Journal of Applied Geophysics 191 (2021) 104358

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Journal of Applied Geophysics

j ou rn al h om e p age : w w w . e l s e v i e r . c o m / l o c a t e / j a p p g e o

Detection of chlorinated contaminants coming from the

manufacture of lindane in a surface detritic aquifer by electrical
resistivity tomography
Bárbara Biosca a, Lucía Arévalo-Lomas b, Miguel Izquierdo-Díaz a, Jesús Díaz-Curiel b,⁎
a
Department of Energy and Fuels Systems, School of Mines and Energy, Universidad Politécnica de Madrid, C/ Ríos Rosas 21, 28003 Madrid, Spain
b
Department of Geological and Mining Engineering, School of Mines and Energy, Universidad Politécnica de Madrid, C/Ríos Rosas 21, 28003 Madrid, Spain

a r t i c l e info
abstract
Article history:
Received 24 February 2020 This work presents a case study using electrical resistivity tomography at a site mainly affected by the
Received in revised form 23 March presence of residual lindane coming from a close landfill constructed by an old pesticide manufacturer. In
2021 Accepted 28 April 2021 addition, the land- fill also collected chlorinated contaminants derived from the same industry. Lindane
Available online 6 May 2021 itself is a highly toxic con- taminant that in small concentrations constitutes a high risk to health,
which together with the other compounds, makes it a site with very hazardous characteristics. The
Keywords: geological distribution, formed by a complex detrital deposited over a marls substrate, is known from the
Lindane existing network of monitoring wells. A geophysical prospecting survey consisting of seven electrical
Electrical resistivity tomography tomography profiles was carried out in the site. The lateral and vertical geometry of the contaminant
Dechlorination
plume was established, and the preferential flow directions were inferred by means of the resistivity
DNAPL
sections obtained. Combining this information with analytical data from water sam- ples, an empirical
relationship between the conductivity value and the dissolved chloride content was developed, and the
distribution of the concentration of chlorinated contaminants in the surface aquifer by isochloride sec-
tions was obtained. The results obtained are a very useful tool as a preliminary stage to remediation
trials.
© 2021 Elsevier B.V. All rights
reserved.

1.Introduction (J. Díaz-Curiel).

Lindane, the gamma isomer of hexachlorocyclohexane (HCH), is

a very widespread organochloride pesticide (Fernández et al., 2013)
and has one of the greatest insecticidal action (Kutz et al., 1991). Both
its production and use generated a global pollution problem for
decades (Breivik et al., 1999; Li, 1999). One of the main problems
associated to lindane is the waste gen- erated by its inefficient
production process: for each tonne of lindane be- tween 8 and 12
t of other HCH isomers that constitute waste are generated
(Bodenstein, 1972; Fernández et al., 2013). In addition to this, it has
a long life and is easily moved over long distances, so it is
incorporated into the food chain (Wycisk et al., 2013; Muñoz-
Morales et al., 2017). Due to the environmental problems generated
by their spills, in the Stockholm Convention of August 2010, lindane
was included in the Persistent Organic Pollutant (POP) list (Vijgen
et al., 2011). Currently, areas with HCH are monitored worldwide,
but researchers encounter problems in explaining the observed data
due to the lack of reliable statistics on production and use of these
pollutants (Breivik et al., 1999; Simonich and Hites, 1995).
Between 1975 and 1992, the lindane production company INQUINOSA
released uncontrolled spills of around 140,000 t in specific areas
around

⁎ Corresponding author.
E-mail addresses: barbara.biosca@upm.es (B. Biosca), lucia.arevalo@upm.es
(L. Arévalo-Lomas), miguel.izquierdo@upm.es (M. Izquierdo-Díaz), j.diazcuriel@upm.es
the town of Sabiñánigo in northeastern Spain (Vijgen et al.,
2019). Sabiñánigo is considered one of the mega-sites existing
in Europe in which lindane constitute an environmental and health
problem. In addi- tion to Sabiñánigo, there are other large
contaminated sites in Europe where sustainable remediation was
not carried out due to the enormous costs involved, and where
only measures to contain the spills were ap- plied (Vijgen et al.,
2019).
An important aspect of lindane spills is the transport of the
dense chloride. It is a complex mechanism that depends on
properties such as density, viscosity (affecting subsoil mobility),
interfacial tension, the nature of the soil and the size and
distribution of its pores, saturation (fraction of pores occupied
by a fluid), relative permeability, and capil- larity (EPA, 2004;
https://doi.org/10.1016/j.jappgeo.2021.104358
0926-9851/© 2021 Elsevier B.V. All rights
reserved.
Engelmann et al., 2019). In addition, these contami- nants are
easily retained in the pores of fine-grained soils. The migration
of the dense components through different routes is facili- tated
by the hydraulic gradient of the area. It has reached the most
per- meable porous media, leaving part of the free phase
impregnated in the grains and pores producing an increase in
resistivity. This will not be sig- nificant unless the proportion of
them is sufficiently large.
Electrical geophysical prospecting methods are presented as
the
most suitable for geological and hydrogeological imaging, for
delineat- ing contaminant plumes and for estimating the main
flow directions (Daily and Ramirez, 1995; Ahmed and Sulaiman,
2001; Frid et al., 2008; Clément et al., 2011; Chibueze, 2013;
Gonzales et al., 2016; Maurya et al., 2017).
B. Biosca, L. Arévalo-Lomas, M. Izquierdo-Díaz et Journal of Applied Geophysics 191 (2021)
al. 104358

A key point in carrying out remediation monitoring at this

sections of chloride concentration in the subsoil. These constitute
type of sites is the prior lithological characterization and
a pre- vious step to the remediation processes and represent an
determination of the petrophysical properties of the terrain in
easy-to-apply reference tool for persons in charge of these
order to delimit the geometry of the contamination plume. The
processes but are not par- ticularly familiar with geophysical
characterization by electrical prospecting techniques of sites
methods. The location of remediation trials will be determined,
affected by the presence of dense non aqueous phase liquid
inter alia, based on the results of this study.
(DNAPL), has become very important in recent years since it
represents a serious environmental problem (Brewster et al.,
1995; Cardarelli and Di Filippo, 2009; Orlando and Viotti, 2009;
2. Site description
Thompson et al., 2011; Johansson et al., 2014; Naudet et al.,
2014; Casado et al., 2015; Park et al., 2016).
The study area is located to the northwest of the Iberian
In this sense, a critical aspect of the chlorinated hydrocarbons
Peninsula, to the south of the Pyrenees. To the west it is
is that they are non-polar fluids (electrical insulators), and hence
bounded by the Sabiñánigo reservoir, fed by the Gállego River,
should have high resistivity values with respect to uncontaminated
and to the east by a road. During the construction of this, in the
areas. However, except when the spill is recent, these plumes
1990s, the landfill was divided into two parts. Some 50,000 m3
tend to show lower resis- tivity values than uncontaminated
of waste was left in this lower part (Guadaño and Gómez, 2016).
areas (Benson et al., 1991; Ajo- Franklin et al., 2006). This is
This landfill was located to take advantage of the morphology of
due to the degradation they suffer in the subsoil and the
a gully of the substrate, and its closure was initially aligned
corresponding increase in the total dissolved solids in the water.
approximately with the outlet of the gully, about 200 m from the
One of the characteristic process in the degradation of
tail of the reservoir (see Fig. 1).
organochloride compounds is dechlorination (Dermietzel and
Although the main contaminant is residual lindane (HCH), it is
Vieth, 2002; Johansson et al., 2014), which produces an enrichment
not the only one, benzene and other organochloride compounds
in chlorine of the formation fluid. This increasing is usually
are also found (Fernández et al., 2013). There are two types
significant enough to identify such areas by geophysical
of lixiviates as established in 2010 by the Directorate General of
techniques and is one of the features on which this study is
Environmental Quality of the Aragon Community: some are
focused.
associated with the manufacture of lindane and others are related
Many of the characteristics of organochloride contaminant
to the chloro-alkyl industry. This mixture of residues generates,
cited above was taken into account since the emergence of
due to the high pH of the chloro-alkali leachates, an alkaline
resistivity tomog- raphy techniques (Chambers et al., 2004;
hydrolysis of the components with more chlorine of the DNAPL
Newmark et al., 1997; Sauck et al., 1998; Yang and You, 1999)
(Lorenzo et al., 2020; Santos et al., 2018b), contributing to the
and continue to be applied today (Arrubarrena-Moreno and
Arango-Galván, 2013; Liao et al., 2018). However, given the presence of free chlorine.
particularities of this type of pollutant, there is no specific A study of the lithological distribution of the site was carried
methodology defined. The results obtained in the laboratory an- out to evaluate the homogeneity or absence of lateral variations. In
alogues (Kang et al., 2018; Luciano et al., 2010; Power et al., 2014) this case, it makes sense to determine the variations in the
have provided valuable results, but transferring these results to a conductivity of the fluid in the formations from the resistivity
field study is not an easy task. values measured from the surface by electrical resistivity
tomography (ERT).
This communication presents the spatial characterization of
Geologically, the site is located on the alluvial plateau of the
the front of the Sardas landfill in Sabiñánigo by the resistivity
Gállego River, where quaternary deposits are divided into two
sections ob- tained from electrical resistivity tomography (ERT).
main horizons. A level of silt, with higher clay content in the
Moreover, based on the analytical values of chloride concentration
shallower area and interca- lations of sandy sections in the rest,
and conductivity mea- sured in water samples extracted from
with one-off presence of edges to- wards the wall, its thickness
more than 60 existing monitor- ing wells, a relationship
varies between 5 and 12 m. A second alluvial horizon formed
between the conductivity values of the formation water and
mainly by gravel with very variable grain sizes and the presence
this concentration was obtained. This relationship, together with
of a clay matrix. It has a thickness between 2 and 4
the results from the ERT, allowed the obtaining of 2D
m. In addition, this level presents intercalations of a medium-fine sand

2
B. Biosca, L. Arévalo-Lomas, M. Izquierdo-Díaz et Journal of Applied Geophysics 191 (2021)
al. 104358

Fig. 1. Location of the study area.

3
level that appears in some locations with a thickness of ~1 m.
Together, both horizons reach a thickness of approximately 15 m Fig. 2. Location map of the geological sections and tomographic profiles.

in the study plot. These are directly superimposed on an erosive

surface of the substrate of the zone constituted by deposits of grey
marls of several hundred me- ters of thickness. In the study area,
the detrital levels are wedged against the marls towards the
southwest. On these quaternary materials, there are different man-
made fill materials, about 4 m thick, coming from the front of
the landfill removed during the construction of the road.
From the borehole lithological columns provided by EMGRISA
Com- pany, it was possible to make four geological sections of the
study area (Fig. 2) whose 2D sections reflects the geological
distribution described above (Fig. 3).
As far as hydrogeological characteristics are concerned, two
types of behaviour can be distinguished. On the one hand, the fill
materials and fluvial-glacial quaternary deposits present primary
porosity permeability, differentiated in two parts, with the alluvial
level located below the silts being the stratum with the highest
permeability. This level acts as an aquifer witha certain degree of
confinement, due to the presence of the overlying silts. On the
other hand, there is the underlying Tertiary sub- strate of grey
marls, which presents some areas with important fracture levels,
acting as a permeable level. In those areas where the marls are
not altered or fractured, they can be considered practically
impermeable. The hydraulic behaviour is mainly characterised by a
water gradient which main component is southeast-northwest, with
some local variations due to the pumping of the monitoring wells
located in the area, and with a strong influence of the water level
height in the reservoir (Casado et al., 2015). The water table in
the study area varies between 5 and 10 m
deep depending on rainfall and the water height in the reservoir.

3.Methodology

3.1. Field Measurements

The survey consisted of seven geoelectric profiles, distributed

through- out the study area, as shown in the situation sketch in Fig.
2. The number of profiles and their distribution and extension was
limited by the character- istics of the area and the constructions
and other elements present in it. Al- though initially the aim was to
measure resistivity and chargeability in time domain, the signal-to-
noise ratio in the area has so far not allowed in- duced polarization
records of acceptable quality to be obtained.
The electrical prospecting equipment used is the Terrameter
SAS 4000 resistivity meter together with the ES646 tomographic
system,
both from ABEM. The used array was Wenner-Schlumberger type, although in the case of profiles P5 and P7, the values of this level
try- ing to reach the maximum lateral resolution for the fixed vary between 20 and 50 Ohm·m. It is located in all the profiles,
depth of study. The distance used between electrodes was 4 m, presenting lateral variations with resistivity drops up to 20 Ohm·m
with measure- ments being made at 10 levels of study, and in profiles P2, P3 and P4. These variations are found be- tween
finally reaching an investi- gation depth of slightly more than 15 metres 24 to 28 and 60 to 72 in profile P2, between metres 48
m. Table 1 shows the length and direction of each profile. The
measurements were made by setting a maximum stacking of 8
and admitting a maximum deviation from the median of 1%. The
percentage of error for each data is recorded, which allows to
clearly identify the points that do not reach the established
minimums of quality.

3.2. Data processing

The geoelectrical profiles obtained were first edited to

eliminate out- lier points due to some isolated problem in the
measurement or in the corresponding electrode, whose are
characterised by having a very dif- ferent resistivity compared
with neighbouring points. The resistivity sections were then
calculated by inverting the data with the Res2Dinv program of
GEOTOMO Software (Loke, 2008). The algorithm available for
inversion reduce the difference between the model response
and the observed data values (Loke and Barker, 1996; Loke
and Dahlin, 2002). The “smoothness-constrained least-squares”
method is used, that minimize the spatial variations in the
model parameters (Ellis and Oldenburg, 1994; Loke, 2011). The
inversion generates a mesh of resistivity values by minimising the
error with respect to the measured apparent resistivity. In the
inversion of all profiles, the same processing parameters were
used. An initial reference model based on the average resistivity
values found was used with a damping factor of 0.01. The in-
crease factor with depth was set to 1.05 for the reference
model. For the inversion an initial damping factor of 0.15 with a
limit value of 0.007 was set, and in some cases, alternatively
the optimization of the damping factor is allowed by the L-
curve method, which application in the inversion of geophysical
data is discussed in Oldenburg and Li (2005). Table 2 shows the
values of the difference between the calcu- lated and measured
apparent resistivity values (Error RMS %) achieved in each
inversion.
The resistivities obtained in the area vary between 147
Ohm·m and 2 Ohm·m values. Although in some areas apparent
resistivity values close to 1 Ohm·m were measured, taking into
account the variations generally found, a range between 4
Ohm·m and 140 was chosen as the most suitable scale.

4.Resistivity results

A preliminary question to evaluate the scope of the

tomographic in- version is that it is carried out under the
hypothesis of absence of dis- continuities in the values of
resistivity of the subsoil. Thus, at points where there is a net
discontinuity of resistivity, the tomographic inver- sion may result
in an image showing a smoother gradation and a greater spatial
extension.
Fig. 4 shows a 3D image of the tomographic sections
obtained ac- cording to their relative position. In this image, it is
possible to differen- tiate the main geoelectric horizons found
and their spatial distribution within the area.
Considering the distribution of the different lithologies within
the area (Fig. 3) and the geoelectric horizons obtained from the
tomo- graphic inversion (Fig. 4), the following correlation can be
established: A resistive surface horizon corresponding to the
man-made filling, with an average thickness of 4 m, although
occasionally it can reach 5 m depth. The resistivity values vary
mostly between 60 Ohm·m and slightly more than 200 Ohm·m,
 Fig. 3. Geological sections obtained from boreholes.

Error RMS (%) 5.5 6.1 4.3 4.0 8.5 5.7 4.6
Table 1
Characteristics of the measured profiles.

Profile Length (m) Number of electrodes Direction

P1 148 38 NE-SO
P2 104 27 NNO-SSE
P3 104 27 NNO-SSE
P4 100 26 NNO-SSE
P5 148 38 N-S
P6 88 23 NO-SE
P7 80 21 NNE-SSO

to 68 in profile P3, and between metres 3 to 60 and from metre

84 to the end in profile P4.
A second conductive horizon, corresponding to the level of
silts. It presents a variable depth, reaching in some cases up to
the maximum depth of study, and a high lateral heterogeneity. This
lateral variability is associated with a considerable increase in
resistivity, with values higher than 3 Ohm·m. This lateral and
vertical heterogeneity is also asso- ciated with granulometric
variations known from the borehole litholog- ical columns, although
this does not explain the recorded conductivities. A third horizon of
intermediate resistivity with resistivity values be- tween 20 and
60 Ohm·m corresponding to the alluvium formed by gravel
with medium-fine sand intercalations. Since this level is minted
and disappears in a southerly direction, it is only clearly detected
in the profile P1, while in the rest it is not sufficiently defined at
the max- imum depth of study. Variations in resistivity within this
level are due to granulometric changes due to the alternation
between gravel and sand. Although the marls substrate should be
appearing in some sections, mainly in those located southern
where silts are directly deposited on marls, however, it is not
well-defined in the resistivity sections. The ex- pected resistivity
values of marls vary over a considerable range. While

Table 2
Error RMS (%) of each resistivity profile.

Profile P1 P2 P3 P4 P5 P6 P7
in the healthy areas located at a greater depth they would be
very high, in the more fractured areas, the resistivity values are
very low due to the presence of a high salinity of the formation
water. The resistivity values associated with the detrital levels
are below those expected, reaching values close to 1 Ohm·m at
the silts level. This conductivity has its origin in the existing
contaminating compounds, and in the reactions that take place.
Fig. 4 shows the possible flow directions indicated by purple
arrows, based on the correlation of the most conductive zones.
The directions are indicated from profile 5 (farthest from the
reservoir) towards profile 6 (closest to the reservoir). It is worth
highlighting one flow in a N80°W direction almost coinciding with
the groundwater flow of the area, and another in a SW direction.
The conductive zones located in positions 68 to 88 of profile P5,
32 to 48 of profile P2, 20 to 32 of profile P3 and 16 to 24 of
profile P4 have been correlated. Those located in the same posi-
tions in profiles P2 and P5 have also been correlated with those
in posi- tions 48 and 54 of profile P3 and between 64 and 76
of profile P4.
In order to obtain an image of the lateral distribution of
these con- taminated zones within the geological levels, a series of
horizontal resis- tivity slices were obtained (Fig. 5). The
resistivity data obtained in the inversion cells in some of the
study depths were extrapolated.
Fig. 5 shows the resistivity variations for some depths. In the
repre- sented slices, it can be seen that the one corresponding
to the depth of
7.3 m shows high conductivity values, mostly located in the silt
level. These high values coincide with areas of residual lindane
accumulation known from the analysis of soil samples extracted
from the piezometers.
Although lindane is characterised by its low solubility, its
resistance to biodegradation, and natural attenuation (Pankow
et al., 1984), trichlorobenzenes are formed in basic media by
alkaline hydrolysis of HCH and pentachlorocyclohexane (Penta
CX), while tetrachlorobenzenes are produced from other
compounds also present in DNAPL such as
heptachlorocyclohexanes (Lorenzo et al., 2020; Santos et al.,
2018a). This is the case of the Sardas landfill, where the presence
of leachate de- rived from the chloro-alkyl industry raises the pH
to values of 13, facilitat- ing the occurrence of such dechlorination
phenomena. Consequently, it increases the chloride content in
the formation fluid, increasing its conductivity.
Areas with higher conductivity values can then be associated
with
areas of lindane accumulation in which the dechlorination
phenomena
Fig. 4. 3D representation of the obtained resistivity sections, all with a common depth scale between 0.66 m and 15.6 m.

are occurring. Given the low permeability of silts, low mobility of

the dense phases in them is to be expected. This means that
obtaining sec- tions with the distribution of chlorides within the
site will have great value in the planning of the remediation
stage.

5.Determination of ISO-chloride sections

Two previous and independent processes have been carried

out to determine the isochloride sections.

5.1. Fluid conductivity from ERT measurements

First, the fluid conductivity was calculated using the formation

factor F= ρ0/ρw defined by Sundberg (1932), where ρW is the
resistivity of the formation fluid and ρ0 the resistivity of the
medium. The low grain size of silt layer confers it a high
porosity value and its very low granulometric classification,
with a classification coefficient (Trask, 1932) equal to ~4,
produce a very low permeability value. This low value of
permeability implies a large residence time of contaminants in
this level and a small influence from the water height of
reservoir. The alluvial material has the opposite characteristics.
For levels that are completely saturated with fluid, Archie's
1st law (Archie, 1942) was used:

ρW ¼ ρ0⋅Øm ð1Þ

where Ø is the total porosity and m is an exponent which, in the

field of oil, where formations are usually consolidated, is called a
cementation exponent, and which in Díaz-Curiel et al. (2016), was
renamed as an ex- ponent of permeability. In this study, for fully
saturated media, the fol- lowing average values have taken for
each lithology: Ø ~ 40% and m =
2.2 for silts, and Ø ~ 25% and m = 1.8 for alluvium.
In the case in which the analysed level is not completely
saturated with fluid, i.e., that the pores contain a significant
percentage of air or gas, the degree of saturation in water (Sw) is
used, which is defined as the fraction of pores occupied by water

W 0 %
 with respect to the total porosity (Archie, 1942). Denoting ρ% to
the resistivity of a partially saturated me-
Fig. 5. Distribution of resistivity values at different dium in water, Archie (1942) established a 2nd law: Sn = ρ /ρ =
depths.
F·ρW/ρ%, the exponent n adopts different values close to 2
due to a ground value independent of the dechlorination
according to the lithology and other characteristics of the
processes. This feature must be taken into account to evaluate
medium.
the remediation de- gree when it is carried out.
Some authors (Daknov and Keller, 1962) considered introducing a
“b” adjustment factor in Archie's 2nd law to improve adjustment
to em- pirical data. However, the consideration that b ≠ 1 leads to 5.3. Iso-chloride sections
a contradic- tion when the degree of saturation is close to 100%,
as is the case for To obtain the isochloride sections, the same subdivision in
Archie's 1st law (see Díaz-Curiel et al., 2016). Therefore, this paper cells of the tomographic inversion was used. Considering the
con- siders that this factor should not be introduced. Then, for the resistivity ob- tained in each cell in the inversion process, the
man-made filling above the water table, combining the formation fluid conductivity is cal- culated according to the criteria
factor and the Archie's 2nd law, the following relationship was established in Section 5.1. Then, the
used:

ρW ¼ ρ%⋅Øm⋅S relationship (Eq. (3)) obtained with the analytical test results
nW
ð2Þ (Section 5.2) is used to calculate the chloride content from these
values of conductivity of the ERT. A chloride content mesh values
is obtained
where it was considered Ø ~ 50%, m = 2, the average water
saturation
Sw = 0.75, and n = 2.
Fig. 6. Curve obtained from the relation conductivity vs. chlorides content, together
5.2. Correlation between conductivity and soluble chloride with the measured data and the curve of the ClNa standard solution.
concentration

For this purpose, an analysis of the conductivity variations was

car- ried out on the huge number of data from the monitoring
wells, espe- cially aimed at differentiating the different types of
saline inputs that may occur depending on the different means
of circulation.
Then, the correlation between the conductivity values and the
solu- ble chloride concentration values was made. By means of
the adjust- ment by least squares of the analytical values of
contaminant concentration versus conductivity of the fluid to a
potential function with an mean deviation of 0.11, the
relationship given by Eq. (3) was obtained with a coefficient R2 =
0.88. This value indicates the high de- gree of correlation
between both parameters.
0:77
σ w ¼ 30 · ðCl‐Þ ð3Þ

where σw is the water conductivity in μS·cm−1, and Cl− is the

concen- tration of soluble chlorides in mg/l.
Fig. 6 shows the results of Eq. (3) versus the measured data,
together with the curve of Eq. (4) corresponding to a solution of
ClNa in distilled water (Díaz-Curiel, 2000) showing the difference
with regard to that standard solution.
ζ CINa σ2 4
ð Þ¼ ðÞ
1500⋅ðσ þ 500Þ

where ζ(ClNa) address the ClNa content in mg/l.

The higher general values show by the formation water
curve in Fig. 6 indicate the presence of other ions in solution,
which increasing with the chloride content, but the different in
gradient seems to be
for each profile. Finally, this mesh of values is represented in a
section of chloride isolines for each of the tomographic profiles.
Of the resulting sections, the chloride content section of the P1
profile (Fig. 7) is shown, as this is the only profile that clearly
intersects the alluvial level. We have also included the
section corresponding to profile P2 (Fig. 8) which shows the
largest extension of the affected area.

6.Discussion

Both the pseudo-section of 3D resistivities (Fig. 4) and the

cuts at dif- ferent depths (Fig. 5) made it possible to determine
the spatial distribu- tion of the most affected areas within the
site. In addition, various control profiles have been carried out
over time, in different seasons, and before and after routine
phase extraction operations within the landfill. These measures
have ruled out the need for monitoring (4D) of the entire study
area, as there are no significant variations in the re- sistivity
values recorded.
From the analysis of the chloride content sections, it can be
deduced that the greatest concentrations take place in the silt level,
to a lesser ex- tent in the alluvium level, and it is not very
relevant in the man-made filling level. In profile P1, an
increase in depth is detected due to the level of sand that is
interspersed between the alluvium. After obtaining these results
a new series of boreholes were drilled on the most contam-
inated area, whose data obtained showed the correlation
made.
However, it should be noted that some of the variations in
chloride concentration found may be due to changes in
permeability, associated with particle size differences within each
of the levels. This influence of changes in permeability, together
with the presence of differentiated flows, may cause a variation
in the degree of accumulation of the pollutant. Thus, at more
permeable levels, the contaminant suffers greater transport, while in
areas of low permeability, the time of residence is longer.
On the other hand, it was possible to estimate the
preferential flow directions corresponding to the highest
concentration of contaminants. These directions were influenced by
the joint effect of the hydraulic gra- dient of the area and the
changes in the local piezometric level due to the pumping
usually carried out in the monitoring wells, and to the var-
iations in the water level in the reservoir. In this way, what
would be a single plume of pollution is transformed into
different trajectories of complex geometry.
With regard to obtaining isochloride sections, it should be
noted that porosity values were established for each level, without
differentiating within them possible local variations. In the case
of detrital materials, these values are the average values
established from the specific tests carried out, whereas for the
man-made filling level, it was estimated from literature values.
Therefore, these sections would better reflect the variations in
the chloride content if there were a greater number of tests
that would allow the porosity to be defined in more detail.
It is also worth highlighting the unique chemical diversity of
this site. This variability means that not all the chlorides present
had their origin in the decomposition of lindane due to the
presence of other organo- chlorinated contaminants. HCH waste
includes several compounds from chlorobenzene to
heptachlorobenzenes, in addition to the chloro-alkali
compounds of different origin. These lixiviates are mixed
 Fig. 7. Iso-chloride section of the P1 profile, with chloride content values measured in the nearest boreholes.

Fig. 8. Iso-chloride section of the P2 profile, with chloride content values measured in the nearest boreholes.

in different proportions, generating new reactions and creating a tool.

great variety of compounds. Individualised allocation was difficult
given the existing complexity; however, these sections of Authors contribution
chlorides are a highly valuable guide to know the distribution of
these pollutants in the subsoil and areas of greater Bárbara Biosca - She has contributed in: Methodology, Formal
accumulation. analysis, Investigation, Writing - Original Draft, Visualization.
The results obtained were used to determine the most suitable Lucía
loca- tion for the follow-up remediation process, so that the
injection bore- holes may take into account the residual lindane
and the preferential directions determined for high chloride
accumulation.
Finally, it should be mentioned that, due to the spatial
limitation for the measurement of longer profiles, the detrital
cover could not be completely studied, leaving some of the
anomalies found in the resolu- tion limits of the tomography. In
order to resolve these ambiguities, it would be necessary to
increase the depth of study until the marls layer is sufficiently
reached.

7.Conclusions

We have confirmed the validity of ERT in the spatial

characterization of sites contaminated by chlorinated compounds,
in a landfill of unique characteristics by the variety of compounds
present. The results ob- tained by ERT have been verified from
lithological columns from bore- holes (such as those used in Fig.
3), analyses in soil and water samples. In addition, we have
obtained an empirical relationship between the conductivity and
the dissolved chloride content using analytical values from water
samples taken from more than 60 monitoring wells. The most
significant achievement is obtaining of 2D sections of chloride con-
centration in the subsoil from the established relationship and the
values determined with geophysics, a methodology applicable in
other sites with pollutants of the same nature. The spatial
information provided by these images is especially useful to
determine the location of future remediation trials. Like any
empirical relationship, it can be improved by increasing the input
data, however, it is verified to be an efficient and easy to apply
Arévalo-Lomas - She has contributed in: Writing - Review &
Editing, Vi- sualization. Miguel izquierdo Díaz - He has
contributed in: Writing - Review & Editing. Jesús Díaz-Curiel -
He is the main researcher of the work, he has contributed in:
Methodology, Writing - Original Draft, Supervision.

Declaration of Competing Interest

The authors declare that they have no known competing

financial interests or personal relationships that could have
appeared to influ- ence the work reported in this paper.

Acknowledgments

Part of this study was supported by “Comunidad de

Madrid” Re- gional Government of Madrid Spain (CARESOIL-CM
S2013/MAE-2739 & P2018/EMT-4317) and by “Ministerio de
Economía y Competitividad” Government of Spain (DENSOIL
CTM2016-77151-C2-2-R). The authors would like to express their
gratitude to the company EMGRISA and Gov- ernment of Aragón
(Spain) for their cooperation in the field survey and for
providing the geochemical data.

References

Ahmed, A.M., Sulaiman, W.N., 2001. Evaluation of groundwater and soil

pollution in a landfill area using electrical resistivity imaging survey. Environ.
Manag. 28 (5), 655–663. https://doi.org/10.1007/s002670010250.
Ajo-Franklin, J.B., Geller, J.T., Harris, J.M., 2006. A survey of the geophysical
properties of chlorinated DNAPLs. J. Appl. Geophys. 59 (3), 177–189.
https://doi.org/10.1016/j. jappgeo.2005.10.002.
Archie, G.E., 1942. The electrical resistivity log as an aid in determining some
reservoir characteristics. Petrol. Technol. 146 (1), 54–62.
https://doi.org/10.2118/942054-G.
Arrubarrena-Moreno, M., Arango-Galván, C., 2013. Use of electrical resistivity
tomogra- phy in the study of soil pollution caused by hydrocarbons: Case
study in Puebla (México). Bol. Soc. Geol. Mex. 65, 419–426.
https://doi.org/10.18268/ BSGM2013v65n2a21.
Benson, A.K., Frederickson, C., Mustoe, N.B., 1991. Ground penetrating radar,
electrical re- sistivity, soil and water quality studies integrated to determine
the source(s) and ge- ometry of hydrocarbon contamination at a site in
north-central Arizona. Proc. 27th Symp. on Engineering Geology and
Geotechnical Engineering (38.1–38-13).
Bodenstein, G., 1972. Disposal of wastes from Lindane manufacture. Lindane
monograph of an insecticide. Schillinger, Freiburg Im Breisgau, Germany. pp.
23–77.
Breivik, K., Pacyna, J.M., Munch, J., 1999. Use of α-, β-, γ-
hexachlorocyclohexane in Europe, 1970–1996. Sci. Total Environ. 239, 151–
163. https://doi.org/10.1016/ S0048-9697(99)00291-0.
Brewster, M.L., Annan, A.P., Greenhouse, J.P., Kueper, B.H., Olhoeft, G.R., Redman,
J.D., Sander, K.A., 1995. Observed migration of a controlled DNAPL release by
geophysical methods. Groundwater 33 (6), 977–987.
https://doi.org/10.1111/j.1745-6584.1995. tb00043.x.
Cardarelli, E., Di Filippo, G., 2009. Electrical resistivity and induced polarization
tomogra- phy in identifying the plume of chlorinated hydrocarbons in
sedimentary formation: a case study in Rho (Milan—Italy). Waste Manag. Res.
27 (6), 595–602.
Casado, I., Mahjoub, H., Lovera, R., Fernández, J., Casas, A., 2015. Use of electrical
tomogra- phy methods to determinate the extension and main migration
routes of uncon- trolled landfill leachates in fractured areas. Sci. Total Environ.
506, 546–553. https://doi.org/10.1016/j.scitotenv.2014.11.068.
Chambers, J.E., Loke, M.H., Ogilvy, R.D., Meldrum, P.I., 2004. Noninvasive monitoring
of DNAPL migration through a saturated porous medium using electrical
impedance to- mography. J. Contam. Hydrol. 68, 1–22.
https://doi.org/10.1016/S0169-7722(03) 00142-6.
Chibueze, Okpoli C., 2013. Application of 2D electrical resistivity tomography in
landfill site: a case study of Iku, Ikare Akoko, Southwestern Nigeria. J. Geol..
Res. 2013. https://doi.org/10.1155/2013/895160.
Clément, R., Oxarango, L., Descloitres, M., 2011. Contribution of 3-D time-lapse ERT
to the study of leachate recirculation in a landfill. Waste Manag. 31 (3), 457–
467. https:// doi.org/10.1016/j.wasman.2010.09.005.
Daily, W., Ramirez, A., 1995. Electrical resistance tomography during in-situ
trichloroeth- ylene remediation at the Savannah River Site. J. Appl. Geophys.
33 (4), 239–249. https://doi.org/10.1016/0926-9851(95)90044-6.
Daknov, V.N., Keller, G.V., 1962. Geophysical well logging. Quarterly of the
Colorado School of Mines. 52 (2). Golden Colorado Press.
Dermietzel, J., Vieth, A., 2002. Chloroaromatics in groundwater: chances of
bioremedia- tion. Environ. Geol. 41 (6), 683–689. https://doi.org/10.1007/s00254-
001-0451-5.
Díaz-Curiel, J., 2000. Teoría Y práctica de la Prospección Geofísica (ISBN:978-84-
692-
7448-4).
Díaz-Curiel, J., Biosca, B., Miguel, M.J., 2016. Geophysical estimation of
permeability in sedimentary basins with porosities from 0 to 50%. Oil Gas Sci.
Technol. Rev. IFP 71, 27. https://doi.org/10.2516/ogst/2014053.
Ellis, R.G., Oldenburg, D.W., 1994. Applied geophysical inversion. Geophys. J. Int. 116
(1), 5–11. https://doi.org/10.1111/j.1365-246X.1994.tb02122.x.
Engelmann, C., Händel, F., Binder, M., Yadav, P.K., Dietrich, P., Liedl, R., Walther, M.,
2019. The fate of DNAPL contaminants in non-consolidated subsurface
systems–Discussion on the relevance of effective source zone geometries for
plume propagation. J. Hazard. Mater. 375, 233–240.
https://doi.org/10.1016/j.jhazmat.2019.04.083.
EPA, 2004. Site characterization technologies for DNAPL investigations. Technical
report under contract numbers 68-W-00-084 and 68-W-03-038. downloaded
from. http://www.clu-in.org.
Fernández, J., Arjol, M.A., Cacho, C., 2013. POP-contaminated sites from HCH
production in Sabiñánigo, Spain. Environ. Sci. Pollut. Res. Int. 20 (4), 1937–1950.
https://doi.org/ 10.1007/s11356-012-1433-8.
Frid, V., Liskevich, G., Doudkinski, D., Korostishevsky, N., 2008. Evaluation of landfill
dis- posal boundary by means of electrical resistivity imaging. Environ. Geol.
53 (7), 1503–1508. https://doi.org/10.1007/s00254-007-0761-3.
Gonzales, Amaya A., Dahlin, T., Barmen, G., Rosberg, J.E., 2016. Electrical resistivity
tomog- raphy and induced polarization for mapping the subsurface of alluvial
fans: a case study in Punata (Bolivia). Geosciences 6 (4), 51.
https://doi.org/10.3390/ geosciences6040051.
Guadaño, J., Gómez, J., 2016. El vertedero de Sardas y el problema del lindano.
Revista Técnica de Medio Ambiente 192, 14–19.
https://www.retema.es/articulo/el- vertedero-de-sardas-y-el-problema-del-
lindano-JURHG.
Johansson, S., Fiandaca, G., Dahlin, T., 2014. Field application of resistivity and
spectral time domain IP to investigate geoelectrical signatures of free-phase PCE.
Near Surface Geoscience 2014-20th European Meeting of Environmental and
Engineering Geo- physics https://doi.org/10.3997/2214-4609.20142049.
Kang, X., Shi, X., Deng, Y., Revil, A., Xu, H., Wu, J., 2018. Coupled hydrogeophysical
inver- sion of DNAPL source zone architecture and permeability field in a 3D
heterogeneous sandbox by assimilation time-lapse cross-borehole electrical
resistivity data via en- semble Kalman filtering. J. Hydrol. 567, 149–164.
https://doi.org/10.1016/j. jhydrol.2018.10.019.
Kutz, F.W., Wood, P.H., Bottimore, D.P., 1991. Organochlorine pesticides and
polychlorinated biphenyls in human adipose tissue. Rev. Environ. Contam.
Toxicol., 120 https://doi.org/10.1007/978-1-4612-3080-9_1.
Li, Y.-F., 1999. Global technical hexachlorocyclohexane usage and its contamination
con- sequences in the environment: from 1948 to 1997. Sci. Total Environ.
232, 121–158. https://doi.org/10.1016/S0048-9697(99)00114-X.
Liao, Q., Deng, Y., Shi, X., Sun, Y., Duan, W., Wu, J., 2018. Delineation of
contaminant plume for an inorganic contaminated site using electrical
resistivity tomography: compari- son with direct-push technique. Environ.
Monit. Assess. 190 (4), 187. https://doi. org/10.1007/s10661-018-6560-3.
Loke, M.H., 2008. Res2DInv ver. 3.57, Rapid 2-D Resistivity and IP inversion
using the least-squares method. Geoelectrical Imaging 2D and 3D Geotomo
Software Malaysia http://www.geoelectrical.com.
Loke, M.H., 2011. Electrical resistivity surveys and data interpretation. In: Gupta, H.
(Ed.), Solid Earth Geophysics Encyclopaedia (2nd edition) “Electrical and Electromagnetic”.
Springer-Verlag, pp. 276–283.
Loke, M.H., Barker, R.D., 1996. Rapid Least-squares Inversion of Apparent
Resistivity Pseudosections by a Quasi-Newton Method. Geophys. Prospect. 44,
131–152. https://doi.org/10.1111/j.1365-2478.1996.tb00142.x.
Loke, M.H., Dahlin, T., 2002. A Comparison of the Gauss-Newton and Quasi-
Newton Methods in Resistivity Imaging Inversion. J. Appl. Geophys. 49, 149–162.
https://doi. org/10.1016/S0926-9851(01)00106-9.
Lorenzo, D., García-Cervilla, R., Romero, A., Santos, A., 2020. Partitioning of
chlorinated or- ganic compounds from dense non-aqueous phase liquids and
contaminated soils from lindane production wastes to the aqueous phase.
Chemosphere 239, 124798.
https://doi.org/10.1016/j.chemosphere.2019.124798.
Luciano, A., Viotti, P., Papini, M.P., 2010. Laboratory investigation of DNAPL
migration in porous media. J. Hazard. Mater. 176 (1–3), 1006–1017.
https://doi.org/10.1016/j. jhazmat.2009.11.141.
Maurya, P.K., Rønde, V.K., Fiandaca, G., Balbarini, N., Auken, E., Bjerg, P.L.,
Christiansen, A.V., 2017. Detailed landfill leachate plume mapping using 2D and
3D electrical resis- tivity tomography-with correlation to ionic strength
measured in screens. J. Appl. Geophys. 138, 1–8.
https://doi.org/10.1016/j.jappgeo.2017.01.019.
Muñoz-Morales, M., Braojos, M., Sáez, C., Cañizares, P., Rodrigo, M.A., 2017.
Remediation
of soils polluted with lindane using surfactant-aided soil washing and
electrochemi- cal oxidation. J. Hazard. Mater. 339, 232–238.
https://doi.org/10.1016/j. jhazmat.2017.06.021.
Naudet, V., Gourry, J.C., Girard, F., Mathieu, F., Saada, A., 2014. 3D electrical
resistivity to- mography to locate DNAPL contamination around a housing
estate. Near Surf. Geophys. 12 (3), 351–360. https://doi.org/10.3997/1873-
0604.2012059.
Newmark, R.L., Daily, W.D., Kyle, K.R., Ramirez, A.L., 1997. Monitoring DNAPL
pumping
using integrated geophysical techniques. J. Environ. Eng. Geophys. 3 (1), 7–
13. https://doi.org/10.4133/JEEG3.1.7.
Oldenburg, D.W., Li, Y., 2005. Inversion for applied geophysics: A tutorial. Near
Surf.
Geophys., 89–150 https://doi.org/10.1190/1.9781560801719.ch5.
Orlando, L., Viotti, P., 2009. DNAPL Detection and Monitoring Using Electrical
Resistive Tomography–A Case Study in North Italy, Rho-Milan. Near Surface
2009-15th EAGE European Meeting of Environmental and Engineering
Geophysics https://doi.org/ 10.3997/2214-4609.20147111.
Pankow, J.F., Isabelle, L.M., Asher, W.E., 1984. Trace organic compounds in rain. 1.
Sampler design and analysis by adsorption/thermal desorption (ATD). Environ.
Sci. Technol. 18 (5), 310–318. https://doi.org/10.1021/es00123a005.
Park, S., Yi, M.J., Kim, J.H., Shin, S.W., 2016. Electrical resistivity imaging (ERI)
monitoring
for groundwater contamination in an uncontrolled landfill, South Korea. J.
Appl. Geophys. 135, 1–7. https://doi.org/10.1016/j.jappgeo.2016.07.004.
Power, C., Gerhard, J., Tsourlos, P., Soupios, P., Simyrdanis, K., Karaoulis, M.,
2014. Im-
proved time-lapse ERT monitoring of dense non-aqueous phase liquids
(DNPLs) with surface-to-horizontal borehole arrays. Near Surface Geoscience
2014-20th European Meeting of Environmental and Engineering Geophysics
https://doi.org/ 10.3997/2214-4609.20142054.
Santos, A., Fernandez, J., Guadaño, J., Lorenzo, D., Romero, A., 2018a. Chlorinated
organic compounds in liquid wastes (DNAPL) from lindane production dumped
in landfills in Sabiñanigo (Spain). Environ. Pollut. 242, 1616–1624.
https://doi.org/10.1016/j. envpol.2018.07.117.
Santos, A., Fernandez, J., Rodriguez, S., Dominguez, C.M., Lominchar, M.A., Lorenzo,
D., et al., 2018b. Abatement of chlorinated compounds in groundwater
contaminated by HCH wastes using ISCO with alkali activated persulfate. Sci.
Total Environ. 615, 1070–1077.
https://doi.org/10.1016/j.scitotenv.2017.09.224.
Sauck, W.A., Atekwana, E.A., Nash, M.S., 1998. High electrical conductivities
associated
with an LNAPL plume imaged by integrated geophysical techniques. J. Environ.
Eng. Geophys. 2, 203–212.
Simonich, S.L., Hites, R.A., 1995. Global distribution of persistent organochlorine
com-
pounds. Science 269 (5232), 1851–1854. https://doi.org/10.1126/science.7569923.
Sundberg, K., 1932. Effect of impregnating waters on electrical conductivity of
soils and rocks. Trans. Am. Inst. Min. Metal. Eng. 97, 367–391.
Thompson, P., Tull, K., Calkin, S., 2011. Application of geophysics for environmental
char-
acterization, remedial design, and remedial implementation at three fractured
bed- rock sites impacted by chlorinated solvents in New England. Symposium
on the Application of Geophysics to Engineering and Environmental Problems
2011. Society of Exploration Geophysicists, p. 319
https://doi.org/10.4133/1.3614093.
Trask, P.D., 1932. Origin and Environment of Source Sediments of Petroleum.
Houston Gulf Publications Co., Houston.
Vijgen, J., Abhilash, P.C., Li, Y.F., Lal, R., Forter, M., Torres, J., Singh, N., Yunus, M.,
Tian, G., Schäffer, A., 2011. Hexachlorocyclohexane (HCH) as new Stockholm
Convention POPsda global perspective on the management of Lindane and its
waste isomers. En- viron. Sci. Pollut. Control Ser. 18 (2), 152–162.
https://doi.org/10.1007/s11356-010-
0417-9.
Vijgen, J., Borst, B., Weber, R., Stobiecki, T., Forter, M., 2019. HCH and lindane
contami- nated sites: European and global need for a permanent solution for a
long-time neglected issue. Environ. Pollut. 248, 696–705.
https://doi.org/10.1016/j. envpol.2019.02.029.
Wycisk, P., Stollberg, R., Neumann, C., Gossel, W., Weiss, H., Weber, R., 2013.
Integrated methodology for assessing the HCH groundwater pollution at the
multi-source con- taminated mega-site Bitterfeld/Wolfen. Environ. Sci. Pollut.
Res. 20, 1907–1917. https://doi.org/10.1007/s11356-012-0963-4.
Yang, C.H., You, J.I., 1999. High resistivities associated with an LNAPL plume
imaged by geoelectrical tomography. SEG Technical Program Expanded
Abstracts 1999. Society of Exploration Geophysicists, pp. 469–472
https://doi.org/10.1190/1.1821055.