Journal of Hydrology 547 (2017) 269–279

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Journal of Hydrology
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Research papers

Solute transport characterization in karst aquifers by tracer injection

tests for a sustainable water resource management
T. Morales a, B. Angulo a, J.A. Uriarte a,⇑, M. Olazar b, J.M. Arandes b, I. Antiguedad a
a
Hydrogeology and Environment Group, Department of Geodynamics, University of the Basque Country (UPV/EHU), P.O. Box 644, E-48080 Bilbao, Spain
b
Department of Chemical Engineering, University of the Basque Country (UPV/EHU), P.O. Box 644, E-48080 Bilbao, Spain

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

Article history: Protection of water resources is a major challenge today, given that territory occupation and land use are
Received 31 May 2016 continuously increasing. In the case of karst aquifers, its dynamic complexity requires the use of specific
Received in revised form 2 January 2017 methodologies that allow establishing local and regional flow and transport patterns. This information is
Accepted 7 February 2017
particularly necessary when springs and wells harnessed for water supply are concerned. In view of the
Available online 9 February 2017
This manuscript was handled by Corrado
present state of the art, this work shows a new approach based on the use of a LiCl based tracer injection
Corradini, Editor-in-Chief, with the test through a borehole for transport characterization from a local to a regional scale. Thus a long term
assistance of Dongmei Han, Associate Editor tracer injection test was conducted in a particularly sensitive sector of the Egino karst massif (Basque
Country, Spain). The initial displacement of tracer in the vicinity of the injection was monitored in a sec-
Keywords: ond borehole at a radial distance of 10.24 m. This first information, assessed by a radial divergent model,
Tracers allows obtaining transport characteristic parameters in this immediate vicinity during injection. At a lar-
Injection test ger (regional) scale, the tracer reaches a highly transmissive network with mean traveling velocities to
Solute transport the main springs being from 4.3 to 13.7 m/h. The responses obtained, particularly clear in the main spring
Water management used for water supply, and the persistence of part of the tracer in the injection zone, pose reconsidering
Karst the need for their protection. Thus, although the test allows establishing the 24-h isochrone, which is the
ceiling value in present European vulnerability approaches, the results obtained advise widening the
zone to protect in order to guarantee water quality in the springs. Overall, this stimulus-response test
allows furthering the knowledge on the dynamics of solute transport in karst aquifers and is a particu-
larly useful tool in studies related to source vulnerability and protection in such a complex medium.
Ó 2017 Elsevier B.V. All rights reserved.

1. Introduction
Karst aquifers supply water to more than 25% of the world pop-
ulation. In Europe, some countries meet up to 50% of their demand
in drinking water from karst aquifers (European Commission,
1995). Protect these resources against pollution and maintain
water quality, particularly in environments with an increasing
demographic pressure, is not an easy task due to the peculiar karst
flow features and their low self-purification capacity. Thus,
although water incoming could have a general diffuse nature, local
inflows by cracks, solution chimneys, vertical shafts and swallow
holes allow for a rapid access of water into the aquifer (Ford and
Williams, 1989). In the same way, although the development of
soils and subsuperficial epikarst elements in the infiltration zone
may favor a certain delay in water evolution (Mangin, 1974;
Bakalowicz, 2005), the most common features in karst aquifers
⇑ Corresponding author.
E-mail address: jesus.uriarte@ehu.eus (J.A. Uriarte).
are open conduits, which provide low resistance pathways for
groundwater flow and transport (Huntoon, 1995, 1999; White,
2002; Field and Feike, 2014). The resulting flow pattern as a whole
is characterized in most karst aquifers by a high vulnerability to
contamination.
Concerning the term vulnerability, the intrinsic vulnerability
could be defined (Zwahlem, 2003) as the sensitivity of an aquifer
to contamination, taking into account its geological, hydrological
and hydrogeological characteristics, regardless of the nature and
scenario of the contamination. In any case, when the main goal is
the protection and management of karst groundwater, a clear dis-
tinction should be made between resource and source vulnerabil-
ity (Daly et al., 2002). In the first case, the target to protect is the
top of the saturated zone. Concerning source vulnerability, the tar-
get to protect is the karst water supply (borehole or spring).
Although these two concepts are closely related, the analysis of
vulnerability around sources is a more urgent and priority item
to be accomplished, particularly when water is used for drinking
water or it is essential to maintain sensitive ecological environ-

http://dx.doi.org/10.1016/j.jhydrol.2017.02.009
0022-1694/Ó 2017 Elsevier B.V. All rights reserved.
270 T. Morales et al. / Journal of Hydrology 547 (2017) 269–279
ments. In this sense, according to the Water Framework Directive
on groundwater (European Commission, 2007), protection mea-
sures should be focused on safeguard zones, normally linked (but
not necessary restricted) to existing drinking water abstractions
that are at risk of deterioration.
In this context, different methodologies have been developed
over the past two decades for vulnerability assessing and mapping:
EPIK (Doerfliger and Zwahlen, 1997), PI (Goldscheider et al., 2000),
KARSTIC (Davis et al., 2002), the Slovene Approach (Ravbar and
Goldscheider, 2007) and COP + K (Andreo et al., 2009), among
others. Anyway, when the delineation of protection perimeters
and safeguard zones around groundwater sources in karst aquifers
is the goal, vulnerability assumptions must be verified and
weighted based on travel time determinations. At this point, as sta-
ted by Marín et al. (2015), despite increasing scientific contribu-
tions are being made in terms of groundwater protection, there
is still a need for new ideas, methods and strategies when facing
the practical challenges of karst spring protection.
In this context, tracer tests make observable water displace-
ment through the different elements travelled, the so-called trac-
ing subsystem (Castany and Margat, 1977; Lepiller and Mondain,
1986), and they are therefore an effective search tool to get direct
information on flow and transport in karst aquifers. Furthermore,
in contrast to natural tracers, the input signal in these tests is con-
trolled by the operator and the interpretation of the results
becomes more precise as uncertainties at this crucial point are lim-
ited. Thus, tracer tests have been used extensively to establish
groundwater trajectories and define catchment areas. They have
been proven to be especially useful in the characterization of flow
and transport in karst conduits (Field and Pinsky, 2000; Hauns
et al., 2001; Birk et al., 2005; Massei et al., 2006; Geyer et al.,
2007; Göpper and Goldscheider, 2008; Morales et al., 1997, 2007,
2010). Less frequent has been its use in the karst vadose zone
and cave environments (Botrell and Atkinson, 1992; Cencur Curk
et al., 2001; Perrin et al., 2004; Goldscheider et al., 2008; Flynn
and Sinreich, 2010; Kogovsek and Petric, 2014). In most cases,
the application of these tests has been restricted to well developed
accessible karst features. Nevertheless, the possibility of injecting
tracers from boreholes allows expanding its use, selecting the envi-
ronment to be characterized and acquiring direct information
about its dynamic behavior. In this way, injection experiments,
sometimes implemented in injection-pumping schemes, have been
used to investigate flow and transport characteristics in the vicin-
ity of the injection point (Seaman et al., 2007; Hartmann et al.,
2007; Huang et al., 2010; Sharifi Haddad et al., 2013, 2015), includ-
ing biogeochemical transformations (Oya and Valocchi, 1998;
Vandenbohede et al., 2008; Phanikumar and McGuire, 2010;
Wallis et al., 2013).
This work shows the results of a tracer injection test for a par-
ticularly sensitive sector in a karst aquifer. Apart from characteriz-
ing the vicinity of the injection borehole, the principal aim of the
test planned is to mark this sector of aquifer with the objective
of analyzing its evolution in the short, medium and long term,
and obtain direct information about travel times and transport
dynamics related to its connection with water sources. Thus, the
characterization process evolves from a local to a regional scale
by expanding the investigation scope of these tests and providing
representative values of flow and transport required for the devel-
opment of management strategies, especially those directed to
safeguard and protect water supply sources in karst aquifers.
2. Field site
To perform the tracer injection test, the karst massif of Egino
was selected. This massif is part of the Aizkorri-Aratz mountain
range (Fig. 1) located in the eastern part of the Basque Country
(northern Spain) and declared Natural Park in 2006. Placed in the
Cantabrian-Mediterranean watershed, with summits up to
1550 m, the climate is humid temperate. Mean annual precipita-
tion, greatly influenced by the topography and the proximity to
the sea, varies from 1800 mm in the northern part of the range
to 1200 to the south.
Geologically, materials in this sector exhibit an anticlinal-fault
structure, which extends towards NW–SE and the main reliefs
are massive limestone outcrops corresponding to the Urgonian
Complex (Aptian-Albian) that holds an area of 54.6 km2. Specifi-
cally, the Egino massif is associated with an isolated outcrop of
limestone belonging to a late Urgonian facies episode with an
extension of 4.5 km2. This outcrop is composed of biothermal lime-
stone which exhibits a lenticular morphology steeply dipping to
the south. North to the limestones, the Balmaseda Formation is
located, which is composed of terrigenous sediments consisting
of predominantly sandstones and lutites; these materials form part
of the Supra-Urgonian Complex and show an overall low perme-
ability. To the south, more modern Upper Cretaceous materials
composed of grey marls and calcareous marls limit the massif.
From a hydrogeological point of view, regional groundwater
resources have been evaluated in 78 h m3/year, 7 of which corre-
spond to the Egino massif. Limestones exhibit, in general, signifi-
cant processes of fracturing and karstification, which favor the
development of a notable network of flow conduits, caves and
underground galleries inside the massif, resulting in a well-
developed karst aquifer. Focusing on the Egino karst aquifer,
recharge takes place by direct percolation in the massif and allo-
genic contributions coming from the north and sinking in well
developed swallow holes, which increases the recharge area to
9.6 km2. Inside the massif, the most evident groundwater flow
paths have a predominant direction north-south and the most
striking feature is the impressive karst conduit that leads water
from La Hoya de La Lece swallow hole (732 m amsl) to La Lece
spring (625 m amsl). The aquifer discharge takes place naturally
through springs located at the south, on the border between the
limestone massif and the low permeable Upper Cretaceous marls.
The main discharges correspond to La Lece spring, with 106 L/s
mean flow rate, and Arbara, with 85 L/s. In any case, both sources
show a high variability in flow discharges (Fig. 2), proving a high
degree of functional karstification. Nevertheless, water quality is
overall good and these two springs are the main sources of water
supply to the surrounding villages.
Another remarkable element is the existence of several calcite
dykes in the massif. These dykes are made of white massive calcite
and reach several meters thick. One of the dykes with the greatest
development crosses the massif at the east of La Lece spring. The
actual possibility of mining this dyke required an analysis of its
impact on drinking water sources in order to objectively validate
the implementation of protection measures beyond a subjective
assessment of vulnerability.
3. Material and methods
3.1. Tracer injection design and monitoring strategy
In order to examine the sector subject to investigation and ana-
lyze its connection with the springs, two boreholes 50.5 mm in
radius at both sides of the calcite dyke were drilled (Figs. 1 and
3a): borehole Br-1, located at 732 m amsl with a depth of
101.5 m and tilted 77° towards N83°E, and the borehole Br-2, also
732 m amsl with a depth of 120.75 m and tilted 85° towards
N120°E. Both boreholes cut the calcite dyke and reach the sur-
rounding limestone.
 T. Morales et al. / Journal of Hydrology 547 (2017) 269–279
Fig. 1. Egino karst massif site: geographical and hydrogeological context. Location of La Lece and Arbara springs and Br-1 and Br-2 boreholes.
Both boreholes were characterized by geophysical logging and
permeability tests (Angulo et al., 2011). These studies allowed
determining the permeability profile of the calcite dyke and its sur-
rounding medium. Overall, the hydraulic conductivity results were
very low, almost all below 2.0
105 cm/s. In the shallower section
of the boreholes (up to a depth of 24 m) some intervals showed
higher values of hydraulic conductivity, up to 1.6
104 cm/s. In
this superficial stretch, significant processes of fracture washing
out were recorded during tests, increasing the hydraulic conductiv-
ity values by nearly one order of magnitude. Concerning the natu-
ral change in piezometer level, both boreholes register a similar
evolution. The maximum levels reach almost 20 m depth in both
boreholes and the minima are close to 90 m in the borehole Br-2,
with average levels around 60 m depth. The tracer injection test
was precisely carried out under these average level conditions.
In the test, a solution of lithium chloride is injected to this sys-
tem with the aim of marking a volume of aquifer in the vicinity of
the injection borehole and observe its evolution throughout time
271
and space. Accordingly, lithium has several advantages as a tracer.
Very low concentrations of this metal (up to 0.1 lg/L) are detected
by ICP-MS (inductively coupled plasma mass spectrometry), which
allows working with relatively small amounts of product. Besides,
this tracer is not present in these waters and moderate amounts
allow obtaining well defined tracer breakthrough curves: lithium
has been successfully used in previous research works carried
out in nearby aquifers (Morales et al., 2007), which will also allow
comparing results. Concerning its toxicity, lithium is not expected
to bioaccumulate and its human and environmental toxicity is low
(Aral and Vecchio-Sadus, 2008). Thus, the German Environmental
Protection Agency recommends carrying out injections with
lithium concentrations below 0.5 mg/L in the springs used for
water supply; although ten times higher concentrations are toler-
able for short periods of time (Käss, 1998). The high solubility of
lithium chloride in water (832 g/L; 20 °C), its moderate cost and
its easy preparation and transportation are positive aspects for
its use. Furthermore, as the two closer springs are used for water
272 T. Morales et al. / Journal of Hydrology 547 (2017) 269–279
Fig. 2. Flow rate and electrical conductivity at La Lece (a) and Arbara (b) springs during the first year after tracer injection.
supply and, in fact, they are the basic source of water in the vicin-
ity, no dye tracers were used, thus avoiding the alarm that may be
caused.
In accordance with the hydrogeological framework, and given
the proximity of La Lece spring, tracer was injected in the borehole
Br-1, the farther from this spring (454 m in a straight line, Fig. 1). In
order to directly inject the tracer in the saturated zone of the mas-
sif, a basal stretch of 41.5 m was isolated by packers. From the sur-
face, water reaches the injection chamber through a pipe of
25.4 mm inner radius. After the system was filled with water and
given the low medium permeability, the lithium chloride solution
was injected at a pressure of 1 MPa applied for 45 min at the head
of the injection well. The resulting injection flow rate was 45.8 L/
min. After pressure injection, water remaining in the pipe was left
to evolve gravitationally and water level decline inside the pipe
was periodically recorded, thereby enabling to determine the sub-
sequent evolution of injection flow rate. The lithium concentration
in the solution was 398 mg/L and the total amount of lithium
injected was 0.82 kg.
With reference to the monitoring scheme, the first control point
was established in the borehole Br-2, closer to La Lece spring
(442 m in a straight line). Thus, a conductivity-temperature-
depth (CTD) diver device was placed 90 m deep, which allows fol-
lowing tracer evolution through the saturated zone. Previously,
this borehole was completed by installing a continuous slotted
pipe with a bentonite sealing ring in the upper 20 m. Given the
expected high flow velocities and concentration changes at the ini-
tial moments of the test, the use of groundwater samplers was dis-
carded. Nevertheless, lithium chloride provides a clear electrical
signal which allows tracer tracking almost continuously. Regis-
tered electrical conductivity values at 25 °C (EC) in lS/cm can be
converted into concentration values using a calibration curve made
for this purpose with water from the spring of La Lece: [Li+] = 0.074
EC  30.83; R2 = 0.995. Monitoring in this borehole was completed
with the realization of systematic vertical well logs by means of a
conductivity-temperature probe, which was used to register data
bimonthly every 0.5 m in depth, and subsequent sampling at the
CTD-Diver depth with a discrete interval sampler, which confirmed
the validity of the previous relationship.
Finally, the monitoring scheme was completed with a continu-
ous flow rate recording at the aquifer main springs and a periodic
water sampling for a month. Accordingly, two automatic samplers
were placed at La Lece and Arbara springs, with the latter being at
1750 m in straight line from the injection borehole, and manual
sampling was performed to complete and control the results. Sam-
ples were daily sent to the laboratory, which, depending on the
results, allowed for altering the period of time between samples
from 1 h, when the beginning of trace passage has been detected,
to more than one day to the end of the test, and for confirming
the tracer–cloud passage at the observation points. Water samples
were analyzed in the laboratory by inductively coupled plasma
mass spectrometry (ICP-MS), with a detection limit of 0.1 lg/L.
3.2. Transport modeling around injection borehole
For modeling transport in the surroundings of the injection
borehole, a divergent radial flow is considered. The advection-
dispersion equation that describes tracer evolution in cylindrical
coordinates is generally given as (Chen et al., 2007):


1 @ @Cðr; tÞ @Cðr; tÞ @Cðr; tÞ
rDL  v r ðr; tÞ ¼ Rf ; ð1Þ
r @r @r @r @t
where C(r, t) is the concentration at the position r at time t; DL is the
longitudinal dispersion coefficient; Rf is the retardation factor and
vr(r, t) is the groundwater flow velocity:
Q ðtÞ
v r ðr; tÞ ¼ ; ð2Þ
2pB/f r
with Q(t) being flow rate, B the thickness of the injection chamber
and /f the effective bulk fracture porosity, which is related to the
number of hydraulically active fractures (N) in the test interval (L)
and hydraulic aperture (2b) by (Quinn et al., 2011):
 T. Morales et al. / Journal of Hydrology 547 (2017) 269–279 273

Fig. 3. (a) Injection details. (b) Water level and electrical conductivity (EC) registered in the monitoring borehole after injection. (c) Long term electrical conductivity
evolution and representative electrical conductivity profiles at Br-2 borehole.

Nð2bÞ parameter array option is used to change the number of finite-

/f ¼ ð3Þ
L difference segments. The Runge-Kutta algorithm was used in the
Furthermore, when molecular diffusion is negligible compared integration process and the one by Nealder-Mead for optimization
to mechanical dispersion, the longitudinal dispersion coefficient (Nelder and Mead, 1965).
is assumed to be linearly dependent on the advective velocity as: Thus, the mass balance in each layer is given by:

DL ¼ v r ðr; tÞ aL ; ð4Þ   dC n ðtÞ

pB/f r2n  r2n1 Rf ¼ Q ðtÞ½C n1 ðtÞ  C n ðtÞ
dt
where aL is the longitudinal dispersivity.

C n1 ðtÞ  C n ðtÞ C n ðtÞ  C n1 ðtÞ
Finally, the retardation coefficient Rf is approximated by Freeze þ aL Q ðtÞ 
Dr Dr
and Cherry (1979):
ð6Þ
Rf ¼ 1 þ AK a ð5Þ
The inner layer in contact with the borehole (n = 1) satisfies the
where A is the surface area to void space ratio [1/L] for the fracture boundary condition:
opening and Ka is the ratio of the mass of solute in the solid phase
dC 1 ðtÞ C 1 ðtÞ  C 2 ðtÞ
per unit area of solid phase to the concentration of solute in the pB/f r21 Rf ¼ Q ðtÞC 1 ðtÞ  aL Q ðtÞ ; ð7Þ
solution.
dt Dr
Eq. (1) is solved by using the software package Berkeley- where C1(t) is the tracer concentration in the injection borehole.
Madonna developed at the University of California at Berkley by The outer layer (n = N) contains the monitoring point and the
Robert Macey and George Oster (Ingham et al., 2008). It numeri- mass balance is expressed as:
cally solves ordinary differential equations and difference equa-
  dC N ðtÞ
tions, allowing the use of different fitting algorithms. In this pB/f r2N  r2N1 Rf ¼ Q ðtÞ
½C N1 ðtÞ  C N ðtÞ
study, the dynamic component balance is finite differenced into dt
shells of thickness Dr, with the inner satisfying the boundary con- C N1 ðtÞ  C N ðtÞ
þ aL QðtÞ ð8Þ
ditions, S0, and the outer shell being the monitoring point. The Dr
274 T. Morales et al. / Journal of Hydrology 547 (2017) 269–279
The concentration values obtained by the model for the last
layer, CN(t), are fitted to experimental data, thus obtaining optimal
values for the fitting parameters as well as the corresponding rel-
ative error. The deviation is the root mean square (RMS) of the dif-
ferences between individual data points in the dataset and those
corresponding to the best fit given by the model.
3.3. Transport characterization at springs
From the monitoring carried out at springs four characteristic
curves could be obtained (Morales et al., 2007): tracer concentra-
tion curve (tracer breakthrough curve), flow rate curve (hydro-
graph), tracer flow rate curve (mass flow curve) and residence
time distribution (RTD) curve.
The concentration curve allows for directly obtaining parame-
ters related to transit time and velocity (leading edge, trailing edge
and peak velocities), tracer concentration (maximum and mean)
and the duration of the recovery. In instantaneous injections, times
are measured by taking the injection time (t = 0) as reference. In
our test, and given the complexity of the input signal, pressure
injection mean time and mean time of the main washing event
at Br-2 borehole are considered as reference values. The distance
(x) used for calculating the velocities is the straight line between
the injection point and the sampling points. Consequently, the val-
ues obtained for velocity are minimum values and the real values
of velocity, depending on the tortuousness of the drains (Field
and Nash, 1997), may be from 1.3 to 1.5 times higher (Sweeting,
1973; Field, 1999; Field and Pinsky, 2000).
The curve of tracer mass flow rate is obtained as a product of
concentrations and discharge flow rates at each point at time (t).
The integration of this curve allows for calculating the mass of tra-
cer recovered:
Z 1
Mr ¼ Q ðtÞCðtÞdt ð9Þ
0 lous points with excessively high concentrations (above 25 lg/L),
The ratio between this mass recovered and the initially injected
mass is the recovery rate:
Mr
Rr ¼ ð10Þ
M0
Finally, the RTD curve is obtained by relating the mass flow rate
to the recovered tracer mass:
CðtÞQ ðtÞ
EðtÞ ¼ ð11Þ
Mr
It has reverse time units and represents the probability density
function that a traced water element stays in the system for a time
between t and t + dt (Molinari, 1976). The RTD allows for calculat-
ing the mean residence time:
Z tion implemented in the program Berkeley-Madonna. Thus, con-
1
tm ¼ tEðtÞdt; ð12Þ
0 were fitted to experimental values recorded at the CTD-Diver, once
and mean transit velocity:
Z 1
1 injection at a constant concentration of 398 mg/L with a flow rate
vm ¼ x EðtÞdt ð13Þ
0 t
4. Results
4.1. Experimental results
The first signal of tracer evolution after injection was registered
by the CTD-Diver placed in the borehole Br-2. This device shows
baseline values ranging from 387 to 403 lS/cm and then a rapid
increase in conductivity just 30 min subsequent to the injection
start in Br-1 (Fig. 3b). This first tracer signal reveals traveling veloc-
ities of up to 0.34 m/min by assuming a radial evolution of tracer
between boreholes, with the radial distance to the monitoring
device being 10.24 m (Fig. 3a). Afterwards, and once injection
under pressure had been finished, traced water remaining in the
injection pipe evolved into the aquifer and conductivity steadily
increased for 112 h. The maximum conductivity value reached
was 1531.3 lS/cm. In the following days, a significant part of tracer
remained marking the injection area. In any case, the gentle
decrease in levels registered in the borehole implies a slow contin-
uous evolution of traced water from this sector to the aquifer.
First rains after injection drastically changed this evolution
(Fig. 3b). Thus, simultaneously to a 24 m rise in water level, con-
ductivity dropped to values approaching the initial conductivity
baseline. Likewise, throughout the first hydrological cycle after
injection, conductivity values show clear dilutions and recoveries
after main rainfall events, although progressively smaller (Fig. 3c);
particularly noticeable is the recovery at the end of the first low
water period. Heavy rains at the beginning of the second cycle gen-
erate a widespread decline in conductivity values. These events of
washing and conductivity recovery are also observed along the
borehole, as are evidenced by vertical well logs registered (Fig. 3c).
As of that moment maximum values reached at the end of dry peri-
ods are clearly lower than those registered at the end of the first
cycle.
In the spring, lithium background concentrations prior to the
test ranged between 3.5 lg/L (La Lece) and 1.5 lg/L (Arbara). After
injection, an irregular response was obtained in both springs
(Fig. 4). The first noticeable increase in concentration at La Lece
spring was registered 30.5 h after injection, and the maximum con-
centration value attained was 8.71 lg/L after 88.75 h. At Arbara,
the first significant increase was recorded 46.33 h after injection.
Overall, the values of concentration registered are slightly lower
than those at La Lece. It should be noted that there are two anoma-
which have been excluded in the subsequent discussion and
interpretation.
With the first rains after injection, flow rates at the springs
increased. Tracer concentration at La Lece began to experience a
new net increase reaching peak concentrations of 20.7 lg/L,
316.83 h after injection. Recording at Arbara is unclear and more
irregular. Tracer concentrations at springs were no longer signifi-
cant 432 h after injection, although certain values are slightly
above the background concentration.
4.2. Results from the numerical model
The evolution of tracer in borehole Br-2 during the first days
after injection was modelled by using the divergent transport solu-
centration values obtained by the model for the last layer, CN(t),
conductivity values have been transformed into lithium concentra-
tion as indicated previously. The input tracer function was an
of 0.76 L/s for the initial 37 min (8 min were required for traced
water to reach the diver level) and a subsequent exponential
decrease: Q(t) = 0.76
e0.04(t0.62) L/s, which fits data obtained dur-
ing water column emptying in the pipe after injection.
The model fitting process to the experimental data requires
three input parameters: effective porosity (/f), dispersivity (aL)
and retardation factor (Rf), whose most feasible values were con-
strained based on field and literature data. Thus, the value of effec-
tive porosity in fractured media, which provides the cross sectional
area for water flow, can be determined from the hydraulically
active fracture aperture and frequency (Hartmann et al., 2007;
 T. Morales et al. / Journal of Hydrology 547 (2017) 269–279 275

the number of finite-difference sections considered (arrays), rang-

ing from 10 (1.024 m) to 140 (7.31
102 m). As can be seen in
Fig. 5 and Table 1, only the results obtained with the lower number
of segments show low convergence with experimental data. The
error decreases in a pronounced way as the number of segments
is increased (Fig. 5b). The best fit is obtained for a dispersivity
(aL) of 0.173 m, a retardation value (Rf) of 1.82 and a fracture
porosity (/f) of 1.02
104, with RMS deviation being 2.31 mg/L.
Once the parameters of best fit are obtained, a sensitivity anal-
ysis of the model is conducted in order to determine the robustness
of the model to changes in the fitting parameters. Accordingly, the
uncertainty in the output has been determined by changing the
values of the parameters around those corresponding to the best
fit, i.e., by increasing and decreasing ±10%, ±20% and ±50%. These
values are within the range (constrains) considered in the model
formulation (/f  7.71
104, 0.01  aL  102 m, Rf  1). The
results of the sensitivity analysis are shown in Fig. 6. As observed,
the model parameters have a reasonable effect on the output,
which means that there is no need to remove redundant parts in
the model structure. Furthermore, the output (evolution of tracer
concentration) follows the trend expected for the changes in the
parameters. Thus, an increase in dispersivity leads to an increase
in the range of concentrations at the measuring point (a), whereas
a decrease in fracture porosity, /f (b) and retardation, Rf (c)
enhances a faster evolution of the tracer in the medium.

4.3. Transport velocities and recovery rates at springs

Tracer breakthrough curves obtained at springs allow analyzing

water evolution throughout the traced system and obtaining trans-
port characteristic values. Accordingly, the tracer curve obtained at
La Lece is clearly bimodal and may be subdivided into two
successive signals (Fig. 4): a first one, related to the initial pressure
Fig. 4. Flow rate and lithium concentration at La Lece (a) and Arbara (b) springs
after injection. Main characteristic values: mean travel time after injection (tm.i.),
mean travel time after washing event mean time (tm.w.) and recovery rate (Rr).
Lithium baseline concentration at La Lece: 3.5 lg/L; lithium baseline concentration
at Arbara: 1.5 lg/L. Outlier concentration points at Arbara are indicated with grey
points.

Quinn et al., 2011). Freeze and Cherry (1979) consider usual values
of /f for rock range from 102 to 105. In our case, considering an
injection stretch of 41.5 m length with a total of 128 narrow to
very narrow (<0.25 mm) fractures identified, a value of
7.71
104 is a reasonable estimating of the maximum effective
fracture porosity. Regarding dispersivity, its value is typically
obtained by model calibration because appropriate physical con-
straints cannot be established directly (Field and Pinsky, 2000).
In any case, there is a clear trend of increase in longitudinal disper-
sivity with scale (Gelhar et al., 1992; Schulze-Makuch, 2005), with
values ranging from 0.01 m at metric field-scale tests to above
103 m at 105 m at larger field-scale tests. In our approximation, dis-
persivity was allowed to vary in a range from 0.01 to 102 m, which
is well above the distance between boreholes. Finally, the retarda-
tion factor reaches a minimum value of 1.0 for non-reactive sub-
stances. This value increases with fracture surface area and
distribution coefficient (Ka). In contexts where transport velocity
is rapid, as in the over-pressured part of the test, Ka ? 0 and sorp-
tion kinetics tends to be negligible (Field and Pinsky, 2000).
With these constraints, the three parameters were introduced
as fitting parameters in the modeling process. The spatial dis-
cretization was performed by the method of finite-difference and
the optimization process was completed by minimizing the sum Fig. 5. (a) Model results for different arrays ranging from 10 to 140 (section size
of squared differences between calculated and experimental val- from 1.02 m to 7.31
102 m). (b) Corresponding root mean square deviation
ues. Model solutions were obtained for different grid meshes, i.e., (RMSD).
276 T. Morales et al. / Journal of Hydrology 547 (2017) 269–279

Table 1
Main results of the tracer injection test.

Main characteristic parameters in the surroundings of the injection test

Fitted values Model summary
Dispersivity aL (m) Effective fracture porosity /f Retardation factor Rf Root mean square deviation RMSD (mg/L)
0.173 1.02
104 1.82 2.31
Main characteristic parameters at springs
Breakthrough curve after injection Breakthrough curve after main washing event
Time (h) Velocity (m/h) Recovery rate (%) Time (h) Velocity (m/h) Recovery rate (%)
La Lece 105.5 4.3 2.6 85.7 5.3 18,6
Arbara 128 13.7 2.0 – – –

The signal obtained at the other main spring is lower and

unclear. Thus, an irregular signal is obtained at Arbara only after
injection, with a 2.0% recovery rate, a maximum velocity of
37.8 m/h and a 13.7 m/h mean velocity.
The relatively high velocities at La Lece are comparable to the
results obtained from tracer tests conducted at nearby karst con-
duits (Morales et al., 2007). This similarity would indicate that
water reaches a preferential drainage network in its way to the
spring (Fig. 7).

5. Discussion

5.1. Concerning flow and transport dynamics in the karst

According to the objectives, the tracer injection test allowed

Fig. 6. Sensitivity analysis for aL (a), /f (b) and Rf (c) parameters.
injection and a second related to the thrust produced by the first
rains. In the first case, the amount of tracer recovered by the spring
was as low as 2.6%, with 13.7 m/h maximum velocity, 4.3 m/h
mean velocity and 105.5 h mean travel time, measured from the
pressure injection mean time. In the second part of the curve
recovery reaches a value of 18.6%, with a mean velocity of 5.3 m/
h and a mean travel time of 85.7 h, established from the mean time
of the main washing event at Br-2 borehole.
marking the karstic aquifer sector under investigation, analyzing
tracer evolution in the short, medium and long term, and assessing
their spatial reach in relation to aquifer major springs.
Concerning the initial displacement of the tracer in the vicinity
of the injection borehole, its extent was limited. Therefore,
although the low effective fracture porosity of the medium (/f:
1.02
104) and the low retention of tracer (Rf: 1.82) favored its
rapid displacement, the limited injection time did not allow reach-
ing the values of injection concentration at borehole Br-2. Never-
theless, the signal obtained by the electrical conductivity probe is
sufficient to obtain basic transport parameters by considering the
transport equation for a divergent flow from the injection well
for this initial period. The mentioned low value obtained for the
effective fracture porosity is related to a very limited number of
hydraulically interconnected active fissures in which transport is
highly efficient due to the high solubility of lithium chloride and
the injection conditions that inhibit the solute contact with frac-
tures surface.
In regard to the springs, a portion of tracer reaches the aquifer
most transmissive network during the injection and arrives to La
Lece spring by a well developed drainage path, as evidenced by
the high travel velocities (vm: 4.3 m/h). In these initial moments,
the percentage of tracer that reaches both the most transmissive
network and the springs is small (recovery rate at La Lece: 2.6%,
and at Arbara: 2.0%).
With the first rains a major tracer washed away was registered
at Br-2 borehole and a second marked breakthrough curve is
observed at La Lece (recovery rate: 18.6%). Tracer velocities are
similar to those obtained in the first curve after injection (vm:
5.3 m/h). At Arbara, the absence of a clear tracer signal may be
related to certain compartmentalization of the massif in this direc-
tion, and consequently a worse connection of the injection area
with the spring, or a higher tracer dilution due to the incorporation
of water contributions, especially in rainy events, from other sec-
tors of the aquifer in a longer path to the spring.
Finally, despite the high solubility of lithium chloride and low
initial retention, part of the tracer injected into the aquifer satu-
 T. Morales et al. / Journal of Hydrology 547 (2017) 269–279
Fig. 7. (a) Conceptual flow model after injection and main characteristic values. (b)
Conceptual flow model after first main washing event. (c) 24-h isochrone position
and minimum high vulnerability area to be considered based on test results.
rated zone persisted in the field for the first hydrological cycle and
was gradually being washed away by rain. Thus, along with a well
developed conduit network, a significantly less transmissive net-
work of fissures poorly connected to their surrounding influences
the tracer evolution in the aquifer in the medium and long term.
5.2. Concerning karst vulnerability and protection
The protection of water resources in karst areas requires
detailed flow and transport information to be implemented in vul-
277
nerability maps and protection schemes. This information is partic-
ularly necessary when drinking water supplies are concerned.
Thus, according to the Water Framework Directive (WFD) on
groundwater (European Commission, 2007) and other guidance
and recommendation documents, the definition of protection
zones of drinking water supply in karst aquifers is based on the
source (spring or well) vulnerability maps (Marín et al., 2015).
Thus, although different approaches have been applied to identify
the most vulnerable zones in karst catchment areas and elaborated
resource vulnerability maps (Doerfliger and Zwahlen, 1997;
Goldscheider et al., 2000; Davis et al., 2002), additional information
is deemed necessary to elaborate more specific source vulnerabil-
ity maps (Vías et al., 2006; Ravbar and Goldscheider, 2007; Kavouri
et al., 2011) and delineate the corresponding source protection
zones. Specifically, flow velocities and transit times within the sat-
urated zone are considered priority issues; thus, in most adapta-
tions of intrinsic resource vulnerability maps for source
vulnerability applications, the definition of flow isochrones around
sources, by joining as many transit time data as possible, is
required. However, the development of methods and protocols
aimed to ascertain flow velocities and transit times in these com-
plex contexts is still an ongoing challenge. In this field, injection
tests present two main advantages: they can be performed in the
sectors required and they allow obtaining direct objective informa-
tion on flow and transport dynamics, including transport velocities
towards springs and recovery rates. This information could be
incorporated, along with the remaining hydrogeological informa-
tion available, during the preparation phase of vulnerability maps
or could be used to validate them and solve uncertainties. It is also
important information to be included in broader karst assessment
works (Angulo et al., 2013).
Accordingly, this study confirms a direct relationship between
the injection sector and La Lece spring and a less marked and more
complex connection with Arbara spring. Concerning La Lece spring,
and based on the values of the mean velocity, the 24-h isochrone
was delineated for two events, i.e., the injection (Fig. 7a) and the
first washing event (Fig. 7b). This 24-h isochrone is considered as
a reference value in current approaches on source protection
(Andreo et al., 2009; Marín et al., 2015) to delineate the highest
vulnerability zone regarding groundwater flow within the satu-
rated zone. Nevertheless, the net arrival of tracer and relatively
high recovery rate, which is almost 20% after the washing event,
do not allow guaranteeing water quality at the spring if a contam-
ination event takes place. Thus, when source protection is the goal,
there are three main questions to be considered (Daly et al., 2002;
Brouyère, 2004): the time taken by a pollutant to reach the source,
proportion of contaminant arriving and duration of the contamina-
tion episode. In our case, the 24-h reference time must be neces-
sarily increased, given that a clear tracer signal was obtained at
La Lece spring. Besides, although no significant presence of tracer
was later registered at the spring, the tracer signal at the injection
zone lasted for a hydrological year, despite the high tracer solubil-
ity. Extrapolating this information to the potential behavior of a
contaminant highlights the need to expand the limit of the highly
vulnerable area beyond the 24-h isochrone limit and at least to
include the sector investigated, in order to ensure the quality of
water supply (Fig. 7c).
6. Conclusions
Tracer injection tests are proven to be an excellent tool for
obtain detailed knowledge on flow and transport in karst aquifers
from a local to a regional scale, including direct information on
transit times and velocities, and are particularly necessary when
dealing with water supply sources.
278 T. Morales et al. / Journal of Hydrology 547 (2017) 269–279
Thus, the injection of a LiCl solution directly into the saturated
zone of a karts massif at an initial pressure of 1 MPa allows observ-
ing a fast evolution of tracer in the borehole surroundings, which is
related to a very low effective fracture porosity (/f = 1.02
104),
and low dispersion (aL) and retardation (Rf) of tracer under these
initial test conditions. The signal registered in the springs is espe-
cially clear in the case of La Lece, where two unimodal break-
through curves were registered: the first one subsequent to the
injection (recovery rate: 2.6%) and a better delineated second one
(recovery rate: 18.6%) subsequent to the first rains that washed
the injection sector. The fast evolution of the tracer in both cases
allows confirming the direct connection of the injection sector with
this spring. Thus, although previous water injection results evi-
denced a medium of low permeability (k: 2.25
105 cm/s,
Angulo et al., 2011) and the absence of geomorphological evi-
dences of a highly functional underground network in the sector
assayed, the clear response obtained advices to include this sector
in the highly vulnerable area around the spring in order to safe-
guard its water quality beyond 24-h isochrone (ceiling value in
the European vulnerability maps). Furthermore, it should be also
noted that a small fraction of the tracer remains in the injection
zone and its presence with a decreasing trend is monitored for a
whole hydrological year.
The fact that this methodology may be implemented in selected
specific zones within the aquifers and the possible extrapolation of
the information obtained to the potential behavior of contaminants
in the short-, medium- and long-term highlights its interest, spe-
cially for the development and validation of source protection
schemes in these complex environments.
Acknowledgements
This study has been carried out by the UPV/EHU Research
Group IT-1029/16 supported by the Government of the Basque
Country. The authors also thank the Department of Environment
of the Basque Government (IHOBE) and the University of the Bas-
que Country for their financial support.
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