Water Air Soil Pollut (2016) 227:379

DOI 10.1007/s11270-016-3077-7

A Methodological Approach to Assess the Dissolution

of Residual LNAPL in Saturated Porous Media and Its Effect
on Groundwater Quality: Preliminary Experimental Results
Eleonora Frollini & Daniela Piscitelli & Iason Verginelli &
Renato Baciocchi & Marco Petitta

Received: 13 May 2016 / Accepted: 9 September 2016

# Springer International Publishing Switzerland 2016

Abstract In this paper, we present a simple methodo-
logical approach to assess the dissolution behaviour of
residual light nonaqueous phase liquid (LNAPL)
sources entrapped in saturated porous media and to
estimate the actual risk to human health by water inges-
tion related to their presence in the subsurface. The
approach consists of collecting experimental data on
the release kinetics through lab-scale column tests and
including these data in a modified version of the analyt-
ical model used to describe the groundwater ingestion
pathway in risk analysis. The approach was applied to
different test scenarios using toluene as a model com-
pound and three types of porous media, i.e. glass beads
and two sandy soils with slightly different textures. The
experimental results showed that the concentration of
toluene in the eluted water was far from the solubility
value after a limited number of pore volumes. Further-
more, different behaviour was observed for the three
types of porous media. In particular, higher residual
saturation and a slower dissolution rate were observed
for the soil characterized by the finest texture. This
behaviour suggests that the release rate is inversely
proportional to the total residual saturation due to the
E. Frollini : M. Petitta (*)
Earth Sciences Department, Sapienza University of Rome, P.le
Aldo Moro 5, 00185 Rome, Italy
e-mail: marco.petitta@uniroma1.it
D. Piscitelli : I. Verginelli : R. Baciocchi
Laboratory of Environmental Engineering, Department of Civil
Engineering and Computer Science Engineering, University of
Rome BTor Vergata^, Via del Politecnico 1, 00133 Rome, Italy
reduction in the porosity available for water flow and the
permeability of the porous media. Using these data in a
modified risk-based model showed that a remarkable
reduction of the hazard index related to the water inges-
tion pathway can be achieved for a relatively high
groundwater velocity and a small contamination source.
Keywords LNAPL . Dissolution experiments . Porous
media . Column test . Risk assessment
1 Introduction
The accidental release of petroleum hydrocarbons in the
subsurface due to leaking underground storage tanks,
accidental spills or improper surface applications is a
widespread environmental problem (Karapanagioti
et al. 2003). Soil contamination by petroleum products
poses potential threats to safety, human health and nat-
ural ecosystems when improperly managed (Baciocchi
et al. 2010). At relatively low concentrations, petroleum
hydrocarbons are present in the subsurface as dissolved
phase in soil pore water, as vapour in the soil pore air
and sorbed to the organic carbon of the soil. Linear
equilibrium partitioning between these phases is pre-
sumed at soil pore vapour concentrations and at pore
water concentrations below saturation (ASTM 2000).
At higher concentrations, a light nonaqueous phase
liquid (LNAPL) may be detected. Up to a given mass,
although an LNAPL is present, the hydrocarbon com-
pounds may be retained in an immobile condition in the
unsaturated zone due to capillary, viscous and gravity
379 Page 2 of 11
forces acting on the bulk free phase (Verginelli and
Baciocchi 2013). The LNAPL is immobile (Feenstra
2005) provided that its saturation in the soil is lower
than residual saturation, which is the fraction of avail-
able soil pore volume taken up by the immobile NAPL
(ASTM 2000). The LNAPL becomes mobile and can be
transported in the subsurface if its saturation exceeds the
residual saturation. For this reason, the first action to be
conducted at a site characterized by the presence of an
LNAPL is the recovery of the free product. Neverthe-
less, the complete recovery of all the NAPL is difficult
(Seagren et al. 1999) and usually results in the develop-
ment of residual NAPL in the soil. Although it is not
mobile, the residual phase can serve as a long-term
source of dissolved hydrocarbon plumes unless it is
removed from the subsurface, isolated from the ground-
water system or treated in situ. Due to its very limited
mobility in porous media, the removal of the residual
phase from an aquifer is not easy, and it represents a key
environmental issue at most sites contaminated by hy-
drocarbon compounds. In addition, the LNAPL residual
phase distribution is conditioned by the microscale and
macroscale heterogeneity of the subsoil, defined in
terms of the porous medium-size distribution, hydraulic
conductivity and pore structure (Jones and Smith 2005;
Nambi and Powers 2000; Powers et al. 1992), which
influence the behaviour and transport of contaminants.
Low-permeability materials protect the underlying aqui-
fer from contamination, but they can also act as a source
of contamination. Aquitards that are exposed to contam-
inated groundwater for a long time can become a sec-
ondary source of contamination due to the back diffu-
sion activated by aquifer remediation, which leads to the
release of contaminants that are temporarily
immobilized in the low-permeability materials
(Chapman et al. 2012; Cherry et al. 2006; Liu and Ball
2002; Parker et al. 2008). In addition, as LNAPL is
typically found in the largest pores, which mostly con-
tribute to the water flow in porous media, its presence
can lead to a reduction of the relative permeability to
water (Saba and Illangasekare 2000; Zhang et al. 2014)
and to an increase in heterogeneity in the soil (Nambi
and Powers 2000). For these reasons, many studies have
been conducted to evaluate the interaction between the
geological framework and the migration of NAPLs in
the subsurface. A number of studies were focused on
chlorinated solvents, which form dense nonaqueous
phase liquid (DNAPL) phases (Bao et al. 2003;
Chapman et al. 2012; Page et al. 2007; Parker et al.
Water Air Soil Pollut (2016) 227:379
2008; Puigserver et al. 2013; Thomson et al. 1992).
Furthermore, several laboratory and field studies aimed
at assessing the LNAPL behaviour in the subsurface
were performed in unsaturated (Adepelumi et al. 2006;
Kamaruddin et al. 2011; Kechavarzi et al. 2005) and
saturated zones (Carroll and Brusseau 2009; Mobile
et al. 2016; Nambi and Powers 2003; Powers et al.
1992; Sulaymon and Gzar 2011).
In this work, we propose a simple methodological
approach to evaluate the behaviour of the residual phase
of LNAPL and the impact related to its presence in the
phreatic zone. Specifically, lab-scale column tests were
conducted to collect data on the behaviour and dissolu-
tion profiles of hydrocarbons from the residual LNAPL
phase over time. Toluene, a member of the benzene,
toluene, ethylbenzene and xylene (BTEX) group, was
chosen as the model compound due to its widespread
presence in hydrocarbon-contaminated sites. These data
were combined with a simple kinetic model to evaluate
the cumulative mass of contaminant released as a func-
tion of the number of pore volumes delivered. Finally,
this information was included in the risk assessment
procedure of a model site to evaluate the risks to human
health related to the presence of residual LNAPL in
groundwater. The approach proposed in this work ac-
counts for mass transfer and dissolution kinetics, thus
greatly improving the predictive capability of the current
risk assessment procedures (ASTM 2000), which al-
ways assume equilibrium partitioning of the contami-
nants between the different phases of the soil system. In
this way, a more realistic assessment of the risks related
to groundwater contaminated by residual LNAPL is
made possible, while maintaining the simplicity of the
ASTM-risk-based corrective action (RBCA) procedure
(ASTM 2000).
2 Materials and Methods
2.1 Materials
Toluene (C6H5CH3 or C7H8) (99.8 %, Sigma-Aldrich) is
characterized by a density that is lower than that of water
(856 g/l) and a solubility in water of 526 mg/l at 20 °C
(EPA 2015). Toluene was chosen as the model com-
pound due to its widespread presence in hydrocarbon-
contaminated sites as a member of the BTEX group.
BTEXs, although generally present at relatively low
percentages in gasoline mixtures, represent the main risk
Water Air Soil Pollut (2016) 227:379
drivers at petroleum-contaminated sites due to their
chemical and toxicological properties (Verginelli and
Baciocchi 2014; Verginelli et al. 2016). Fluorobenzene
(C6H5F) (99 %, Sigma-Aldrich) was used as the internal
standard. Toluene and deionized water, produced by
reverse osmosis (Zeneer Power System), were used for
all experiments. The tested porous media were glass
spheres (φ = 6 mm) and sandy soils.
The sandy soils, obtained by mixing fluvial deposits
and rock avalanche deposits collected from different
sites of central Italy, were reconstructed in the laboratory
by sieving the material with ASTM sieves from n 10
(φ = 2 mm) to n 200 (φ = 0.075 mm) and then washing
and drying them at 110 °C to reproduce two grain size
curves that were representative of two poorly sorted
sands with a fine-grained matrix (see Table 1 for
details): the first (A) was 9 % silt and 1 % clay, and
the second one (B) was 14 % silt and 2 % clay (Table 1).
The ASTM granulometric scale, which has 2 mm as the
coarse sand/medium sand limit, 0.425 mm as the medi-
um sand/fine sand limit, 0.075 mm as the fine sand/silt
limit and 0.005 mm as the silt/clay limit, was adopted.
T h e u n i f o r m i ty c o e ff i c i e n t s , c a l c u l a t e d b y
HydrogeoSieveXL (Devlin 2015), were 7.93 and
12.73, respectively. The uniformity coefficient corre-
sponds to the ratio between d60 (the diameter at which
60 % of the sample mass is composed of smaller parti-
cles) and d10 (the diameter at which 10 % of the sample
mass is composed of smaller particles) and represents
the degree of uniformity in the granular material. The
higher the value, the lower the soil uniformity; a soil
with a uniformity coefficient less than 2 is typically
considered uniform (Lambe and Whitman 1969). The
sandy soil samples, consisting mainly of minerals such
as quartz, calcite, feldspars, muscovite and augite, were
Table 1 Properties of the reconstructed soils A and B
Parameter Soil A
Grain size distribution Medium sand 50 %
Fine sand 40 %
Silt 9 %
Clay 1 %
Uniformity coefficient 7.93
Minerals Quartz (52 %), calcite (28 %), feldspars (11 %), muscovite (5 %) and augite (4 %)
Total organic carbon (TOC) 0.192 %
Specific gravity (γs) 2.735 g/cm3
−5
Hydraulic conductivity 6 × 10 m/s
Page 3 of 11 379
characterized by low total organic carbon (TOC): 0.192
± 0.01 % for soil A and 0.189 ± 0.01 % for soil B. TOC
was calculated as the difference between the total carbon
and the inorganic carbon measured by an infrared ana-
lyzer (Shimadzu TOC-VCPH SSM5000) assuming a
specific gravity (γs) of 2.735 g/cm3 and 2.743 g/cm3
for soil A and soil B, respectively, calculated by the
ASTM D 854-06 method. The hydraulic conductivity,
estimated by HydrogeoSieveXL (Devlin 2015), was
approximately 6 × 10−5 m/s in soil A and approximately
half that value (3 × 10−5 m/s) in soil B, in agreement
with literature data (Spitz and Moreno 1996).
2.2 Experimental Procedures
The dissolution kinetics of the residual toluene NAPL
were investigated through column experiments per-
formed in 12.7-cm-long cylindrical glass columns with
an inner diameter of 2.9 cm (Fig. 1). Three tests were
conducted: two tests were performed using sandy soils
with different grain sizes (A and B), and one test was
performed using glass spheres φ = 6 mm (control test).
The column was packed, from bottom to top, with 2 cm
of large glass spheres (φ = 5 mm), 1 cm of small glass
spheres (φ = 3 mm), 2 glass microfibre filters (0.7 μm),
and 6.7 cm of soil (dried in an oven at 110 °C) corre-
sponding to approximately 74 g of soil (glass spheres
φ = 6 mm in the control test), 2 glass microfibre filters
(0.7 μm), 1 cm of small glass spheres and 2 cm of large
glass spheres (Fig. 1).
The total porosity (n), calculated based on the
weight and the specific gravity (γs) of the soil in
tests A and B, was approximately 0.38. For the
control test with glass spheres, we assumed a total
Soil B
Medium sand 48 %
Fine sand 36 %
Silt 14 %
Clay 2 %
12.73
0.189 %
2.743 g/cm3
3 × 10−5 m/s
379 Page 4 of 11
Fig. 1 Column setup for the
experiments
porosity of approximately 0.36–0.40, indicative of
random packing (Zhang et al. 2006).
In each experiment, the column was first saturated
with demineralized water from the bottom to remove
gas bubbles trapped in the porous matrix and to estimate
(based on the water trapped in the column) the pore
volume of the column. Saturation was performed using
a peristaltic pump connected to the column with tubes in
Iso-Versinic, which is a synthetic fluorocarbon polymer
that is resistant to toluene. Then, toluene was fed into the
column to simulate the movement of organic liquid into
the saturated zone (USEPA 1990). To maintain a stable
displacement front, toluene was injected with the peri-
staltic pump from top to bottom under sufficient head to
reduce the fraction of pore space occupied by water to
the so-called irreducible water saturation (USEPA
1990). Toluene was then continuously fed until the
water present in the column was completely displaced
by toluene, indicating complete saturation with the or-
ganic liquid (Powers et al. 1992 and USEPA 1990).
The column was then flushed from the bottom with
demineralized water at relatively high flow rates (from
0.5 to 1 ml/min) for approximately 25 pore volumes to
displace the free phase of toluene. After this flushing
step, it was possible to calculate the residual saturation,
as defined by Mercer and Cohen (1990), i.e. the satura-
tion at which the NAPL becomes discontinuous and is
immobilized by capillary forces under ambient ground-
water flow conditions.
The residual toluene saturation (Sres) was calcu-
lated following the method proposed by the
USEPA (1990) and used by Boving et al. (1999),
Water Air Soil Pollut (2016) 227:379
Boving and Brusseau (2000) and Carroll and
Brusseau (2009):
V rt V it −V d
S res ¼ ¼ ð1Þ
V it V it
where the volume of organic liquid in the soil (Vrt)
was determined from the difference between the
volume injected into the column (Vit ) and the
volume displaced from the column (Vd), which
were measured with a graduated glass cylinder.
Next, to assess the dissolution kinetics of toluene
from the residual phase entrapped in the column,
demineralized water was fed into the column at different
flow rates (0.2–2 ml/min in the soil tests and 0.2–13 ml/
min in the glass sphere test), and effluent samples were
collected in vials at regular intervals and analyzed for
toluene, as described. All experiments were run with the
column in a vertical position for approximately 900 pore
volumes.
2.3 Sample Analysis
The toluene in the water samples collected at the column
outlet was measured by static headspace gas
chromatography-mass spectrometry (HSS-GC-MS)
with fluorobenzene as an internal standard.
For the headspace analysis, 10-ml samples were
stirred for 40 min at 70 °C in 20-ml headspace
vials containing 2.5 g NaCl to increase the vapour
phase concentration through the salting-out effect
(Piscitelli et al. 2015). The headspace gas (250 μl)
was injected (split 1:10) with an autosampler
Water Air Soil Pollut (2016) 227:379
(AOC-5000 plus) into a Shimadzu GC/MS
(GC_QP2010SE) equipped with a TR-5MS column
(30 m × 0.25 mm ID × 0.25-μm film thickness:
5 % phenyl (equiv) polysilphenylene–siloxane).
Helium (0.9 ml/min) was used as the carrier gas.
The initial oven temperature of 35 °C was held for
3 min and was then ramped to 180 °C (at 10 °C/
min) and maintained for 2 min. The MS settings
were as follows: ionization voltage, 0.87 kV; in-
terface temperature, 230 °C; and detector tempera-
ture, 200 °C (Shin and Kim 2009). Selected ion
monitoring (SIM) acquisition mode was used, and
the selected ion fragments were 91 (toluene) and
96 (fluorobenzene). All GC-MS analyses were per-
formed in duplicate.
2.4 Modelling
For each test, the cumulative mass of the contaminant
(mg) eluted from the column was estimated as follows:
X
n cancer during life due to the exposure to the substance
M out ðcum; measuredÞ ¼ C measured;i ΔV i
i
where Cmeasured (mg/l) is the toluene concentration mea-
sured at the column outlet at the ith interval and ΔV (l) is
the volume of water fed into the column during the ith
interval.
Following the approach adopted in the risk as-
sessment procedures based on the traditional
ASTM-RBCA approach, the same cumulative mass
can be estimated assuming that the contaminant
concentration in the eluate from the residual phase
is equal to its solubility, which corresponds to
assuming a release at equilibrium conditions and
leads to the following equation:
M out ðcum; equilibriumÞ
X
¼ C sol ⋅ΔV ¼ C sol ⋅npv ⋅PV
where Csol (mg/l) is the solubility of the contam-
inant in the water, ΔV (l) is the volume of water
fed into the column during the ith interval, npv (−)
is the number of pore volumes fed into the col-
umn, and PV (l) is the pore volume of the column.
By combining Eqs. (2) and (3), it is possible to
estimate the ratio (CF) between the theoretical
cumulative mass assuming saturation conditions
and the experimental cumulative mass, both
Page 5 of 11 379
calculated for a specific number of pore volumes
delivered (npv*):
 
  M out cum; equilibrium; npv *
C F npv * ¼   ð4Þ
M out cum; npv *
The higher the CF values obtained through Eq. (4),
the greater the overestimation of the mass release calcu-
lated assuming equilibrium conditions between the elu-
ate and the NAPL.
2.5 Risk Calculation
Based on the traditional ASTM-RBCA approach, the
human health risk due to the ingestion of contaminated
water from wells located downstream a LNAPL source
is calculated, assuming that the concentration in ground-
water is equal to the solubility value for the entire
exposure duration. Under this assumption, in the case
of carcinogenic compounds, the risk for human health,
which represents the probability of incremental cases of
ð2Þ compared to the usual conditions of life, is given by the
following equation (ASTM 2000):
R ¼ C sol ⋅S FIng  EMIngw ð5Þ
where Csol (mg/l) is the solubility of the contaminant,
SFIng (1/[mg/kg day]) is the slope factor for ingestion,
and EMIngW(l/kg day) is the water ingestion rate factor.
For noncarcinogenic effects, the hazard index (HI)
can be calculated using the following equation:
EMIngW
HI ¼ C sol  ð6Þ
R f DIng
where RfDIng (mg/kg/day) is the reference dose for
water ingestion.
The water ingestion rate factor in Eq. (5) and Eq. (6)
can be calculated as follows (ASTM 2000):
ð3Þ IRw  E F  ED
EM IngW ¼ ð7Þ
day
BW  AT  365
year
where IRw (l/day) is the water ingestion rate, EF (day/
year) is the exposure frequency, ED (years) is the expo-
sure duration, BW (kg) is the body weight, and AT
(years) is the averaging time (assumed equal to ED for
noncarcinogenic compounds).
The above equations are valid for a contaminant
release from the residual phase under equilibrium
379 Page 6 of 11
conditions (i.e. for dissolved concentrations in ground-
water equal to the solubility). To evaluate the effective
risks in the presence of a residual phase, it is possible to
combine these equations with the dissolution profiles
obtained from the lab-scale column tests. By assuming a
linear and proportional relation between the effective
cumulative release observed in the experiment and the
theoretical release based on continuous release at the
solubility value, the effective risk (Reff) and hazard
index (HIeff) can be calculated as follows:
M out * ðcumÞ
Reff ¼ RðASTMÞ⋅
M out * ðcum equilibriumÞ
RðASTMÞ
¼   ð8Þ
C F npv *
M out * ðcumÞ
HIeff ¼ HIðASTMÞ⋅
M out * ðcum equilibriumÞ
HIðASTMÞ
¼   ð9Þ
C F npv *
where CF (−) is the correction factor estimated using
Eq. (4), which is a function of the pore volumes deliv-
ered (npv*). The reference number of expected pore
volumes delivered (npv*) in the field can be calculated
as follows:
vgw ED
npv * ¼ ð10Þ
L⋅θe
where ED (years) is the exposure duration, vgw (m/year)
is the groundwater velocity, L (m) is the length of the
source along the groundwater direction, and θe (−) is the
effective porosity in the saturated zone.
3 Results and Discussion
3.1 Experimental Results
3.1.1 Residual Saturation
The residual saturation data of toluene (Sres), expressed
in percentage, measured during the lab-scale column
tests are reported in Table 2. These results show that
the interaction between toluene and different porous
media is affected by the porous media type. In the
control test, where large glass spheres were used, the
Water Air Soil Pollut (2016) 227:379
Table 2 Residual saturation estimated from the different lab-scale
column tests carried out
Material Residual saturation (%)
Glass spheres 36
Soil A 70
Soil B 77
residual saturation was approximately 36 %, whereas it
was much larger in the column tests conducted with
soils, with average values of approximately 70 % for
soil A (with a lower content of fine-grained material)
and approximately 77 % for soil B (with a higher
content of fine-grained material). As expected, the sandy
soils had higher residual saturation than the glass
spheres; it is possible that this is not due to the presence
of organic carbon in the soils (approximately 0.2 %) but
to the presence of higher capillary forces that act to hold
toluene. In addition, the residual saturation increases
with decreasing grain size, although this effect is not
very relevant due to the small difference in the particle
size distribution of the two tested sandy soils.
3.1.2 Dissolution Profiles
Figure 2 shows the toluene concentration trends ob-
served in the experiments. During the first part of the
experiments performed on the column packed with glass
beads or soil A, the dissolved toluene concentrations in
water were higher than solubility in some samples. This
suggests that a small amount of mobile LNAPL was
present during the first phase of the column tests, lead-
ing to the elution of toluene droplets that were inadver-
tently caught in the collected samples and dissolved
after the dilution process for the analysis. In reference
to the results obtained in the control test (glass spheres),
the toluene concentration quickly dropped to less than
100 mg/l after approximately 50 pore volumes were
delivered (PV) and then remained below 20–30 mg/l
for the rest of the experiment. In the column test with
soil A, a slower decrease of the toluene concentration
with time was observed, and a toluene concentration of
100 mg/l was achieved after approximately 250 PV.
Then, the toluene concentration continued to slowly
decrease, reaching less than 1 mg/l at approximately
880 PV.
In the column test performed with soil B, a different
release trend was observed. In this experiment, the
Water Air Soil Pollut (2016) 227:379
Fig. 2 Toluene concentration vs
npv in the column tests
toluene concentration was always well below the solu-
bility value, ranging between 150 and 400 mg/l in the
first part of the test up to 225 PV and then slowly
decreasing to approximately 1 mg/l after 774 PV.
These results are in agreement with the fact that a
higher Sres leads to a reduction in the relative permeabil-
ity in water (Zhang et al. 2014) and consequently de-
creases the amount of the toluene in contact with
demineralized water because it bypasses the contami-
nated zone with lower permeability (Saba and
Illangasekare 2000). This process leads to a lower dis-
solution of the residual phase and lower concentrations
measured in the eluted water.
Page 7 of 11 379
3.2 Modelling Results
Figure 3 reports the experimental toluene cumulative mass
measured in the different tests at increasing pore volumes
eluted from the column; the curve (red line) shown in the
figure was obtained by fitting the data with a first-order
kinetic model. A good correlation was observed between
the measured and simulated data, with coefficients of de-
termination (r2) ranging between 0.9680 (in the glass
spheres column test) and 0.9977 (in the soil A column test).
This suggests that a simple first-order kinetic model can be
used to describe the release of toluene from the residual
LNAPL phase. Furthermore, Fig. 3 also shows the
379 Page 8 of 11 Water Air Soil Pollut (2016) 227:379

Fig. 3 Mout(cum) vs PV.

Experimental data, first-order
model and expected release
assuming equilibrium conditions.
npv is the number of pore volumes
delivered in the column

cumulative mass values expected when assuming equilib-
rium conditions (i.e. assuming a constant release of the
solution saturation conditions, as in the ASTM-RBCA
approach). In all cases, the cumulative release estimated
when assuming equilibrium conditions was higher than the
actual trend observed in the test, confirming that the release
occurred under nonequilibrium conditions.
Finally, the experimental release data and those calcu-
lated assuming equilibrium conditions, both reported in
Fig. 3, were used to estimate the CF ratio, defined in
Eq. (4), for the different numbers of pore volumes (npv)
delivered. The results are presented in Fig. 4, which shows
that the assumption that the eluate from the residual
NAPL is saturated with toluene may lead to CF values
much greater than unity, i.e. to a relative overestimation of
the true dissolved toluene concentration in water. More-
over, CF increases for increasing numbers of pore volume
delivered and can reach values of 200 (soil A) and 400
(soil B) at 10000 pore volumes (npv) delivered.
3.3 Risk Analysis Results
The HI for toluene due to accidental ingestion of
groundwater from wells located close to a residual
Water Air Soil Pollut (2016) 227:379 Page 9 of 11 379

Fig. 4 Derived correction factors (CF) to be used in the risk

assessment

LNAPL source was calculated for different contamina-

tion scenarios (Table 3) using either Eq. (6) or Eq. (9). Fig. 5 Risk analysis. Hazard index of the two different soils
The former corresponds to assuming a release from considering different groundwater velocities (vgw) and different
source lengths (L)
the residual LNAPL phase under equilibrium conditions
(i.e. the ASTM-RBCA approach); the latter accounts for
the CF data obtained from the actual release kinetics HI was up to two to three orders of magnitude lower
obtained from column tests, which was discussed and is than the HI obtained assuming a release from the resid-
shown in Fig. 4. ual phase at solubility. Specifically, the effective HI for
The results of the risk analysis are presented in Fig. 5. soil A ranged from 0.2 to 124.8 for a source zone length
The HI value calculated using the traditional ASTM of 10 m, from 3.8 to 145.9 for a source zone length of
approach (dotted red line) was approximately 180 and 50 m and from 10.8 to 148.9 for a source zone length of
was the same for both soils. The HI values estimated 100 m. For soil B, the effective HI ranged from 0.1 to
considering the empirical CF values (HIeff) were depen- 92.4, from 1.5 to 118.1 and from 4.5 to 122.1 for source
dent on the assumed groundwater velocity. The effective zone lengths of 10, 50 and 100 m, respectively.
The overestimation of the hazard index (HI) with
respect to the results, including the CF, is particularly
Table 3 Simulation conditions used for the HI calculation
significant for sources characterized by lower lengths
Parameter Values along the groundwater direction and in scenarios char-
acterized by higher groundwater velocity. In these sce-
Ingestion reference dose (RfDIng) (mg/kg day) 0.08a narios, the dissolved concentration of the contaminant
Water ingestion rate (IRw) (l/day) 2b quickly drops to values that are significantly lower than
Exposure frequency (EF) (day/year) 350b the solubility values. Based on these findings, the ap-
Body weight (BW) (kg) 70b proach proposed in some countries (Carlon 2007) to
Exposure duration (ED) (years) 30b estimate the risk to groundwater resources based on
Defined averaging time for noncarcinogenic 30b conservative concentration thresholds may provide an
(AT) (years) inaccurate perception of the effective impact on ground-
Groundwater velocity (vgw) (m/day) 0.02; 0.2; 2; 5
water quality at the point of compliance. Indeed, the use
Length of source zone area (L) (m) 10; 50; 100
of steady-state fate and transport models combined with
Effective porosity (θe) (−) 0.2
linear equilibrium partitioning model results in a situa-
a
According to ISS-INAIL (2015) tion that is representative only of the very early stages
b
According to APAT (2008) after the contamination event. The results indicated that
379 Page 10 of 11
after a relatively short time, the contaminant concentra-
tions in groundwater are expected to decrease by orders
of magnitude. This behaviour cannot be properly eval-
uated by a simple comparison with threshold values,
whereas it can be easily accounted for by adopting a
risk assessment procedure (especially if coupled with
the approach proposed in this work) that calculates the
risk based on the effective cumulative dose over the
entire exposure duration.
4 Conclusions
The experimental results obtained from lab-scale col-
umn tests conducted on soils contaminated by a residual
toluene LNAPL phase showed that the actual concen-
tration of toluene in the eluted water was well below
solubility after a limited number of pore volumes were
delivered. Overall, the amount of toluene released was
much lower than expected when assuming equilibrium
between the dissolved phase and the residual LNAPL.
Additionally, the soil properties (such as the grain
size distribution and permeability) affect the release of
the contaminant from the residual LNAPL phase. These
properties affect the residual saturation and release ki-
netics of the contaminant. A higher toluene residual
saturation (Sres) and slower dissolution of the residual
phase were observed for the soil sample characterized
by a finer texture when compared to the other tested
porous media. This behaviour suggests that the release
rate is inversely proportional to the total residual satura-
tion because a higher concentration of the latter reduces
the porosity available for water flow, lowering the per-
meability of the porous media. A remarkable reduction
of the HI related to the water ingestion pathway was
achieved by using these data in the risk analysis proce-
dure and adopting a new modified model that accounted
for the observed experimental release. This reduction is
particularly relevant for relatively high groundwater
velocities and for contamination source with limited
mass and extension.
In conclusion, the simple methodological approach
proposed in this work represents an easy-to-use tool to
evaluate the behaviour of LNAPL in the saturated zone
and to reduce uncertainty and to refine the assumptions
used in the traditional risk assessment procedure. Future
research should address the applicability of the method-
ological approach presented in this work to other types
Water Air Soil Pollut (2016) 227:379
of contaminants and porous media, possibly at a larger
scale, up to a field test.
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