Water Air Soil Pollut (2008) 187:65–80

DOI 10.1007/s11270-007-9497-7

Characterization of the Salinisation Processes in Aquifers

Using Boron Isotopes; Application to South-Eastern Spain
Ignacio Morell & Antonio Pulido-Bosch &
Francisco Sánchez-Martos & Angela Vallejos &
Linda Daniele & Luis Molina &
José María Calaforra & Antoni Francesc Roig &
Alejandra Renau

Received: 8 May 2007 / Accepted: 13 August 2007 / Published online: 15 September 2007
# Springer Science + Business Media B.V. 2007

Abstract Use of δ11B provides a solid tool for dis-
criminating hydrogeochemical processes in complex
coastal aquifers. Its efficiency increases markedly
when it is applied along with other major or minor
constituents. Nevertheless, various factors may affect
its interpretation: the presence of clays, which favour
adsorption and desorption, the influence of waste-
waters, and even the presence of geothermalism.
The δ11B has been applied to the study of a series
of aquifers in south-eastern Spain: Castell de Ferro
(Granada), Campo de Dalías, Lower Andarax and
Sorbas (Almería), all of which are complex and hete-
rogeneous. The results obtained demonstrate that the
concentration of Br, the SO4/Cl and Cl/Br ratios are
good indicators of marine intrusion. Inland some
negative values of δ11B (−16.7 and −8.1‰) are re-
lated to a geothermal influence (34.8 and 51.5°C).
The boron solubility is directly related to temperature
favours boron mobilization, even from the associated
I. Morell : A. F. Roig : A. Renau
Department of Environmental Sciences,
University Jaume I,
Castellón, Spain
A. Pulido-Bosch : F. Sánchez-Martos : A. Vallejos (*) :
L. Daniele : L. Molina : J. M. Calaforra
Department of Hydrogeology, Escuela Politécnica Superior,
University of Almería,
04120 Almería, Spain
e-mail: avallejo@ual.es
metapelitic deposits. The difference in the boron iso-
tope content in two carbonate units must be caused by
the different composition of the carbonate rocks, as
well as a long residence time.
Keywords Boron isotopes . Tracers .
Hydrogeochemical processes . Coastal areas .
Seawater intrusion
1 Introduction
The study area runs along the coastline of Mediterra-
nean south-eastern Spain (provinces of Almería and
Granada). This is an arid region, where rainfall does
not normally exceed 300 mm/year, and where surface
water resources are very scarce and normally absent.
Water demand from tourism, and especially from the
intensive agriculture has developed considerably over
the last two decades, is almost completely met from
groundwater. In many cases, there are water quality
problems. It is clear that the economic development of
the region is closely linked to the availability of good-
quality groundwater.
The hydrogeology of these heterogeneous aquifers is
complex, with frequent hydraulic connections between
the detrital and carbonate aquifers. Salinisation can be
due to evaporite deposits (Sorbas, Lower Andarax),
thermalism (Lower Andarax, Campo de Dalías), slow
water circulation (Campo de Dalías), marine intrusion
66
(Castell de Ferro, Delta del Andarax, some parts of the
Campo de Dalías) and localised nitrate and wastewater
pollution. Therefore, characterisation of the hydro-
geochemistry is also complex, as can be seen from the
numerous published studies dealing with these aquifers,
by the Group Water Resources and Environmental
Geology at the University of Almería (Calaforra and
Pulido-Bosch 2003; Sánchez-Martos and Pulido-Bosch
1999; Sánchez Martos et al. 2002; Molina et al. 2002,
2003; Pulido-Bosch et al. 2000; Pulido-Leboeuf et al.
2003; Pulido-Leboeuf 2004; Vallejos et al. 1997).
The salinisation processes affecting these aquifers
have been studied using multiparametric approxima-
tions based on the major and certain minor ions (B,
Br, Sr, and Li). These studies have established that
the main processes involved are the presence of ma-
rine deposits, evaporite salts and present-day marine
influence.
Groundwater samples were taken from the areas
of Castell de Ferro, Campo de Dalías, Lower Andarax
and Sorbas (Fig. 1), with the aim of comparing the
hydrogeochemical processes implicated and analy-
sing variations in the boron isotope ratios in order to
understand these processes.
The main aim of this article is to report on the
usefulness of boron and its isotopes for identifying and
discriminating the hydrogeochemical processes occur-
ring in complex coastal aquifers. It considers the impact
of man (fertilizer use, irrigation using water from
different sources), as well as natural impacts, such as
the incorporation of brines, inflows of thermal waters,
dissolution of evaporite deposits, present-day marine
intrusion, and mobilisation of brines trapped in low-
permeability coastal sediments. Man has also played
some part in accelerating such processes, through
pumped abstractions and intensive exploitation.
1.1 Boron in Groundwater
Boron in groundwater is normally found at very low
concentrations, as a trace element or minor ion. How-
ever, natural inputs from seawater, brines, geothermal
fluids or from evaporite deposits can appreciably
increase concentrations to above the mean value for
seawater. The two main sources of boron are seawater
(4.5 mg l−1), and evaporites or brines of marine or
continental origin, in which boron tends to be con-
centrated (Ulhman 1991). Thus, boron has been used
as an indicator of the source of salinity in ground-
Water Air Soil Pollut (2008) 187:65–80
water (Arad et al. 1986). Boron can also have an
anthropogenic origin, as in the case of pollution by
wastewater, which is enriched in boron (1–2 mg l−1)
due to presence of detergents manufactured using
borax; the use of fertilisers applied to compensate for
deficiencies of boron in the soil; or the discharge of
effluent from cleaning industries that use sodium
perborate. Boron is also found in residues from paper
mills and, sometimes, in effluents from nuclear power
stations. Of particular importance is the influence of
waste from the ceramics industry, which uses borax
as flux: the liquid effluents can contain more than
10 mg l−1 boron, while the gaseous effluents (more
than 24 m3B year−1) released into the atmosphere can
later reach the ground in rainfall. Concentrations in
rainwater of up to 7 mg l−1 boron have been recorded
in Castellón province. With respect to water–rock
interactions, various authors have pointed out the
significant role that temperature can play (Arnorsson
and Andresdottir 1995), and indeed, many thermal
waters have elevated boron concentrations (Kakianha
et al. 1989; Murray 1996; Sánchez-Martos and
Pulido-Bosch 1999; Vengosh et al. 2002).
Natural boron has two stable isotopes – 10B and
11
B – whose relative abundance is 20 and 80%,
respectively. Variations in the ratio of the two isotopes
is normally expressed as a deviation per mil (δ11B)
compared to standard boric acid (NIST SRM or NBS
951), which has a 11B/10B ratio of 4.04367. The nota-
tion for δ11B is:
h
10  .
 i
δ11 B ¼ 11
B B sample 11 B 10 B NBS 951  1  1; 000
Because of the marked difference in mass between
the two isotopes and the high geochemical reactivity
of boron, the isotopic fractionation leads to significant
variations in the 11B/10B ratio for natural waters from
different geological environments (Vengosh et al.
1994a; Basset et al. 1995; Barth 1998a, b).
In the open sea, the present-day Mediterranean
yields a constant δ11B of around +37.7‰ (Barth 1993).
This high values is attributable to isotopic fractionation
associated with boron adsorption in detrital clays, se-
condary minerals formed due to alterations at low
temperature of the ocean’s crust and carbonate min-
erals. Given that 11B and 10B preferentially partition
as species with coordination 3 and 4 (B(OH)3 and
BðOH Þ 4 , respectively), and that it is the tetrahedral
Water Air Soil Pollut (2008) 187:65–80
Fig. 1 Location of the aquifers under study, from West to East,
including sampling points. a Castell de Ferro (1: metapelites, 2:
marbles, 3: alluvial); b Campo de Dalías (1: metapelites; 2:
Carbonates, 3: Miocene calcarenites, 4: Pliocene calcarenites,
5: Quaternary sediments); c Lower Andarax (1: limestones and
67
dolomites; 2: phyllites and calcoschists; 3: marls; 4: limestones
and calcarenites; 5: sandy marls; 6: plioquaternary conglom-
erates, sands, muds and clays); d Sorbas (1: silt and marls, 2:
limestone, 3: gypsums, 4: sandstones and marls)
68
species that is preferentially involved in the adsorp-
tion processes, dissolved marine boron becomes
enriched in the trigonal species, which in turn gives
rise to very high δ11B values. Very high values have
been calculated for saline lakes (e.g. Dead Sea),
while in fresh groundwater, highly variable values
(between −27‰ and +44‰) depend on the geochem-
ical medium in which they are found (lithology), on
the isotopic fractionation they have undergone, and on
the degree of mixing with water with a different iso-
tope profile. Waters of hydrothermal origin normally
have values of between −10 and +10‰ (Barth, op. cit.).
Urban wastewaters and borate fertilisers are important
anthropogenic source of boron, and these usually give
very low δ11B values (−15 a +5‰; Vengosh et al.
1994a; Leenhouts et al. 1998).
For all these reasons, the boron isotope ratio (δ11B)
is used as a tracer of the evolution of natural systems,
and to identify processes of groundwater pollution.
There are numerous studies showing the potential
of the boron isotopes as tracers of hydrogeochemical
processes in a range of very different hydrogeological
situations. These situations include salinisation due
to marine intrusion, marine and non-marine brines
(Vengosh et al. 1991a, b, 1995, 1998, 1999), urban
wastewater pollution (Vengosh et al. 1994a; Basset
et al. 1995; Eisenhut et al. 1996), nitrate pollution
(Leenhouts et al. 1998), differentiation of fresh waters
(Pennisi et al. 2000; Larsen et al. 2001), water–rock
interactions (Barth 1998a), and thermalism (Kakianha
et al. 1989; Oi and Kakianha 1993; Oi et al. 1996;
Vengosh et al. 1994b, 2002).
2 Hydrogeological Settings
Figure 1 shows the location of the aquifers in this
study, namely (from west to east), Castell de Ferro,
Campo de Dalías, Lower Andarax and Sorbas. The
detrital coastal aquifer of Castell de Ferro lies in
the southeast of Granada province. It lies in the
Alpujarride Domain of the Betic Cordillera. The pre-
orogenic rocks belong to the Alpujarride Complex
and comprise marbles and metapelites with some
limestone and gypsum intercalations. The most im-
portant post-orogenic materials are the alluvial depos-
its, the very heterometric fill in the “ramblas” or gullies
(Pulido-Leboeuf et al. 2003). These deposits form the
Water Air Soil Pollut (2008) 187:65–80
Castell de Ferro aquifer, which occupies a surface
area of around 3 km2. It extends nearly 5 km N–S and
its maximum width is around 700 m. Here, the detrital
deposits reach their maximum thickness (some 60 m,
according to mechanical borehole logs). The outcrop
of karstified marbles that underlies the village of
Castell de Ferro constitutes a preferential path for
fluid exchange between these two rock types, since it
is in contact with both the detrital aquifer and with the
sea (Calvache and Pulido-Bosch 1994). This means
that the small aquifer is highly suited for studies
comparing the marine intrusion processes in karstic
and detrital aquifers.
The Campo de Dalías is a coastal plain of 330 km2
situated to the west of the bay of Almería. Three
hydrogeological units are distinguished: Balerma-Las
Marinas, Balanegra and Aguadulce (Pulido-Bosch
et al. 1991; Molina et al. 2002). The first occupies
the central-southern part of the Campo. It consists of
100–150 m Pliocene calcarenites, with localised
Quaternary detrital deposits. Pliocene marls form the
impermeable base of this unit. The Balanegra Unit
occupies the western half and is basically composed
of Alpujarride carbonates, whilst the eastern half, the
Aguadulce Unit, consists of Alpujarride dolostones of
the outcropping in the Sierra de Gador, calcarenites
and Miocene volcanic rocks, and calcarenites with
episodes of Pliocene sandy marls, and Quaternary
sediments. Tectonically, this is the most complex
unit and its geometry is the least well-known. In
some parts, it is a truly multilayer aquifer, in which
various aquifer formations are separated by other low-
permeability layers.
The Basin of Lower Andarax covers approximately
250 km2. Its western limit corresponds to the Sierra of
Gádor; its eastern edge is delimited by the Sierra
Alhamilla, and the southern limit corresponds to the
Mediterranean Sea. Three hydrogeological units are
distinguished: the carbonate aquifer, the detrital
aquifer and the deep aquifer. The detrital aquifer is
formed by a variety of sediments, including sandy-
conglomerate Pliocene deposits and alluvial from the
river Andarax. At its mouth, the aquifer consists of
deltaic deposits with a clear marine influence, which
are in lateral continuity with the alluvial deposits
(Sánchez-Martos 1997). The carbonate aquifer ex-
tends along the entire edge of the mountains, con-
sisting of Triassic dolomites and limestones and, in
places, Miocene calcarenites. It is an unconfined aqui-
Water Air Soil Pollut (2008) 187:65–80 69

fer, though in places it contains confined impervious

marly intercalations. The deep aquifer corresponds to a
limestone-dolomite Alpujarride formation that makes
up the Betic substrate between the Sierra of Gádor
and the Sierra Alhamilla. It is in the order of 100 m in
thickness, and overlies on a formation of phyllites and
quartzites. Over the dolomites are Miocene calcarenites
and conglomerates (Sánchez-Martos, op. cit.).
The Basin of Tabernas-Sorbas is located in the most
desertified locality in Europe. The so-called gypsum
aquifer of Sorbas (Yesares member) occupies part of this
basin and dates from the Messinian. The area is little
affected by folding and the gypsum forms a large syn-
cline. The most important gypsum massif is composed
of gypsiferous strata with very continuous marly
interstrata. More than 1,000 caves have been invento-
ried over an area of some 12 km2. The total length of
subterranean passages in the caves is more than 50 km,
of which 8.3 km correspond to the Cueva del Agua.
Gypsum possesses good water-bearing capacity due to
karstification across the discontinuities. Water flows
both through the large channels and in the gypsum
matrix (Calaforra and Pulido-Bosch 2003). The main
spring, Los Molinos, is located in a gypsum canyon
excavated by the river Aguas. At this point, impervious
marls and silt lie very close to the surface. The spring
of the river Aguas is the lowest topographical point of
the gypsum outcrop. Its flow remains above 40 l/s,
even through prolonged periods of drought (Pulido-
Bosch et al. 2004).
In the carbonate aquifers, especially in the Campo Fig. 2 Piper diagram of groundwater in the study area. a
of Dalías, the dominant water types are calcium or Eastern area: Lower Andarax (1: detrital aquifer, 2: Alhamilla
calcium–magnesium bicarbonate, with a tendency spa, 3: deep aquifer, 4: spring in the Tabernas rambla) Sorbas
Gypsums (5). b Western area: Campo de Dalías (1: Balanegra,
towards sodium chloride facies in sectors influenced 2: Balerma, 3: Aguadulce) Castell de Ferro (4)
by marine intrusion. In Castell de Ferro there is a
progression from calcium bicarbonate waters towards
sodium chloride (Fig. 2b), due to marine intrusion 3 Sampling and Analytical Procedures
(Pulido-Leboeuf 2004). In the Lower Andarax, mixed
facies predominate due to the presence of associated A total of forty water samples were taken in March
evaporite deposits; the evaporitic influence can be 2002 (Table 1). These came from four springs (at
distinguished by water of calcium–magnesium sul- Alhamilla spa and Rambla de Tabernas in the Lower
phate type (Fig. 2a). On the Andarax delta, the marine Andarax; Cueva del Agua and Los Molinos in the
influence leads to calcium chloride and sodium Sorbas depression), with the remainder being taken
chloride facies. The waters in the karstic gypsums of from boreholes (e.g. Campo de Dalias, Castell de
Sorbas are calcium sulphate type. Thermalism in the Ferro), some of which were sampled at various depths
deep carbonate aquifer of Campo of Dalías and, (Andarax delta and Castell de Ferro). On the Andarax
particularly, in the Lower Andarax even has some delta, samples were taken at different depths from
influence on the relative abundance of certain minor the three piezometers drilled to feed seawater to the
ions (e.g. boron and lithium). Desalination Plant that will supply the city of Almería.
 70
Table 1 Chemical and isotopic data of groundwater

No. Sampling Temp Cond. pH Cl SO4 HCO3 Ca Mg Na K Sr Sr/Ca Br B B SO4/Cl B/Cl B/SO4 Cl/Br δ11B SIcal SIdol SIgyp
site (°C) (microS (meq (meq (meq (meq (meq (meq (meq (meq (meq (meq (mg (meq (meq (meq l−1) (meq (meq (‰)
cm−1) l−1) l−1) l−1) l−1) l−1) l−1) l−1) l−1) l−1) l−1) l−1) l−1) l−1) l−1) l−1)

Bajo Andarax
1 Detrital 14.6 1,303 7.63 5.77 6.94 4.83 10.24 4.93 2.07 0.09 0.046 0.004 0.004 0.20 0.06 1.20 0.0096 0.008 1,647.8 14.6 0.62 0.91 −0.87
Aquifer
2 Detriatal 24.6 2,740 7.26 28.71 15.25 5.60 9.35 8.07 19.81 0.23 0.089 0.009 0.019 0.71 0.20 0.53 0.0069 0.013 1,534.2 2.1 0.29 0.63 −0.77
Aquifer
3 Detrital 18.3 3,670 7.22 36.16 10.42 6.42 8.69 8.55 19.53 0.24 0.089 0.010 0.020 0.78 0.22 0.29 0.0060 0.021 1,834.6 −11.3 0.21 0.46 −0.93
Aquifer
4 Detrital 20.9 3,770 7.13 14.30 16.47 4.68 16.01 12.17 11.18 0.18 0.098 0.006 0.023 0.70 0.19 1.15 0.0135 0.012 625.9 10.0 0.27 0.49 −0.53
Aquifer
5 Detrital 22.8 12,830 7.19 99.49 23.52 3.91 14.96 26.86 91.05 0.69 0.108 0.007 0.107 2.22 0.62 0.24 0.0062 0.026 926.5 22.5 0.09 0.55 −0.68
Aquifer
6 Detrital 20.8 20,300 7.12 175.84 30.06 6.32 19.34 36.70 119.26 1.16 0.108 0.006 0.281 0.55 0.15 0.17 0.0009 0.005 625.8 20.6 0.25 0.87 −0.57
Aquifer
7 Detrital 20.6 47,600 7.13 401.80 43.41 4.99 30.24 90.22 336.78 7.17 0.166 0.006 0.695 2.66 0.74 0.11 0.0018 0.017 578.5 36.1 0.22 1.03 −0.49
Aquifer
8 Detrital 20.4 50,800 7.49 440.71 45.97 3.39 24.70 91.23 361.83 10.44 0.187 0.008 0.799 4.47 1.24 0.10 0.0028 0.027 551.3 33.5 0.31 1.31 −0.57
Aquifer
9 Detrital 21.3 9,000 7.09 60.90 22.23 5.40 23.86 21.10 37.16 0.68 0.110 0.005 0.106 0.67 0.19 0.37 0.0031 0.008 572.2 10.9 0.36 0.76 −0.42
Aquifer
10 Detrital 20.7 49,800 7.52 508.67 44.93 4.37 24.43 82.69 395.96 9.25 0.119 0.005 0.792 3.40 0.94 0.09 0.0019 0.021 642.0 44.7 0.45 1.55 −0.59
Aquifer
11 Detrital 21.1 52,900 7.48 561.35 51.16 2.98 25.16 86.54 384.96 11.22 0.173 0.007 0.878 4.76 1.32 0.09 0.0024 0.026 639.2 36.7 0.25 1.18 −0.53
Aquifer
12 Detrital 22.1 6,270 7.03 24.63 29.34 5.81 22.54 19.08 21.54 0.24 0.120 0.005 0.064 0.87 0.24 1.19 0.0098 0.008 386.4 26.0 0.33 0.67 −0.29
Aquifer
13 Detrital 21.2 31,100 7.24 331.52 34.72 3.49 23.87 47.14 262.57 4.90 0.100 0.004 0.484 1.67 0.46 0.10 0.0014 0.013 684.8 42.1 0.13 0.68 −0.58
Aquifer
14 Detrital 20.6 49,500 7.39 389.14 41.78 3.60 22.95 70.57 320.48 9.87 0.102 0.004 0.749 3.77 1.04 0.11 0.0027 0.025 519.4 37.5 0.23 1.07 −0.59
Aquifer
15 Deep Aquifer 34.8 3,870 6.68 23.59 12.32 8.58 8.92 5.37 20.63 1.18 0.141 0.016 0.012 4.76 1.32 0.52 0.0561 0.107 1,942.8 −16.7 0.02 0.04 −0.87
16 S. Alhamilla 51.5 1,539 6.81 14.04 4.37 7.50 3.05 4.07 11.87 0.21 0.041 0.013 0.002 0.58 0.16 0.31 0.0115 0.037 6,230.8 −8.1 −0.05 0.32 −1.59
Spa
17 R. Tabernas 15.9 9,390 8.02 59.82 32.04 5.55 1.28 19.67 67.02 0.44 0.179 0.008 0.062 5.38 1.49 0.54 0.0250 0.047 971.5 10.8 1.11 2.20 −0.34
spring
Campo de Dalías
18 Aguadulce 20.8 522 7.84 2.67 0.92 3.75 1.81 2.31 0.33 0.03 0.017 0.009 0.003 0.04 0.01 0.34 0.0039 0.011 1,016.2 −0.4 0.22 0.62 −2.22
Unit
19 Aguadulce 22.0 476 7.86 2.01 1.23 3.75 1.88 2.29 0.39 0.03 0.008 0.004 0.001 0.04 0.01 0.61 0.0055 0.009 1,605.4 4.7 0.27 0.72 −2.09
Unit
Water Air Soil Pollut (2008) 187:65–80
 20 Aguadulce 23.0 652 7.77 5.30 1.02 4.27 1.93 3.06 1.50 0.06 0.016 0.009 0.003 0.11 0.03 0.19 0.0055 0.029 1,692.9 7.4 0.23 0.77 −2.21
Unit
21 Balerma Unit 22.3 4,620 7.15 25.87 12.94 5.50 11.34 17.64 22.92 0.43 0.264 0.023 0.040 0.82 0.23 0.50 0.0088 0.018 646.1 25.6 0.22 0.72 −0.82
22 Balerma Unit 20.5 2,450 7.6 14.20 5.04 4.99 4.61 9.16 9.83 0.21 0.049 0.011 0.026 0.45 0.12 0.36 0.0088 0.025 553.5 31.6 0.33 1.04 −1.39
23 Balanegra 22.0 1,316 7.48 21.73 1.15 4.06 3.42 4.54 4.38 0.04 0.036 0.010 0.020 0.38 0.11 0.05 0.0048 0.092 1,065.1 36.1 0.08 0.39 −2.05
Unit
24 Balanegra 33.5 1,871 8.14 14.14 2.63 3.55 3.03 2.89 11.85 0.26 0.050 0.017 0.015 0.27 0.07 0.19 0.0053 0.028 941.7 33.6 0.75 1.70 −1.75
Unit
25 Balanegra 32.0 1,655 7.59 11.88 2.33 3.60 2.74 2.99 9.79 0.21 0.050 0.018 0.014 0.16 0.04 0.20 0.0037 0.019 870.6 8.2 0.18 0.61 −1.82
Unit
26 Balanegra 35.3 1,544 7.39 10.95 1.96 3.60 2.43 2.81 8.40 0.18 0.046 0.019 0.020 0.18 0.05 0.18 0.0045 0.025 536.7 21.3 −0.01 0.28 −1.92
Unit
27 Balanegra 37.6 1,391 7.42 27.32 1.29 3.70 2.64 2.99 8.81 0.20 0.052 0.020 0.009 0.17 0.05 0.05 0.0017 0.036 2,950.3 20.8 0.06 0.43 −2.13
Water Air Soil Pollut (2008) 187:65–80

Unit
28 Balanegra 35.1 2,180 7.45 17.40 1.36 3.55 2.95 3.28 14.14 0.26 0.056 0.019 0.021 0.15 0.04 0.08 0.0024 0.031 827.3 30.5 0.10 0.48 −2.06
Unit
Castell de Ferro
29 S-4-30 18.1 1,590 7.39 10.59 3.12 5.50 5.26 4.09 6.43 0.17 0.008 0.002 0.008 0.11 0.03 0.29 0.0029 0.010 1,387.6 33.4 0.24 0.41 −1.44
30 S-4-40 18.5 2,900 7.38 47.90 4.38 5.34 7.45 6.27 22.28 0.35 0.013 0.002 0.018 0.21 0.06 0.09 0.0012 0.013 2,639.4 36.6 0.26 0.50 −1.33
31 S-4-45 18.5 28,200 7.15 94.87 11.38 5.09 20.13 22.88 188.35 1.77 0.058 0.003 0.323 0.83 0.23 0.12 0.0024 0.020 294.2 35.7 0.22 0.57 −0.91
32 S-4-60 18.6 37,900 7.11 480.75 39.58 4.01 20.82 80.49 356.96 8.12 0.094 0.005 0.640 3.30 0.91 0.08 0.0019 0.023 751.7 35.7 −0.07 0.53 −0.68
33 CASE-1 19.0 2,300 7.41 18.73 2.94 5.50 4.84 5.53 10.73 0.22 0.018 0.004 0.019 0.15 0.04 0.16 0.0022 0.014 971.8 40.2 0.21 0.53 −1.56
(10 m)
34 CASE-1 19.2 21,400 7.1 169.44 10.31 4.99 14.61 38.56 170.15 2.75 0.057 0.004 0.311 1.01 0.28 0.06 0.0016 0.027 545.7 38.2 0.01 0.53 −1.15
(40 m)
35 CASE-1 18.8 33,900 7.14 460.81 36.48 4.42 17.70 67.06 293.26 6.29 0.087 0.005 0.526 2.60 0.72 0.08 0.0016 0.020 875.8 36.0 −0.05 0.57 −0.73
(55 m)
36 CASE-2 21.1 2,120 7.25 20.68 5.60 4.88 10.80 6.99 7.14 0.12 0.027 0.003 0.013 0.04 0.01 0.27 0.0006 0.002 1,620.1 36.0 0.33 0.55 −1.03
37 Well 18.3 1,049 7.8 2.48 1.77 5.29 5.04 3.26 1.97 0.04 0.017 0.003 0.000 0.04 0.01 0.71 0.0041 0.006 9,907.7 14.6 0.67 1.20 −1.62
Aquifer of Sorbas
38 Well La 20.1 4,240 7.05 24.49 26.17 4.47 29.79 6.86 11.37 0.08 0.284 0.010 0.012 0.42 0.12 1.07 0.0048 0.004 1,976.3 33.8 0.35 0.14 −0.16
Cumbre
39 Los Molinos 20.1 3,530 7.20 21.93 30.04 4.01 32.83 6.49 6.72 0.08 0.168 0.005 0.007 0.34 0.09 1.37 0.0043 0.003 2,969.6 17.5 0.48 0.33 −0.07
Spring
40 Cueva del 14.3 2,430 7.85 3.42 17.38 1.85 28.40 0.70 0.87 0.02 0.062 0.002 0.001 0.10 0.03 5.07 0.0081 0.002 4,560.7 30.0 0.75 −0.12 −0.20
Agua Spring
Seawater 568.49 59.71 2.75 25.95 112.10 458.78 10.59 0.183 0.007 0.847 4.50 1.25 0.11 0.002197 0.021 670.9 39.0
71
72
Temperature, electrical conductivity and pH were
determined in situ, whilst bicarbonate was analysed in
the field by volumetry using methyl orange as
indicator. Chloride, sulphate and nitrate were deter-
mined in an ALKEMP 501 autoanalyser. Sodium,
potassium, magnesium, calcium, strontium and lithi-
um were analysed by spectrophotometry by atomic
absorption; iodide and bromide, by Mass ICP. Lastly,
total boron was determined by colorimetry using the
azomethine-H method.
Boron isotope ratios were measured with an HP-
4500 ICPMS. Highly saline samples (with widely
ranging concentrations) were pre-treated with a boron-
specific resin (Amberlite IRA 743) to avoid matrix
induced mass discrimination (Kiss 1988). Instrumental
parameters (nebulizer and ion optics) were optimized
to achieve the maximum signal for boron and the best
precision for the measurement of the 10B/11B ratio. A
MCN 100 microconcentric nebulizer fed by a peristal-
tic pump from the instrument was used for sample
introduction. Resolution of the quadrupole was set to
0.5 uma (10% peak height) to prevent 12C overlap.
Instrumental mass discrimination was corrected using
the reference solution NIST SRM 951 that is certified
for its boron isotope ratio (Gregoire 1987) using a
solution of 200 ppb of B. To eliminate mass dis-
crimination induced by excess HCl from the resin
treatment, the boron standard was also prepared in that
medium. Samples with high boron concentrations were
diluted using 0.7 M HCl to reduce the boron con-
centration to around 200 ppb. Isotope measurements
were carried out in quintuplicate. The integration time
for 10B was 8 s and for 11B, 5 s in order to obtain the
same precision in counting statistics for both masses.
Three points per peak were measured for each mass in
Fig. 3 Plot of Cl vs SO4
(in meq l−1). Key: Lower
Andarax (1: detrital aquifer,
2: deep aquifer 3: Alhamilla
spa, 4: spring in the
Tabernas rambla); Campo
de Dalías (5: Aguadulce, 6:
Balerma, 7: Balanegra);
Castell de Ferro (8) and
Sorbas gypsums (9)
Water Air Soil Pollut (2008) 187:65–80
IR mode (dwell time 10 ms). Overall precision ob-
tained for the isotope ratio measurements was around
0.2% RSD. All the analyses were undertaken in the
laboratories of the University Jaume I of Castellón.
4 Results and Discussion
4.1 General Comments on Salinisation
in Groundwaters
The general model for salinisation of groundwater in
coastal aquifers of south-eastern Spain can be cha-
racterised based on their chloride and sulphate content.
In coastal aquifers, both ions can come from seawater,
though there are other mechanisms that contribute
to the salinisation. These include natural processes
(presence of brines, liberation of saline water from
aquitards) and man-made (agriculture, discharges).
Fresh waters unrelated to seawater can also show a
certain degree of mineralization, especially if they are
influenced by evaporite deposits.
Figure 3a shows the relationship between chloride
and sulphate. It highlights how the most saline
samples (>200 meq l−1 Cl) fit the theoretical line of
conservative mixing between fresh water and seawa-
ter. These saline samples come from the Castell de
Ferro aquifer and the delta portion of the Lower
Andarax detrital aquifer, where marine intrusion is
well documented (Calvache and Pulido-Bosch 1994;
Sánchez-Martos et al. 2002).
The other aquifers in the study lack any marine
influence and, here, sulphate concentrations are high
in comparison to chloride, suggesting the presence of
a saline member that is sulphate in nature (Fig. 3b).
Water Air Soil Pollut (2008) 187:65–80
Fig. 4 Plot of Cl vs SO4/Cl ratio (in meq l−1). Key: Lower
Andarax (1: detrital aquifer, 2: deep aquifer, 3: Alhamilla spa,
4: spring in the Tabernas rambla); Campo de Dalías (5:
Aguadulce, 6: Balerma, 7: Balanegra); Castell de Ferro (8)
and Sorbas gypsums (9)
The highest sulphate concentrations correspond to the
saline spring in the Tabernas rambla (Lower Andarax)
and to samples taken in the Sorbas depression from
the Messinian gypsums. However, elevated concen-
trations are also found in the Lower Andarax detrital
aquifer, and this may be related to agricultural practices,
as may also be the case for water in the uppermost
aquifer unit of the Campo de Dalías (Balerma-Las
Fig. 5 Plot of a Cl vs B
and b Cl vs B/Cl ratio
(in meq l−1). Key: Lower
Andarax (1: detrital aquifer,
2: deep aquifer 3: Alhamilla
spa, 4: spring in the
Tabernas rambla); Campo
de Dalías (5: Aguadulce, 6:
Balerma, 7: Balanegra);
Castell de Ferro (8) and
Sorbas gypsums (9)
73
Marinas Unit). Sulphate concentrations in the Castell
de Ferro aquifer and the carbonate units of the Campo
de Dalías (Balanegra and Aguadulce Units) are very
low (Fig. 3b) and this points to the absence of inflows
of water that dissolve evaporite rocks.
In the most saline samples, with a clear marine
influence, as well as in some fresh water samples
from the Castell de Ferro Aquifer and the Balanegra
unit of Campo de Dalías, the SO4/Cl ratio is similar to
that of seawater (Fig. 4). The highest values come
from the gypsum karst aquifer of Sorbas, (the sam-
pling point at the Cueva del Agua spring has SO4/Cl=
5.07), where magnesium, potassium, chloride and
bicarbonate content is low. This suggests a short
residence time for water in this aquifer. In the Lower
Andarax, elevated SO4/Cl ratios are also recorded.
These exceed 1.0 at some points in this detrital aqui-
fer away from the coastal zone.
4.2 Boron
The highest boron concentrations are found in sam-
ples from three sectors of the Lower Andarax, namely
the saline Tabernas spring (5.38 mg l−1), the deep
aquifer (4.76 mg l−1) and boreholes supplying water
to the desalination plant on the Andarax delta (4.47–
4.76 mg l−1). 70% of all the samples analysed
exhibited concentrations of less than 1 mg/l. The re-
maining samples were taken from the Lower Andarax
and from three borehole samples taken near Castell de
Ferro.
Broadly speaking for B and Cl (Fig. 5a), one can
distinguish two distinct origins of boron: one is sea-
74
water, which accounts for the most saline samples of
the Lower Andarax from the delta and Castell de
Ferro. The second origin is the sulphate waters or
unidentified anthropic sources (agriculture, wastewater
re-use?). Figure 5b shows this multiple origin and
reveals that, except for samples affected by marine
influence, there is enrichment in boron with respect to
chloride, and that this occurs differentially in each of
the aquifers considered, leads to the idea that the boron
may result from a number of different mechanisms.
Some of the sampling points in the detrital aquifer
of the Lower Andarax have a SO4/Cl ratio that is
lower than the Sorbas gypsums (Table 1), while the B
and B/Cl ratios are higher. This suggests that the
boron here is directly related to the Cl content. These
points are found over the Pliocene marine deposits
that form the distal facies of the river Andarax delta,
and this would explain why Cl and B are higher than
in the Messinian gypsums around Sorbas. In addition,
some of the sampling points register slightly elevated
temperature, which would favour the mobilisation of
B (Oi et al. 1996; Vengosh et al. 2002).
No close relationship between boron and sulphate
can be detected from Fig. 6a, but rather, each aquifer
shows its own distinct trend. This suggests either the
boron has a different origin or that mechanisms dif-
ferentially affect its concentration, such as the effect
of water temperature on boron mobilization. It is in-
teresting to note that the boron concentration in the
deep aquifer of Lower Andarax is 4.76 mg l−1, while
the B/Cl ratio is very high (0.06). This boron is
accompanied by high concentrations of strontium and
Fig. 6 Plot of a SO4 vs B
and b Ca vs B (in meq l−1).
Key: Lower Andarax
(1: detrital aquifer, 2: deep
aquifer 3: Alhamilla spa,
4: spring in the Tabernas
rambla); Campo de Dalías
(5: Aguadulce, 6: Balerma,
7: Balanegra); Castell de
Ferro (8) and Sorbas
gypsums (9)
Water Air Soil Pollut (2008) 187:65–80
potassium and relatively low calcium and sulphate
concentrations. All these factors suggest that, in this
case, the boron does not derive solely from evapo-
rites, but that its mobilisation is favoured by the high
water temperature (34.8°C, measured in the only
borehole that taps this aquifer).
The saline spring in the R. Tabernas is the most
sulphate-rich of all the non-marine samples. Its high
boron concentration (5.4 mg l−1) indicates that the
strata drained by this spring are, at least locally,
boron-enriched. The other points in the Lower
Andarax give a lower B/SO4 ratio (Table 1) and,
therefore, the possibility that boron is implicated in
the adsorption process cannot be rejected, since these
sampling points are located in Pliocene delta deposits
that contain some more lutitic layers.
The relationship between calcium and boron
(Fig. 6b) reveals some interesting aspects. The boron
also seems to be related to the calcium ion, except
in the saline Tabernas spring and the deep Andarax
aquifer. This could be a result of differential enrich-
ment of boron with respect to calcium and magnesium,
which could be involved in precipitation of calcite and
dolomite. In the Tabernas spring the water is super-
saturated in both species (SIdol and SIcal, 2.20 and 1.11,
respectively; Table 1); while in the deep aquifer it is in
equilibrium with both these minerals. The most saline
samples – in which the boron has a basically ma-
rine origin – have elevated calcium concentrations
compared to the line of FW–SW (where the least
saline sample analysed is taken to be fresh water).
This is probably a result of reverse ion exchange, which
Water Air Soil Pollut (2008) 187:65–80
has been noted in both the Andarax Delta (Sánchez-
Martos 1997) and the Castell de Ferro aquifer (Pulido-
Leboeuf 2004).
4.3 Other Ions
Seawater contains an average of 67 mg l−1 bromide,
while fresh water contains very low concentrations.
The bromide–chloride ratio can be used to identify
fresh water – seawater mixing (Morell et al. 1986), to
study brines (Hsissou et al. 1999) and to identify
evaporitic inputs; it can also be used in fresh waters to
classify waters according to their origin (Custodio and
Herrera 2000). This is because seawater is the only
significant source of bromide and because bromide
behaves as a conservative ion; moreover, neither the
dissolution of halites during the formation of saline
waters and brines, nor its precipitation during evap-
oration, include the bromide ion, which therefore ac-
cumulates in the residual brine (Sanders 1991; Richter
and Kreitler 1993).
The Cl/Br ratio in seawater is in the order of 650
(Davis et al. 2001). In Fig. 7, one can see that the
saline samples approximate to this value quite well,
which indicates the marine origin of both ions in the
Castell de Ferro and Lower Andarax aquifers. A low-
Fig. 7 Plot of Cl vs Cl/Br (in meq l−1). Key: Lower Andarax
(1: detrital aquifer, 2: deep aquifer, 3: Alhamilla spa, 4: spring
in the Tabernas rambla); Campo de Dalías (5: Aguadulce, 6:
Balerma, 7: Balanegra); Castell de Ferro (8) and Sorbas
gypsums (9)
75
er ratio for some fairly fresh waters near the coast
could be due to the effect of marine aerosols (Duce
and Hoffman 1976). However, such differential frac-
tionation and enrichment of bromide could not be
appreciable (Custodio and Herrera 2000) and it could
be possible that infiltration water passes through soil
horizons that are rich in organic matter within which
Br is found (Gerritse and George 1988).
In samples of waters unassociated with marine
intrusion the Cl/Br ratio is normally greater, and this
could be due to the dissolution of evaporites that are
relatively rich in halites, such as in the case of Sorbas
and the deep Andarax aquifer (Cl/Br=2,000–4,500).
Sampling points in the detrital Andarax aquifer away
from the delta also give high ratios (1,600–1,800),
and this is probably due to the dissolution of eva-
porites in which halites may be present, since they
come from marine Pliocene deposits. Along the coast-
al fringe of the delta the ratio is low (400–700) and
close to the value for seawater, this is due to recent
marine influence.
Figure 7 shows the sample from Alhamilla spa to
have a very high ratio of 6,230, which is because
the water has a sodium chloride facies and contains
very little Br. Likewise, the Castell de Ferro samples
have a much higher Cl/Br ratio than other samples
from the same area. This is because the sample is
not influenced by the sea and has a very low Br
concentration.
Figure 8 shows the relationship between chloride
and strontium. The most saline samples from the
detrital aquifer of the Lower Andarax give a ratio in
keeping with fresh water–saltwater mixing (in seawa-
ter, Sr=8 mg l−1 =0.1826 mmol l−1), with a range of
between 2 and 5 mg l−1 in the Lower Andarax. In the
Castell de Ferro aquifer, the alignment of points is
similar, though the range of concentration of Sr is 0.3
to 4.1 mg l−1. The elevated concentrations in the
Lower Andarax waters seem to be directly related to
inputs of Sr from evaporite deposits, which are also
the source of the high sulphate concentrations. The
presence of strontium in evaporites is well known,
both as a trace element in solution and as celestine
(SrSO4), which may be precipitated along with the
sulphate. This hypothesis is confirmed by the fact that
the highly sulphated samples come from the gypsum
aquifer in Sorbas and that the Balerma–Las Marinas
aquifer in the Campo de Dalías yields the highest
strontium concentration (between 8 and 13 mg l−1).
76 Water Air Soil Pollut (2008) 187:65–80

4.4 Boron Isotope Ratio

The B/Cl ratio of waters furthest from the sea in the

detrital aquifer of the Lower Andarax ranges from
0.006 to 0.01 (B/Cl in seawater=0.0022; see Table 1),
while the value of δ11B varies from −11.3 to 44.7‰
(Fig. 10, Table 1). The highest B/Cl ratios and the
lowest δ11B correspond to the presence of silty–clays,
which favour “desorption”, where 10B is preferential-
ly given up, leading to a fall in δ11B (Vengosh et al.
1991a, Barth 2000; Williams et al. 2001). In the other
samples from the detrital Andarax aquifer, δ11B is
lower and may even be negative. Higher temper-
atures are registered at these points because of a
significant geothermal anomaly, close to the Sierra
Alhamilla Spa.
Along the coast of the Andarax delta, the influence
Fig. 8 Plot of Cl vs Sr (in meq l−1). Two lines are shown
of marine intrusion is clear and both the B/Cl ratio
representing the fit of the data in the areas of Castell de Ferro
(discontinuous line) and detrital aquifer in the Lower Andarax and the isotope ratio are close to that of seawater
(solid line). Key: Lower Andarax (1: detrital aquifer, 2: deep (Fig. 10b). Samples 8 and 11, which correspond to
aquifer, 3: Alhamilla spa, 4: spring in the Tabernas rambla); seawater taken from piezometers below the fresh
Campo de Dalías (5: Aguadulce, 6: Balerma, 7: Balanegra);
water – seawater interface, yield δ11B in the order
Castell de Ferro (8) and Sorbas gypsums (9)
of 35–37‰, which are close to that of seawater
The carbonate rocks can also be a significant source (δ11B +39‰; see Table 1). Samples taken from
of strontium, since this element can be incorporated piezometers 10 and 13, which are mixed with fresh
into the carbonates, mainly as aragonite. The concen- water in small proportions, give values of 42 to 44‰.
tration of Sr in aragonite is in the order of 8,000–
1,000 mg l−1, whilst in calcite it is 280–700 mg l−1
and in dolomites, 100–300 mg l−1 (Arad et al. 1986).
The incongruent dissolution of aragonite and the sub-
sequent precipitation of calcite in which Sr does not
tend to replace Ca in the matrix, means that the con-
centration of Sr in solution increases (Plummer et al.
1978). In fact, the elevated Sr/Ca ratio is attributable
to advanced states of calcite precipitation and may
be used as an indicator of residence time. In turn,
secondary dolomitisation leads to differential enrich-
ment in Sr (Kastner et al. 1990).
Water samples from the Balanegra carbonate aqui-
fer, in the Campo de Dalías, yield the highest Sr/Ca
ratios (Fig. 9), and this may be due to a superposition
of incongruent aragonite dissolution and calcite and/
or dolomite precipitation, mentioned above, favoured
by a long residence time (Molina et al. 2002). All the
samples are saturated in calcite and dolomite, with the
highest saturation values being SIcal =0.75 and SIdol = Fig. 9 Plot of SO4 vs Sr/Ca (in meq l−1). Key: Lower Andarax
(1: detrital aquifer, 2: deep aquifer 3: Alhamilla spa, 4: spring in
1.7, respectively. The elevated temperatures (between
the Tabernas rambla); Campo de Dalías (5: Aguadulce, 6:
32 and 38°C at these points) also favours these Balerma, 7: Balanegra); Castell de Ferro (8) and Sorbas
processes. gypsums (9)
Water Air Soil Pollut (2008) 187:65–80
Fig. 10 Plot of a Cl vs.
δ11B (‰) and b B/Cl vs.
δ11B (‰). Two lines are
shown representing the fit
of the data in the areas
of Castell de Ferro
(discontinuous line) and
detrital aquifer in the Lower
Andarax (solid line). Key:
Lower Andarax (1: detrital
aquifer, 2: deep aquifer 3:
Alhamilla spa, 4: spring in
the Tabernas rambla); Cam-
po de Dalías (5: Aguadulce,
6: Balerma, 7: Balanegra);
Castell de Ferro (8) and
Sorbas gypsums (9)
This indicates differential enrichment has taken place
due to the adsorption of boron into the aquifer matrix
and the consequent fall in the B/Cl ratio (0.0014–
0.0019). The process is not evident in sample 7,
perhaps due its proximity to the coast and the short
trajectory of the mixing water. In the piezometers
with the least saline water (9 and 12), δ11B falls
between +11 and +26‰, and the B/Cl ratio (0.0031–
0.0098) is higher than that of seawater (0.0022). This
is also explained by the influence of lutites that favour
“desorption”, and act to decrease δ11B and increase
the B/Cl ratio. The influence of mixing with waste-
waters can also be added to the list: these are used for
irrigation throughout the delta and their δ11B is lower.
The saline spring in the Tabernas rambla gives a
B/Cl ratio of 0.025, with elevated Cl and SO4 con-
centrations. The value of δ11B (+10.8‰) is quite low
considering the spring’s association with marine evap-
orites. It is believed that mobilisation of boron fixed
in the abundant clay of the Miocene sediments leads
to an increase in the B/Cl ratio and a fall in δ11B.
The waters of Sierra Alhamilla Spa and Deep
Aquifer of Lower Andarax yield elevated B/Cl ratios
of 0.011 and 0.056, respectively and negative δ11B
of −8.1 and −16.7‰, both in sharp contrast to other
sampling points. These data support the hypothesis
that the boron does not originate solely from the ma-
rine evaporites, but is probably due to mobilization of
boron favoured by the elevated temperatures, which
cause the values of δ11B to decrease (Oi et al. 1996;
Vengosh et al. 2002).
The isotope ratio for samples taken from the Sorbas
depression (+17.5 to +34‰) are lower than expected
77
for an aquifer consisting of gypsums of marine origin.
The lowest values of δ11B point to the existence of a
further process that decreases δ11B, probably related
to adsorption in clayey intercalations present in the
gypsum (Pennisi et al. 2006a, b).
In the aquifer of Castell de Ferro the boron comes
almost exclusively from a marine source and, in fact, the
B/Cl ratio is very similar to that of seawater. The δ11B
falls between +33.4 and +40.2‰, including the diluted
mixing waters, where the values can even slightly ex-
ceed that of seawater. This could be due to adsorption
of boron in the clayey matrix of the aquifer. The only
sample not influenced by seawater yielded a δ11B
of +14.6‰. This may indicate contamination of the
groundwater due to wastewaters seepage that have a
high B/Cl ratio and a possible anthropogenic isotopic
indicator, which reduces the δ11B (Vengosh et al.
1994a; Leenhouts et al. 1998).
In the Campo of Dalías a wide range of values of
δ11B is recorded. In the Aguadulce unit, δ11B falls
between −0.4 and +7.4‰, suggesting a non-marine
origin – the waters here come from carbonate rocks.
Contamination by wastewater is not suspected in this
case because the boron concentrations are very low
(0.01 a 0.03 meq l−1). In the Balerma-Las Marinas
unit δ11B ranges between +25.6 and +31.6‰. This
unit seems to be affected by mobilization of synsedi-
mentary marine brines that saturate the basal aquifer
and have been remobilised by the intensive pumping.
A hypothesis of present-day marine intrusion in not
consistent since there is no land–sea gradient inversion,
nor is there hydraulic continuity between the Pliocene
calcarenites and the sea. In the Balanegra unit there is a
78
wider range of variation (+8.2 a 36.1‰). The boron
here may be a result of inputs from the carbonate strata
itself, facilitated by the high base temperatures.
5 Conclusions
The δ11B provides a solid discriminatory tool of the
hydrogeochemical processes at work in complex
coastal aquifers. The efficiency of this tool markedly
increases when it is used alongside other major
components (chlorides, sulphates, sodium, calcium,
magnesium or their interrelationships) and minor con-
stituents (bromides and strontium, for example).
Nevertheless, to interpret it properly, various factors
need to be considered. In coastal areas, the presence
of clayey deposits is significant, and these affect
the fractionation of B isotopes due to adsorption–
desorption. This can change the value of δ11B in
either direction, depending on which process is pre-
dominant. The presence of wastewaters can also be
significant and these always reduce the values of
δ11B. The influence of geothermal anomalies can also
bring about a decrease in δ11B, though their effect in
coastal areas tends to be limited.
Br concentration and SO4/Cl and Cl/Br ratios are
shown to be good indicators of intrusion in the Castell
de Ferro aquifer and in the Andarax delta, where their
values are close to that of seawater (0.1 and 655,
respectively) for the most saline samples. Likewise,
the boron isotope ratio (δ11B) is in the order of + 37
a +39‰, close to the value for seawater. In the mixing
waters containing a high proportion of seawater, the
ratio is higher (+44.7‰ in Andarax and +40.2‰ in
Castell de Ferro), which is probably due to boron ad-
sorption, though the concentration of boron is slightly
less than that of seawater.
The isotope ratio in the inland part of the detrital
Andarax aquifer is unaffected by marine intrusion,
and takes values of between −11.3 and +14.6‰. The
negative values could be the result of a thermal
influence, since the deep Andarax aquifer (−16.7‰)
and the thermal spring at Alhamilla spa (−8.1‰) give
negative values. In addition, at some points in the
detrital aquifer the δ11B is close to zero and their
temperature is slightly elevated (24.6°C). These points
are in a zone where there is a significant thermal anom-
aly, probably due to the intense fracturing (Sánchez
Water Air Soil Pollut (2008) 187:65–80
Martos 1997). Here, it is clear that the origin of boron
must be linked to sulphate inputs (SO4/Cl exceeds 1)
from the Miocene gypsum deposits, represented by the
spring in the Rambla of Tabernas (5.4 mg l−1 of B).
In the gypsum aquifer of Sorbas, boron concentra-
tion is appreciably lower (between 0.1 and 0.4 mg l−1),
while strontium concentration is between 2.7 and
12.5 mg l−1. Given that boron solubility is directly
related to temperature, these differences could be
because the thermalism in the deep system of the
Andarax (34.8°C in the deep aquifer and 51.5°C in
Sierra Alhamilla) favours boron mobilization, even
from the associated metapelitic deposits, while in the
Sorbas gypsums (mean temperature of 20°C) this
effect is more limited. In any case, the boron isotope
ratio in the Sorbas gypsums is +17.5 a +33.8‰.
In the Campo de Dalías, the part of the Aguadulce
unit considered in this study corresponds to an area
unaffected by salinisation, as demonstrated by the
very low chloride concentrations (<6 meq l−1), bo-
ron (0.01–0.03 meq l−1) and strontium (0.008–
0.017 meq l−1), a Cl/Br ratio of more than 1000
and a SO4/Cl ratio of up to 0.6. The boron isotope
ratio is between −0.4 and +7.4‰, which suggests
that the boron is due to impurities in the Gádor car-
bonates. The Balanegra unit exhibits moderate ther-
malism and an elevated Sr/Ca ratio (up to 0.02) that
could indicate a long residence time. The SO4/Cl
ratio (0.05–0.2) and the B concentration (0.15–0.38)
are relatively low, while values of δ11B are clearly
higher (8.2–+36.14‰) than in the Aguadulce unit.
This supports the hypothesis that the boron comes
from the carbonate rocks themselves. The difference
in the boron isotope content between these two units
must be caused by the different composition of the
carbonate rocks (the calcoschists intercalations are
more abundant in the Balanegra unit), as well as
through the influence of temperature, all linked to
the longer residence time of the groundwater in this
unit. Datings undertaken in both units identify rapid
preferential flows in the Aguadulce unit (Molina et
al. 2002). In the calcodetrital aquifer of the Balerma-
Las Marinas unit, a historic marine influence can be
appreciated, giving rise to chloride concentrations of
around 14–26 meq l−1 and Cl/Br ratio of 550–650.
The SO4/Cl ratio of 0.4–0.5, much higher than that
of seawater (0.1); boron and strontium are also
relatively high in concentration (0.5–0.8 mg l−1 and
2.2–11–6 mg l−1, respectively).
Water Air Soil Pollut (2008) 187:65–80
Acknowledgements This article was written within the frame-
work of project HID99-0597-CO2, financed by the Spanish
CICYT Interministerial Commission of Science and Technology.
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