel oil, namely benzene.
The longitudinal dispersivity in water is estimated to be
αL = 0.1 m based on the review by Vanderborght and
Vereecken (2007), while the transverse dispersivity is
assumed to be αT = 0.01 m. The dispersivities in water in the
vadose zone are not well known and the sensitivity of these
parameters will be tested later in this section. Vapour
properties are taken to be those of benzene. The U.S. EPA's
soil screening guidance (US EPA, 1996) provides the diffusion
coefficient in air to be D0a =0.76 m2/d. Henrys constant is
estimated to be KH = 0.15 (−), which is assumed valid for typical
Danish subsurface temperatures of 10–15 °C (Ashworth et al.,
1988; Peng and Wan, 1997), while Koc = 22 (−) (calculated
from logKow = 2.1 and logKoc = 1.04 · logKow − 0.84 (Abdul et al.,
1987)). The diffusion of benzene in water is 8.47 × 10− 5 m2/d
(US EPA, 1996). The sandy soil is estimated to have an organic
carbon fraction foc = 0.02 (−), and a bulk density of ρb = 1.7 kg/l.
The retardation coefficient is calculated to be R = 6.0 using
Eq. (2). A conservative estimate of the first-order degradation
rate for benzene based on literature values is λ = 0.01 d− 1
(DeVaull et al., 1997).
Fig. 2 shows the distribution of contaminant as a function
of vertical distance from the source to the water table at (x,y)
coordinates corresponding to the centre of the contaminant
source. The distribution of contaminant is calculated using
both model 1 (3D) at t = ∞ and model 2 (1D), and is compared
to detailed field measurements collected at the site.
The figure shows that two mechanisms contribute to
the attenuation of concentration with depth: degradation
and horizontal spreading. If there is no degradation and no
spreading, then the contaminant breaks through at source
concentrations (1D λ = 0 d− 1). Horizontal diffusion in the gas
phase results in a substantial decrease in contamination
(Figs. 2 and 3 D λ = 0 d− 1). The contaminant concentration of

Fig. 3. Steady-state concentration of contaminant in the unsaturated zone

along the centreline (x = y = 0) below the source as calculated using the 3D
model for (A) different source areas, for (B) a variety of water contents and for
(C) a variety of transverse dispersivities at two different water contents
(θw = 0.15 and θw = 0.40) and with the longitudinal dispersivity held constant
Fig. 2. Steady-state concentration of contaminant in the unsaturated zone (αL = 0.1 m). Degradation is neglected (λ = 0 d− 1).
along the centreline (x = y = 0) below the source as calculated using the 3D and
the 1D model for a variety of reaction rates. The results are based on a
constant source concentration in the water phase of 75 μg/l, which is the
average of the measured concentrations within the source zone. Also shown
are field measurements of total pore water BTEX concentrations below the
source.
 M. Troldborg et al. / Journal of Contaminant Hydrology 105 (2009) 28–37
the water reaching the groundwater is reduced to below 2 μg/l
solely due to the three-dimensional spreading of contaminants
in the gas phase. The diffusive spreading depends on the source
area (Fig. 3A). Larger sources are less attenuated by horizontal
spreading and the one-dimensional solution (model 2) provides
a reasonable estimate of contaminant distributions. However,
many point contaminant spills occur over a small area and so
horizontal spreading is an important mechanism and in these
cases a full three-dimensional solution is required to properly
assess contaminant breakthrough.
If the contaminant is degradable, then a further attenua-
tion of contaminant occurs. This can be seen in Fig. 2 for cases
where λ N 0. If λ is large, then degradation is the dominant
attenuation mechanism and horizontal spreading becomes
less important. This is seen from Fig. 2 where the 1D solutions
approach the 3D solution for large degradation rates.
Another critical parameter for the attenuation of contami-
nants in the unsaturated zone is the water content (Fig. 3B).
Higher water contents reduce the dispersion coefficients
(Eq. (5)) because the diffusion coefficient in water typically is
several orders of magnitude smaller than the diffusion
coefficient in air. In a fully saturated system (θw = 0.45) the
horizontal spreading therefore is minimal and the transport
will be dominated by advection in the water phase. This means
that in deposits with high water content (such as clay) the 1D
and 3D solution will provide similar contaminant distribu-
tions. From Fig. 3B it is also seen that horizontal spreading in
the gas phase has a great influence on the attenuation even
under relatively high water saturation conditions. For water
contents below 0.3 the three-dimensional solution does not
give substantially different results. However, this is under the
assumption that the soil gas exist as an interconnected phase.
The water content also influences the degree of degradation,
because this is assumed only to occur in the water phase.
The chosen water phase dispersivities are also very
uncertain and only limited literature on dispersivities in the
vadose zone is available. Vanderborght and Vereecken (2007)
present a review of longitudinal (vertical) dispersivities in soils
and conclude that the dispersivity increases with increasing
transport distances in the vadose zone. They also find that the
longitudinal dispersivity is much higher for saturated than for
unsaturated conditions. Studies on transverse dispersivity and
how it might be related to the longitudinal dispersivity in the
vadose zone are lacking.
A sensitivity analysis has been conducted to check how the
contaminant spreading depends on the dispersivities. Fig. 3C
shows the steady-state concentration calculated for a variety of
transverse dispersivities at two different water contents
(θw = 0.15 and θw = 0.40) and with the longitudinal dispersivity
held constant at αL = 0.1 m. At low water content (θw = 0.15) it is
seen that the transverse dispersivity in the water phase does
not influence the model results, because transport is dominated
by gas-phase diffusion. In this case the choice of dispersivity is
irrelevant and the mechanical dispersion in water can be
neglected. However, as seen from Fig. 3C the influence of the
transverse dispersivity is more pronounced when the soil nears
saturation (θw = 0.40). Thus, the effect of mechanical dispersion
in water is important to consider in case of high water contents
and/or for less volatile compounds. A similar sensitivity analysis
for the longitudinal dispersivity showed that the longitudinal
dispersivity does not influence the steady-state concentration
33
distribution. However, the longitudinal dispersivity is impor-
tant for the calculation of transient concentration distributions
and breakthrough times.
Risk assessments typically focus on ensuring that the
maximum concentration levels (MCLs) meet defined quality
criteria. The results shown here demonstrate the importance of
using a three-dimensional approach when assessing the risk to
groundwater of volatile compounds. In some cases it may be
reasonable in risk assessment to ignore the horizontal spread-
ing mechanism and employ the simpler one-dimensional
solution because resultant concentrations at the water table
will be over-estimated. The one-dimensional solution will be
quite accurate for large sources located close to the water table
and for less volatile compounds. However, for many cases
horizontal spreading will be an important attenuation mechan-
ism and so the full 3D solution should be used where possible.
The risk of groundwater contamination by BTEX in the
present case is considered to be very minimal based on the
model calculations. This is supported by field data showing that
no contaminants have been detected in groundwater. The trend
in the measured levels of BTEX in the pore gas is captured by the
models and indicates that degradation and gas spreading are
dominant processes that should be accounted for. Measure-
ments of oxygen and carbon dioxide levels in the pore gas are
shown in Fig. 4. It is seen that the oxygen levels are generally
reduced below atmospheric levels, whereas elevated levels of
carbon dioxide are observed. At and near the depth of the
source zone the oxygen levels is more markedly reduced, while
the carbon dioxide is increased correspondingly compared to
atmospheric levels, clearly indicating that degradation is taking
place. In Fig. 2 the best fit to data is achieved with a first-order
degradation rate of 0.1 d− 1. This rate is in the low end, but
consistent with values reported in the literature (DeVaull et al.,
1997; Hers et al., 2000; Hohener et al., 2006).
3.2. Assessment of horizontal contaminant spreading from a
source located under an impermeable cover — application of
model 4
An extreme case will be where there is an impermeable
cover on the land surface. When the ground surface is sealed,
Fig. 4. Measured pore gas concentrations (%) of oxygen (O2) and carbon
dioxide (CO2).
34 M. Troldborg et al. / Journal of Contaminant Hydrology 105 (2009) 28–37
infiltration rates will be small and volatilisation to the
atmosphere will be hindered. In this case lateral spreading
will be an important mechanism leading to contamination of
far greater areas than are observed where there is an unsealed
surface. In these cases, model 3 or model 4 can be used to
assess the possible extent of contamination.
At a former machine factory a leaking underground vessel
containing TCE has led to a contamination of the unsaturated
zone and a secondary aquifer. From the vessel free phase TCE
has leaked into the unsaturated zone more than 30 years ago.
The unsaturated zone consists of 3 m of nearly water saturated
clay till, followed by 7 m of unsaturated fine sand with porosity
0.4 (estimated from grain size distribution) and a water content
of 0.1 (estimated from measurements of water saturation). The
saturated zone is observed 10 m below ground surface. The site
is located in a paved industrial estate and infiltration through
the contaminant source is negligible. It is expected that free
phase leakage has created a narrow source area that stretches
from the soil surface to the saturated zone. In the unsaturated
zone radial contaminant spreading governed by gas diffusion is
observed, which has led to a large contaminant plume in the
aquifer (Tuxen et al., 2006).
Model 4 has been used to assess the radial TCE spreading
from the source area in the unsaturated sand. The source
area is assumed to be circular with a radius of 1 m and has a
constant pore gas concentration of 300 mg TCE/m3. In a
distance of 100 m from the source the area is no longer paved
and the concentration is here assumed to be 0 mg TCE/m3
because of the free access to the atmosphere.
The diffusion coefficient for TCE in air is D0a =0.68 m2/d (US
EPA, 1996), and Henry's constant is set to KH = 0.24 (−) (Peng and
Wan, 1997; Warneck, 2007). For the sandy soil an organic
carbon fraction of foc = 0.0002 (−) has been measured and
a bulk density of ρb = 1.6 kg/l has been estimated. When
foc < 0.001, it has been suggested that Kd is independent of foc
and can be estimated from logKd = 1.01 · logKow − 3.46 (Piwoni
and Banerjee, 1989). A Kd = 0.12 l/kg has been calculated based
Fig. 5. Radial TCE concentration profile in the unsaturated zone calculated at
different times with model 4. Field TCE measurements along a transect
consisting of 5 wells/geoprobes located respectively at 0, 4, 11, 19 and 34 m
from the source area are shown. The measurements are conducted in the
unsaturated sand at several depths (3–10 m bgs). Note that the stationary
profile is also calculated with model 4 (and not model 3) and results from the
zero concentration boundary at r = 100 m.
on a logKow = 2.53 resulting in a retardation coefficient of
R= 2.99. The diffusion of TCE in water is 7.86 × 10− 5 m2/d (Spence,
2001). Degradation is neglected, because of aerobic conditions
in the unsaturated sand.
Fig. 5 shows the concentration as a function of radial
distance to the contaminant source in the unsaturated sand
calculated with model 4. The results are compared with field
measurements from a cross section consisting of 5 wells/
geoprobes in a 1D radial transect from the source to a radial
distance of 34 m east. Measurements have been conducted in
several depths at each well.
Fig. 5 shows that the spreading by gas diffusion is very fast
and after only 1 year the TCE concentration in the pore water
reaches the drinking water limit value of 1 μg/l in a distance of
25 m away from the source. The fast spreading is caused by the
volatile properties of TCE and the low water content in
the unsaturated zone. In the figure the stationary solution is
also shown where degradation is not included. In the
stationary solution the decrease in concentration with radial
distance is due to the assumption that the concentration is
0 μg/l at a finite distance from the source. At the site, the zero
concentration boundary was set to the distance corresponding
to the end of the impermeable/paved cover over the site,
where it is assumed that gas phase exchange with the
atmosphere occurs.
Although the measured field data do not completely
match the simulations by model 4, it has been possible to give
a fair approximation of the extent of the contaminated area
and demonstrate the trend in measured data. It should be
noted that the measured data along the cross section are not
constant with depth and also vary with time. This variation is
due to heterogeneities in the soil material, varying water
content and advective gas transport governed by barometric
pressure alterations, which leads to oscillations around the
diffusive concentration profile. In a risk assessment context
model 3 and model 4 are considered applicable for situations,
where an impermeable layer hinders infiltration, since they
enable an estimate of the extent of the contaminated area
when spreading of volatile compounds in the unsaturated
zone is significant. The models also provide an estimate of
how fast this spreading occurs.
4. Discussion
4.1. Risk assessment, analytical modelling and parameter choice
Risk assessments are often subject to data limitations and
they therefore typically rely on analytical models, which have
minimal data requirements. Although these models are based
on series of simplifying assumptions they are still considered
appropriate for an initial assessment of the pollution risk.
Besides being straightforward to apply, analytical solutions are
also useful for sensitivity analyses, for determining dominant
processes and for validating numerical solutions. Models for
risk assessment must be applicable using only basic site data.
Although the models presented here describe transport in two
coupled phases, they do not require more site specific input
than other currently available vadose zone risk assessment
models.
In risk assessments the choice of model parameters
is generally very uncertain, because of the limited data available
 M. Troldborg et al. / Journal of Contaminant Hydrology 105 (2009) 28–37
and often it is therefore necessary to resort to values presented
in the literature. However this is not always straightforward,
because some parameters are known to vary orders of
magnitude, whereas others are not very well determined
for the unsaturated zone. For example, in a literature review
DeVaull et al. (1997) report first-order degradation rate
constants for BTEX in the vadose zone between 0.05 and 35 h
−1
based on pore water concentrations under aerobic condi-
tions. This range of (at least) 3 orders of magnitude should be
seen in light of the model calculations in Section 3.1, where
the leachate concentrations were found to be very sensitive to
the degradation rate. In the literature only very few values of
dispersivity have been reported for the unsaturated zone, e.g.
Vanderborght and Vereecken (2007) and Zhan (1996). Most
studies of dispersivity have been focused at horizontal transport
in aquifers, where different relationships between dispersivities
and scale have been suggested (Gelhar et al., 1992; Xu and
Eckstein, 1995). Whether these relationships can be transferred
to the unsaturated zone must be considered questionable.
However, under unsaturated conditions the model calculations
show that the influence of water phase dispersion is minimal
compared to gas phase diffusion, and therefore the uncertain-
ties related to the dispersivities are not significant to the results
presented.
4.2. Coupling to groundwater — 1D vs. 3D
The 3D model (model 1) provides a physically more correct
picture of the contaminant transport and spreading through an
unsaturated zone compared to the 1D model (model 2). In a risk
assessment context, where focus is typically on estimating
maximum contaminant levels (MCLs), accounting for the three-
dimensional spreading is important, since it may reduce the
concentrations reaching the groundwater table considerably.
The inclusion of horizontal spreading could therefore poten-
tially mean that the number of sites considered problematic
to groundwater could be reduced. For example, in developing
Soil Screening Levels (SSL) the US EPA uses a Dilution-
Attenuation Factor (DAF) that describes the relation between
the concentrations of the water reaching the groundwater
table and the acceptable groundwater concentration level
(US EPA, 1996).
Due to the many uncertainties related to risk assessments,
one often makes use of approaches that ensure that
conservative results (i.e. an overestimation of risk) are
obtained, for example through the choice of model para-
meters. In this sense, the 1D model may be reasonable,
because it generally overestimates the impact. It should,
however, be noted that the 3D model also is likely to
overestimate the calculated concentrations. For example,
model 1 does not account for contaminant loss to the
atmosphere. Both field investigations and model studies
have shown that the risk of groundwater contamination
from sources contaminated with VOC is limited in areas with
little or no cover layer due to loss to the atmosphere
(Grathwohl et al., 2002; Lahvis et al., 2004; Christophersen
et al., 2005). Furthermore, most of the assumptions described
in Section 2 ensure that conservative results are obtained e.g.
assuming instantaneous equilibrium, only considering single
components and assuming that degradation and sorption only
occur in the water phase.
35
Fig. 6. Stationary pore gas concentrations at the groundwater table as a function
of the radial distance from the source centre as calculated with model 1. The
calculations are based on the example in Section 3.1 and degradation has been
neglected.
One question related to the three-dimensional vadose
zone model is how to couple the model results to ground-
water. Many risk assessment tools couple a vadose zone
model with a groundwater model to calculate the resultant
concentrations in an underlying aquifer. This is done by
calculating the mass loading Juz-gw (M/T) from the contami-
nant source to groundwater. Assuming that the mass transfer
from the unsaturated zone to the saturated zone is governed
by water phase advection gives:
JuzQgw = Cleach  AuzQgw  qw ð17Þ
where Cleach (M L− 3) is the water phase concentration at
the groundwater table, Auz-gw (L2) is the contaminated area
at the water table and qw (L T− 1) is the infiltration rate. For
the one-dimensional solution (model 2), Auz-gw is identical
to the source area (Asource = X · Y) and the leachate concentra-
tion at the water table is constant within this area, making
the calculation of the mass loading straightforward. For
the three-dimensional solution (model 1), Auz-gw is bigger
than the source area due to the horizontal spreading. The
concentrations reaching the groundwater table within this
area are furthermore not constant. This is illustrated in Fig. 6,
where the concentrations at the groundwater water table
based on calculations from the example in Section 3.1 are
shown. The concentrations at the water table are radial
symmetric due to the diffusive spreading and it is seen that a
large area is impacted. This complicates the calculations of the
resulting concentrations in groundwater. It should be noted
that the mass loading to groundwater is independent of
the model dimensions. If the concentrations from the three-
dimensional model are integrated over the affected area, a
mass loading equal to the one-dimensional mass loading will
be achieved. The choice of dimension has however a big
influence on the resulting concentrations in groundwater,
because the mass loading is distributed over different areas
and therefore is diluted in different ground water volumes.
The calculation of mass fluxes to groundwater is also
complicated by the gradual increase of water content when
36 M. Troldborg et al. / Journal of Contaminant Hydrology 105 (2009) 28–37
approaching the capillary fringe. As discussed in Section 3.1
the water content is critical for the attenuation of contami-
nants and affects both the effective dispersion coefficient and
the degree of degradation. The increasing water content at the
capillary fringe is not accounted for by the models.
5. Conclusions
A general approach has been provided to develop analy-
tical solutions to combined gas and aqueous phase contami-
nant transport in the vadose zone. The approach is based on a
two-phase contaminant transport equation (Eq. (2)), which
has the same general form as the standard advection–
diffusion equation. Many analytical solutions are available to
Eq. (2) for various types of initial and boundary conditions.
Thus it is possible to develop a suite of analytical solutions that
can describe a range of scenarios for gas and water phase
transport of contaminants. Here four such solutions are
presented with the aim of being applicable to risk assessment
for contaminated sites. The four solutions are different from
existing risk assessment models in that they take horizontal
gas spreading and degradation into account. The four new
models have been tested on different sites to evaluate
their applicability. Based on the simulations the following
was concluded:
1. Gas phase transport and degradation are important pro-
cesses in risk assessment contexts.
2. The 3-dimensional solution to the vertical transport equa-
tion (model 1) gives the most realistic picture of contaminant
spreading in an unsaturated zone.
3. A 1-dimensional solution (model 2) is a reasonable approx-
imation when water content is high, source areas are
large, for shallow unsaturated zones and/or easy degradable
compounds.
4. The horizontal diffusive spreading of volatile compounds
in the unsaturated zone overlain by an impermeable
layer is very fast and may lead to large areas affected by
contamination.
5. Risk assessment models and choice of parameters are
uncertain due to limited data. The water content and
degradation rates are found to be critical parameters for
the spreading in the unsaturated zone.
Acknowledgements
This work was conducted as part of a project to develop a
new unsaturated zone contaminated site risk assessment tool
for Denmark and was supported by the Danish Environment
Protection Agency.
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