Journal of Hydrology: Regional Studies 12 (2017) 69–87

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Journal of Hydrology: Regional Studies

journal homepage: www.elsevier.com/locate/ejrh

Groundwater salinization in Graciosa and Pico islands (Azores

T
archipelago, Portugal): processes and impacts
⁎
J.V. Cruz , C. Andrade
IVAR − Research Institute for Volcanology and Hazards Assessment, Department of Geosciences, University of Azores, Apartado 1422, 9501-801
Ponta Delgada, Portugal

AR TI CLE I NF O AB S T R A CT

Key-words: Study region: Graciosa and Pico islands, Azores, Portugal

Groundwater salinization Study focus: Seawater intrusion is a main driver of groundwater salinization in the Azores
Hydrogeochemistry archipelago. In order to characterize the associated geochemical processes through major-ion and
Water quality determination of stable (δ18O; δ2H; δ11B) and radiogenic isotopic ratios (δ87Sr) a total of 46 wells
Volcanic islands
were sampled in Graciosa and Pico, as well as 51 wells from other islands.
Azores
New hydrological insights for the region: The overall groundwater chemistry is mainly controlled
by Cl and Na, which account respectively for 10.4%–46.9% and 16%–39.7% of the relative
major-ion content. Mean electrical conductivity (EC) in Graciosa is in the range 308 − 3462 μS/
cm, while hand-dug wells in Pico are highly mineralized (1758–9732 μS/cm). Drilled wells in
Pico are in the range of 186 μS/cm to 5625 μS/cm. Besides mixture with seawater, groundwater
chemistry is also influenced by dissolution of silicate minerals which also contributes to water
composition. Moreover, 18O and 2H stable isotope data show that a few samples depict an
evaporative effect, resulting in heavier isotopic compositions besides mixing with a marine
source. About 70% of the wells in Graciosa and Pico exceed the 200 mg Cl/L and the EC
Portuguese reference values, severely constraining water supply. The impact on water quality is
also shown by exceedances of the groundwater threshold values derived for the Azores River
Basin District (89%).

1. Introduction

Seawater intrusion is a main driver of groundwater salinization, corresponding to a widespread mechanism that causes the
degradation of water quality all over the main continents (Barlow and Reichard 2010; Bocanegra et al., 2010, Custodio 2010; Steyl
and Dennis 2010; Werner 2010). Nowadays, the litorization process is depicted by an average population density in the near coastal-
area three times higher than the global average (Small and Nicholls 2003). The coupled effect of human population growth and
climate change over the coastal zone, mainly due to sea-level rise, will be responsible for significant and widespread impacts on
groundwater resources in these areas (Green et al., 2011; Ferguson and Gleeson 2012; Rotzoll and Fletcher 2013; Taylor et al., 2013).
Coastal aquifer salinization can also be caused by very large storms (Anderson 2002; Anderson and Lauer 2008), and both the
increasing storm surge levels and the changing pattern of storminess are of concern in the coastal area in Portugal due to climate
change (Andrade et al., 2002).
Country scale case studies have been made worldwide, such as for Brazil (Cary et al., 2015), Spain (Pulido-Leboeuf, 2004), Italy
(Capaccioni et al., 2005), France (Montety et al., 2008), Greece (Duriez et al., 2008), Oman (Shammas and Jacks, 2007), and Korea

⁎
Corresponding author.
E-mail address: jose.vm.cruz@uac.pt (J.V. Cruz).

http://dx.doi.org/10.1016/j.ejrh.2017.04.003
Received 16 September 2016; Received in revised form 5 April 2017; Accepted 7 April 2017
Available online 26 April 2017
2214-5818/ © 2017 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/BY-NC-ND/4.0/).
J.V. Cruz, C. Andrade Journal of Hydrology: Regional Studies 12 (2017) 69–87

(Park et al., 2005). Several approaches were applied in order to characterize groundwater salinization due to mixing with seawater,
from geophysical and coupled geophysical/geochemical tools (Foyle et al., 2002; Cimino et al., 2008; Samsudin et al., 2008) to
geochemical methods (Alcalá and Custodio, 2008; Lu et al., 2008). Recently, an additional seawater intrusion classification scheme
has been proposed (Werner, 2017). Numerical modelling approaches (Gingerich and Voss, 2005) have also being applied, as well as
innovative data handling methodologies (Barzegar and Moghaddam, 2016), but future challenges are still to be addressed by research
through process knowledge, observation and modelling, as well as by application to field-scale occurrences (Werner et al., 2013).
Among geochemical methods, the determination of stable and radiogenic isotopes content has been used as a tool to characterize
salinization processes due to seawater intrusion (Gonfiantini and Araguás Araguás, 1988; Araguás Araguás, 2003; Clark, 2015).
Oxygen and hydrogen isotopes in groundwater can be considered as tracers of the water itself and are useful to characterize mixing
processes as isotopic compositions of mixtures are intermediate between end-members (Kendall and Doctor, 2005). Numerous studies
published in the international literature have shown the usefulness of the pair 18O-2H for the identification of mixing trends
(Jorgensen and Banoeng-Yakubo, 2001; Faye et al., 2005; Montety et al., 2008; Anders et al., 2013).
Besides oxygen and hydrogen other stable isotopes such as boron have proven to be useful in order to characterize the origin of
salinity in groundwater (Barth, 1998; Pennisi et al., 2006; Forcada and Morell, 2008; Morell et al., 2008b; Cary et al., 2013, 2015).
Boron content in groundwater increases as function of natural sources such as seawater, brines, geothermal fluids and evaporitic
rocks, as well as due to anthropogenic sources as wastewater discharges (Morell et al., 2008a). The ratio 11B/10B presents a large
range of values according to the geological and human environment (Vengosh et al., 1991, 1994; Barth, 1993; Basset et al., 1995;
Hogan and Blum, 2003; Williams and Hervig, 2004). Boron isotopic fractionation is favoured by the large relative mass difference
between 10B and 11B and the geochemical reactivity of the solute itself (Xiao et al., 2013), and is driven by reactions between the
dissolved boron and the aquifer matrix (Gonfiantini and Pennisi, 2006).
Non-stable radiogenic isotopes as 87Sr/86Sr have also been widely used in order to constrain salinization processes (Jorgensen and
Banoeng-Yakubo, 2001; Martin and Moore, 2008; Anders et al., 2013; Khaska et al., 2013; Cary et al., 2015), and detailed reviews of
the usefulness of the 87Sr/86Sr isotopic ratio as tracer in geochemical processes are provided in the literature (Blum and Erel, 2005;
Shand et al., 2009). The 87Sr/86Sr ratio of dissolved Sr in groundwater is controlled by the atmospheric input and by water-rock
interaction, namely through the mineralogical composition of the aquifer matrix, mineral dissolution and the residence time (Shand
et al., 2009).
As well as for continental areas, salinization of groundwater has been the focus of research in volcanic islands, determining
several causes from the coupled airborne sea salt deposition, rock weathering and agricultural return flows (Cruz-Fuentes et al., 2014)
to mixing with seawater (Kim et al., 2003; Herrera and Custodio, 2008). Application of isotopic tools was also used in order to
characterize the origin of groundwater salinity in islands (Cruz and Silva 2000; Kim et al., 2003; Condesso de Melo et al., 2008;
Herrera and Custodio, 2008; Heilweil et al., 2009; Carreira et al., 2010; Wu et al., 2016).
Groundwater salinization due to seawater intrusion in the Azores archipelago has been already reported, causing deterioration of
water quality, due to failure to comply with quality regulations, constraining water supply and carrying economical losses to society
in a few islands such as Graciosa and Pico (Cruz and Silva, 2000, 2001; Cruz et al., 2010a, 2011). Salinization also influences mineral
water composition in the coastal aquifers, also constraining the exploitation of these resources (Cruz and França, 2006; Cruz et al.,
2010b). Seawater intrusion is favoured by the hydrogeological characteristics, such as the presence of thin freshwater lenses
overlying salt water within highly permeable coastal aquifers (Cruz et al., 2011).
The Azores Archipelago is made of nine volcanic islands, located in the North Atlantic between latitudes 37° and 40° N and
longitudes 25° and 31°W, spread along a NW-SE trending strip of about 600 km (Fig. E1 –electronic supplementary material). The
islands of Graciosa and Pico are located geographically in the so-called Central Group.
Graciosa island has a total area equal to 60.7 km2, being the second smallest island in the archipelago, and 4344 inhabitants (71.6
inhabitants/km2; SREA, 2015). Water supply is totally dependent on groundwater resources and the total abstracted volume is equal
to 1140 × 103 m3/a (AHA/DRA, 2015). Human supply explains about 68.2% of the total water demand in the island (778 × 103 m3/
a), while agriculture and cattle breeding equals to 18.3% of the total.
Pico has a total area equal to 444.8 km2, being the second largest island in the archipelago, and 13,771 inhabitants (31
inhabitants/km2; SREA, 2015). Supply water abstraction equals 1910 × 103 m3/a, being 91.1% of groundwater origin
(1740 × 103 m3/a) and 8.9% of surface water origin (170 × 103 m3/a), the latter through the exploitation of a lake. Total water
demand was estimated as 1184 × 103 m3/a, whit urban supply (76.3%) and agriculture and cattle breeding (29.7%) as the most
demanding usages (AHA/DRA, 2015).
The main objective of the present paper is to characterize the geochemical processes associated to groundwater salinization in
both Graciosa and Pico islands. Therefore, through the application of hydrogeochemical tools, as the determination of major-ion and
isotopic content, the paper intends to (1) establish the origin of the salinization process, (2) characterize groundwater chemistry and
evaluate the impact of the salinization process on the water quality and, (3) compare data in Pico and Graciosa with groundwater
samples collected during the present study in all drilled wells spread along the other islands of the Azores.

2. Geological and hydrogeological setting

2.1. Geological framework

All of the islands in the archipelago are of volcanic origin, and only in Santa Maria, the easternmost island of the Azores,
sedimentary units are interbedded in the volcanic succession. The oldest volcanic activity in the archipelago is aged about 8.12 Ma

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J.V. Cruz, C. Andrade Journal of Hydrology: Regional Studies 12 (2017) 69–87

(Abdel-Monen et al., 1975). Since the archipelago settlement, that took place in the 15th century, about 30 eruptions have occurred
(Pacheco et al., 2013).
The edification of Pico island was mainly due to Hawaiian and Strombolian type volcanic activity, resulting in pahoehoe and aa
lava flows, of basaltic nature, as well as scoria and spatter cones, often spread along tectonic lineaments. The western region of the
island is dominated by a central volcano (Pico Mountain), about 16 km of maximum diameter and reaching a maximum altitude of
2351 m above seawater level, which corresponds to the so-called Montanha Volcanic Complex. The eastern area corresponds to the
so-called São Roque-Piedade Volcanic Complex, corresponding to a plateau which altitude decreases gradually toward east, made by
eruptive fissures and about 170 spatter and scoria cones spread along WNW-ESE structures, and dated from about 230,000 years ago
(Cruz 1997; Nunes 1999; França, 2000).
The oldest volcanic unit in Pico corresponds to the so-called Topo-Lajes Volcanic Complex, that corresponds to a shield volcano
which outcrops in the south coast of the island, dated from about 300,000 years ago (Cruz 1997; Nunes 1999; França, 2000).
The SE region in Graciosa island is also dominated by an active central volcano, with a summit crater at a maximum altitude of
402 m above sea level, contrasting with the NW plateau, mainly made by Strombolian-type eruptions that originated lava flows and
basaltic pyroclastic deposits (Gaspar, 1996).
Three main volcanic units have been identified over Graciosa (Gaspar, 1996), being the oldest one the so-called Serra das Fontes
Volcanic Complex, dated from 620 000 ± 120 000 years ago (Féraud et al., 1980), corresponding to a succession of subaerial
basaltic lava flows. The Serra Branca Volcanic Complex, dated from 350 000 ± 40 000 years ago (Féraud et al., 1980) where evolved
volcanics as trachytic lava flows and fall and flux pyroclastic deposits dominate. The most recent unit corresponds to the so-called
Vitória − Vulcão Central Volcanic Complex, presenting a wide range of eruptive styles.

2.2. Hydrogeological framework

Groundwater in the Azores occurs in two major aquifer systems (Cruz, 2003, 2004): (1) the basal aquifer system, corresponding to
fresh-water lenses floating on underlying salt water, usually presenting a very low hydraulic gradient and (2) perched-water bodies.
The basal aquifer system is located in the coastal area, and in islands such as Graciosa and Pico is the main source for the water
supply. It is possible to suggest that a hydraulic liaison occurs with the perched-water bodies at altitude, with an eventual release of
water to the basal unit.
Perched-water bodies correspond to pervious units, with impermeable to very low permeable layers at the bottom. Whenever
topographic conditions are favorable, they are drained out by springs spread in the volcano slopes. Therefore, these aquifers at
altitude correspond to unconfined or leaky layers, the latter likely to lose water through aquitards bounding them in the bottom. The
existence of dike-impounded aquifers is not supported by evidence, as in the Hawaiian conceptual model for volcanic islands
(Peterson 1972, 1993). Nevertheless, and considering the present information, such hypothesis is also not excluded (Cruz and Silva
2001).
On Graciosa island, only 28 springs and 21 drilled wells were identified. The spring discharge is usually low (annual mean in the
range of 0.37–0.80 L/s), with a sharp difference between winter and summer periods. On Pico island, the number of springs is even
lower (9), besides a total of 23 drilled wells. In both islands the higher specific well capacity and transmissivity values are associated
to basaltic lava flows, which generally are thin and fractured with frequently interbedded clinker layers, being generally higher than
the ones for the other islands in the archipelago (Table 1). Groundwater resources are estimated at 15 Mm3/a in Graciosa, with
recharge rates in the range between 8.5% and 36.2% for the six groundwater bodies in the island. In Pico, groundwater resources are
estimated as 582 Mm3/a, with recharge rates in the range of 18.5%-62.1% for the six groundwater bodies on the island.
According to the EU Water-Framework Directive, 16.7% and 33.3% of the groundwater bodies were considered to be at poor
chemical status respectively on Graciosa and Pico islands, in both cases due to exceedances regarding chloride content as well as
electrical conductivity, being attributed to a mixture process between fresh water and seawater (AHA/DRA 2015).

3. Methodology

Groundwater samples were bimonthly collected in drilled wells (dw) and hand-dug wells (hdw) in both Graciosa and Pico islands
during year 2014 (Fig. 1). In total, 8 drilled wells and 3 hand-dug wells were sampled on Graciosa island and 19 drilled wells and 16
hand-dug coastal wells on Pico island. In order to further constrain data interpretation a total of 51 drilled wells were also sampled

Table 1
Range for specific well capacity and transmissivity values for drilled wells in Graciosa and Pico islands and comparison to the archipelago (data from Cruz 2004 and
AHA/DRA, 2015).

Island Specific well capacity (L/s.m) Transmissivity (m2/s)

Min. Max. Median Min. Max. Median

−3 −1
Graciosa 1.36 266.7 142.9 1.7 × 10 3.25 × 10 1.02 × 10−1
Pico 6.25 250 61.2 9.4 × 10−3 3.05 × 10−1 1.11 × 10−1
Azores 1.4 × 10−2 266.7 21.9 2.65 × 10−6 3.25 × 10−1 1.62 × 10−2

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J.V. Cruz, C. Andrade Journal of Hydrology: Regional Studies 12 (2017) 69–87

Fig. 1. Location of the sampling wells in Graciosa (A) and Pico (B) islands (see Table 2 for full reference).

once, namely on islands Santa Maria (9 dw), São Miguel (16 dw), Terceira (15 dw), Faial (9 dw) and São Jorge (2 dw) (Fig. E2 −
electronic supplementary material).
Because the water table in the basal aquifer systems is generally close to sea level, well depths depict in the Azores archipelago a
close relationship with surface elevation and distance from the coast (Cruz and Silva, 2000, 2001; Cruz et al., 2011). The average
depth of the studied drilled wells on Pico island is 123.7 m (25–284 m). The average distance to the coast is equal to 1258 m (300 −
5825 m) and the average surface elevation ranges from 17 m to 192.2 m (mean = 119.4 m). In Graciosa island the average depth is
equal to 123.7 m (25–284 m), the average distance to the coast is 2236 m (1575 − 3300 m) and the average surface elevation ranges
from 65 m to 109.6 m (mean = 89.3 m).
Samples were taken after purging wells for a period of time and measurements of temperature, pH and electrical conductivity
(EC), as well as alkalinity titration, were made in the field with specific portable equipment immediately after sampling. Alkalinity
titration was made by adding H2SO4 (0.05 M) until a pH end-point of 4.45 and after the titrant volume is multiplied by 50, following
APHA-AWWA-WPCF (1985).
Cationic analyses were performed using atomic absorption spectrometry while ion chromatography was used for anionic
determination, in both cases after sample filtration in the field with 0.45 μm filters. Samples for atomic absorption analysis were
acidified with suprapur® nitric acid immediately after sampling. Silica was analysed by spectrophotometry, using the silicomolybdic
method.
Determination of δ18O and δ2H over 97 samples collected in Graciosa, Pico, Santa Maria, São Miguel, Terceira, Faial and São
Jorge islands was made by mass spectrometry in the Doñana Biological Station Stable Isotope Laboratory (Spain). δ87Sr and δ11B
measurements over 12 samples from Graciosa and Pico islands were carried out in the ALS Environmental laboratories (ALS

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 Table 2
Groundwater chemical data descriptive statistics for main variables (temperature, pH, electrical conductivity) and major-ion, SiO2, δ18O, δ2H, δ87Sr and δ11B content. Island reference: GRA − Graciosa; PIC − Pico. The typology
of the wells is referred in the name column as dw (drilled wells) and hdw (hand-dug wells).

Island Refª Name Statistics T pH Cond. HCO3 Cl SO4 Na Mg K Ca SiO2 Sr B δ18O (‰) δ2H (‰) δ87Sr δ11B (‰)
J.V. Cruz, C. Andrade

°C μS/cm mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L μg/L μg/L

GRA 1 dw_SG1 Minimum 16.40 6.26 743 169.60 162.58 20.19 81.86 9.11 5.24 3.22 46.17 n.d. n.d. -4.62 -23.00 n.d. n.d.
Maximum 18.70 6.90 1374 295.85 284.00 48.04 135.72 83.69 8.83 66.67 57.04
Mean 18.08 6.59 1205 257.42 244.31 30.89 116.57 62.44 7.11 39.33 50.48
Median 18.35 6.56 1285 275.72 258.38 29.24 124.49 72.37 7.04 39.78 48.96
2 dw_JK5 Minimum 15.30 6.33 934 83.57 201.14 23.69 143.77 5.01 6.50 13.29 26.64 n.d. n.d. -4.46 -22.60 n.d. n.d.
Maximum 19.90 7.20 1423 122.00 418.90 49.95 167.32 34.56 14.76 33.89 39.45
Mean 17.92 6.97 1079 99.33 257.85 32.66 153.24 16.58 8.69 21.09 32.20
Median 17.90 7.10 1021 96.08 232.13 29.19 152.47 13.88 7.47 18.69 31.62
3 dw_JK1 Minimum 19.00 6.47 1378 74.42 308.22 40.63 219.61 36.07 9.48 18.41 33.86 n.d. n.d. -4.51 -22.60 n.d. n.d.
Maximum 19.80 7.09 1537 98.80 368.43 50.07 231.18 52.49 10.62 26.71 36.47
Mean 19.50 6.75 1477 90.27 346.65 44.02 227.31 44.75 10.22 23.25 34.84
Median 19.70 6.69 1515 97.60 363.30 41.35 231.15 45.70 10.56 24.62 34.18
4 dw_ITC2 Minimum 24.20 6.62 3250 74.42 945.84 73.90 386.55 83.30 17.30 92.13 19.79 1090.00 135.00 -4.14 -21.50 0.705105 39.20
Maximum 26.70 7.61 4320 82.35 1133.27 108.67 518.20 197.55 30.18 146.40 33.81
Mean 25.28 7.21 3642 78.18 1032.10 91.67 440.81 145.61 23.37 120.57 24.89
Median 25.20 7.17 3545 78.39 1023.29 95.00 423.44 153.31 22.34 126.23 24.48
5 dw_AC3 Minimum 21.50 6.19 1517 86.60 367.72 36.66 121.24 48.39 7.33 49.92 27.21 472.00 80.60 1.52 -7.90 0.705131 39.10
Maximum 26.10 7.51 1850 107.40 483.31 53.29 224.25 93.87 11.52 68.07 40.44
Mean 24.13 7.10 1652 96.28 427.02 44.78 188.72 78.22 9.25 57.66 32.85
Median 24.55 7.30 1616 94.55 422.12 44.69 195.76 81.69 8.97 57.85 32.75

73
6 dw_JK4 Minimum 21.20 6.42 1740 95.80 404.65 40.49 210.52 69.23 7.34 56.36 27.48 830.00 103.00 -4.40 -22.70 0.705217 39.90
Maximum 27.30 7.47 2400 119.56 728.21 76.48 265.05 113.66 14.74 127.34 37.40
Mean 25.82 7.06 2202 106.14 572.77 56.89 244.45 99.23 11.02 91.86 32.00
Median 26.75 7.14 2270 103.70 605.02 57.02 248.45 106.64 10.76 85.88 32.62
GRA 7 dw_ITC1 Minimum 23.50 6.64 1095 29.89 229.80 23.06 105.97 35.16 6.14 31.19 27.90 265.00 64.70 -4.45 -22.60 0.705064 39.10
Maximum 24.60 7.54 1110 109.80 273.06 35.54 129.62 58.04 7.85 55.34 44.21
Mean 24.26 7.12 1104 80.27 257.74 26.43 120.98 50.16 6.83 41.51 33.43
Median 24.40 7.19 1108 86.01 265.76 23.42 123.00 56.14 6.19 42.35 32.35
8 dw_AC2 Minimum 20.50 6.65 1507 109.19 307.61 41.31 219.57 32.77 10.96 23.80 28.84 n.d. n.d. -1.61 -16.20 n.d. n.d.
Maximum 21.40 7.05 1625 156.77 409.50 53.79 231.87 54.52 14.75 38.14 44.69
Mean 21.00 6.84 1585 131.15 359.03 46.19 225.55 41.30 13.23 32.57 35.60
Median 21.10 6.82 1624 127.49 359.99 43.47 225.22 36.61 13.99 35.78 33.27
9 hdw_Courelas Minimum 17.80 6.85 285 94.60 31.80 8.90 26.20 7.22 10.35 13.77 5.24 n.d. n.d. -4.37 -22.60 n.d. n.d.
Maximum 20.80 7.54 333 104.90 65.26 14.41 39.74 10.13 12.88 20.92 26.83
Mean 19.30 7.11 308 100.14 47.15 11.81 31.07 8.79 11.83 16.95 17.02
Median 19.40 7.06 306 100.94 45.27 11.50 29.89 8.99 12.10 16.46 17.75
10 hdw_Ratinho Minimum 18.00 6.42 492 86.01 64.88 13.01 37.48 12.06 3.72 21.54 30.87 132.00 116.00 -4.32 -22.50 0.705155 27.60
Maximum 21.40 6.95 526 98.20 85.56 19.69 55.52 16.58 5.39 26.80 43.58
Mean 19.18 6.70 509 93.84 75.21 15.79 49.87 15.07 4.64 23.85 36.34
Median 19.00 6.75 512 94.55 75.20 15.07 52.25 15.72 4.65 24.25 35.86
11 hdw_Novo Minimum 17.30 6.22 424 122.60 49.42 7.31 30.90 14.06 13.13 22.27 12.42 n.d. n.d. -1.71 -15.20 n.d. n.d.
Maximum 19.80 7.22 465 158.00 65.09 11.05 32.41 16.36 22.46 36.49 26.73
Mean 18.75 6.78 446 140.60 57.18 9.28 31.34 14.96 16.03 28.21 16.72
Median 19.15 6.74 447 140.59 56.62 9.30 31.22 14.88 14.22 26.27 15.17
PIC 12 dw_JK1 (SRP) Minimum 13.50 6.57 996 181.78 160.41 19.42 127.28 25.93 11.88 18.20 47.51 n.d. n.d. -4.75 -23.8 n.d. n.d.
Maximum 15.40 7.12 1075 218.38 217.26 27.86 154.18 27.23 13.39 28.35 58.45
Mean 14.42 6.80 1037 202.00 194.65 23.94 145.74 26.54 12.56 21.12 50.14
(continued on next page)
Journal of Hydrology: Regional Studies 12 (2017) 69–87
 Table 2 (continued)

Island Refª Name Statistics T pH Cond. HCO3 Cl SO4 Na Mg K Ca SiO2 Sr B δ18O (‰) δ2H (‰) δ87Sr δ11B (‰)

°C μS/cm mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L μg/L μg/L
J.V. Cruz, C. Andrade

Median 14.40 6.77 1032 205.86 203.95 24.08 147.99 26.49 12.50 18.71 48.33
13 dw_JK2 (SRP) Minimum 13.90 6.15 838 129.30 145.95 18.34 98.20 17.45 8.66 11.99 40.54 n.d. n.d. -4.7 -23.6 n.d. n.d.
Maximum 16.50 7.43 905 172.60 200.22 25.94 128.94 19.73 9.97 18.41 53.15
Mean 15.32 6.77 876 144.36 176.65 23.07 117.26 17.96 9.41 14.50 42.91
Median 15.50 6.70 870 140.61 183.24 24.31 124.55 17.63 9.59 13.27 40.95
14 dw_Ribeiras (SRP) Minimum 15.60 7.08 140 43.90 20.26 3.23 12.91 4.31 1.30 8.24 28.64 n.d. n.d. -1.1 -14.2 n.d. n.d.
Maximum 17.10 7.99 337 51.85 69.09 8.65 37.62 7.17 2.65 14.12 37.86
Mean 16.38 7.47 241 48.19 45.61 5.69 23.62 5.74 1.74 10.93 30.99
Median 16.30 7.42 246 48.50 44.30 5.70 23.13 5.82 1.67 10.70 29.85
PIC 15 dw_Rossas (SRP) Minimum 15.10 6.33 430 41.48 82.77 10.00 20.24 5.74 2.40 4.27 23.33 56.20 40.70 -4.27 -19.9 0.706222 37.70
Maximum 15.80 7.37 526 48.80 128.51 14.80 62.28 7.13 3.62 9.00 35.65
Mean 15.38 6.94 473 45.45 101.24 12.41 51.13 6.32 3.28 6.34 26.59
Median 15.35 7.04 462 45.45 99.22 12.09 58.67 6.24 3.41 6.08 24.86
16 dw_JM_ (LP) Minimum 14.90 6.53 2100 358.68 434.77 60.52 188.74 65.54 13.94 33.04 41.91 n.d. n.d. -4.55 -21.8 n.d. n.d.
Maximum 16.40 7.47 2300 426.39 539.60 71.41 263.49 107.65 20.31 53.41 47.33
Mean 15.70 7.01 2192 396.86 472.24 64.76 236.03 88.45 16.09 44.80 44.03
Median 15.60 7.16 2190 389.18 453.61 62.31 260.14 93.10 15.86 43.10 43.45
17 dw_JR (LP) Minimum 15.30 5.93 926 103.09 176.49 24.42 93.65 26.60 7.55 11.73 33.77 114.00 62.30 -4.06 -18.1 0.706802 37.10
Maximum 17.20 7.44 1058 129.32 287.55 36.13 134.55 40.45 9.09 19.66 39.15
Mean 16.18 6.96 999 119.16 226.50 30.88 116.14 30.45 8.26 14.28 36.32
Median 16.20 7.16 994 120.50 227.88 31.05 118.96 29.00 8.24 12.93 36.27
18 dw_JK4 (LP) Minimum 16.20 5.89 2040 76.86 461.48 60.62 209.74 41.37 13.27 22.11 29.43 n.d. n.d. -3.97 -17.7 n.d. n.d.

74
Maximum 17.60 7.53 2130 154.90 631.90 84.03 313.54 51.92 16.53 26.75 45.29
Mean 16.92 6.83 2093 100.85 538.01 66.68 271.90 45.00 15.07 23.69 33.51
Median 16.70 6.96 2100 94.86 545.06 62.62 290.10 43.83 15.35 23.24 30.10
19 dw_JK3 (LP) Minimum 15.50 5.99 589 92.11 101.47 13.64 48.49 20.40 5.38 20.93 33.80 n.d. n.d. -3.99 -17.5 n.d. n.d.
Maximum 16.60 6.33 791 123.22 165.79 23.20 82.33 27.74 6.93 45.22 46.86
Mean 16.03 6.16 656 108.58 129.98 17.82 61.56 22.87 5.99 32.15 37.60
Median 16.05 6.16 634 107.97 132.77 17.53 60.98 22.17 5.90 34.21 35.64
20 dw_JK2 (LP) Minimum 14.80 6.15 1008 34.77 231.30 31.16 101.81 19.04 7.12 12.55 22.59 n.d. n.d. -4.11 -18.2 n.d. n.d.
Maximum 15.80 7.40 1091 51.24 286.84 37.94 187.28 20.63 8.17 17.92 27.52
Mean 15.15 6.62 1061 40.46 260.59 34.36 147.70 19.94 7.73 15.04 24.80
Median 15.10 6.61 1068 39.04 265.76 33.84 151.98 20.09 7.71 14.58 24.63
21 dw_JK1 (LP) Minimum 14.00 6.05 167 65.88 17.48 3.89 15.54 5.69 2.32 3.13 20.39 n.d. n.d. -4.32 -19.5 n.d. n.d.
Maximum 14.50 7.83 196 87.84 30.81 5.28 28.05 6.99 3.90 4.50 32.18
Mean 14.25 6.70 186 74.72 21.76 4.53 21.79 6.42 3.45 3.80 23.86
Median 14.30 6.47 188 73.20 20.38 4.42 22.71 6.45 3.75 3.70 22.30
22 dw_Miragaia (Mad) Minimum 13.00 6.14 422 189.70 26.51 4.78 37.29 16.42 8.05 13.36 51.05 n.d. n.d. -1.86 -17.7 n.d. n.d.
Maximum 14.70 6.83 440 218.99 37.01 6.77 50.31 19.09 20.94 17.75 55.48
Mean 13.52 6.42 428 205.47 32.56 5.91 45.41 17.86 10.71 14.85 52.58
Median 13.25 6.42 427 203.74 33.34 6.07 48.66 17.98 8.46 13.82 52.36
PIC 23 dw_JK1 (Mad) Minimum 13.60 6.09 1566 175.68 343.80 43.21 154.78 30.83 12.83 13.73 44.01 n.d. n.d. -2.48 -18.8 n.d. n.d.
Maximum 14.80 7.36 1620 244.61 356.82 51.87 246.01 41.33 15.53 21.18 49.93
Mean 14.07 6.95 1589 222.05 351.78 45.94 210.72 38.71 14.32 16.12 46.86
Median 13.80 7.02 1584 228.14 353.63 44.56 232.63 39.79 14.49 15.16 46.80
24 dw_AC1 (Mad) Minimum 13.70 6.38 896 146.40 155.78 22.14 105.29 21.41 9.19 7.73 35.97 n.d. n.d. -1.65 -16.8 n.d. n.d.
Maximum 14.60 7.56 1103 182.39 255.60 32.28 155.47 33.37 12.07 13.86 43.11
Mean 14.08 6.96 990 168.46 198.11 27.60 135.28 24.20 9.84 9.43 38.37
(continued on next page)
Journal of Hydrology: Regional Studies 12 (2017) 69–87
 Table 2 (continued)

Island Refª Name Statistics T pH Cond. HCO3 Cl SO4 Na Mg K Ca SiO2 Sr B δ18O (‰) δ2H (‰) δ87Sr δ11B (‰)

°C μS/cm mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L μg/L μg/L
J.V. Cruz, C. Andrade

Median 14.00 6.97 974 171.41 196.38 29.09 140.89 22.23 9.32 8.15 37.63
25 dw_ITC2 (Mad) Minimum 16.50 6.69 1892 459.33 358.19 56.84 272.03 45.71 18.40 14.40 35.79 n.d. n.d. -4.64 -22.4 n.d. n.d.
Maximum 17.20 7.85 3010 549.61 707.16 77.33 370.48 66.40 24.48 21.60 47.30
Mean 16.78 7.35 2225 512.90 459.05 65.70 316.76 52.67 20.33 17.21 39.19
Median 16.70 7.27 2135 524.60 424.31 64.56 320.37 52.10 19.85 15.60 37.11
26 dw_ITC7 (Mad) Minimum 13.60 6.87 199 61.00 34.60 4.64 28.37 4.29 3.46 2.92 33.71 n.d. n.d. -2.73 -18.2 n.d. n.d.
Maximum 15.10 8.63 281 143.96 162.88 8.55 158.34 4.91 4.79 5.31 46.11
Mean 14.42 7.80 344 90.18 76.33 6.69 67.26 4.67 4.14 3.72 37.00
Median 14.40 7.79 352 77.17 63.27 6.74 49.28 4.74 4.09 3.05 35.38
27 dw_ITC5 (Mad) Minimum 14.60 6.47 541 120.78 86.63 31.84 58.10 19.45 5.24 11.14 31.46 n.d. n.d. -4.66 -22.2 n.d. n.d.
Maximum 15.00 7.49 675 134.80 123.54 36.89 66.82 30.54 6.00 17.44 44.75
Mean 14.72 6.89 606 126.47 104.02 34.02 62.22 22.22 5.64 13.87 34.79
Median 14.60 6.86 607 125.05 104.01 33.32 61.93 21.07 5.64 12.60 32.92
28 dw_BSH1 (Mad) Minimum 14.00 6.43 934 117.10 163.42 45.55 90.84 27.63 7.27 17.90 33.97 n.d. n.d. -1.8 -16.5 n.d. n.d.
Maximum 15.30 7.56 1102 132.98 242.82 54.99 126.80 42.49 8.83 29.69 48.19
Mean 14.85 6.99 1002 123.52 203.30 50.45 110.15 31.96 7.83 21.59 38.44
Median 15.05 7.00 996 122.61 202.33 50.54 112.08 29.97 7.79 19.40 36.51
29 dw_BSH2 SM (Mad) Minimum 14.60 6.44 5260 56.73 1593.87 178.34 753.15 86.35 34.28 46.80 25.53 823.00 439.00 -1.17 -13.4 0.707754 37.80
Maximum 15.50 7.99 5890 78.69 1852.72 207.48 1014.40 127.80 43.30 82.35 39.64
Mean 15.13 7.12 5625 67.91 1722.28 190.56 891.16 106.77 39.60 64.74 32.37
Median 15.25 7.18 5650 67.71 1711.69 188.31 907.08 107.24 40.04 60.57 32.29
30 dw_BSH2 CB (Mad) Minimum 13.70 6.39 2225 221.43 555.64 74.52 265.38 34.68 13.88 17.35 39.61 254.00 191.00 -4.78 -23.9 0.706495 37.30

75
Maximum 15.10 7.69 2500 257.42 674.50 82.96 403.08 64.94 22.03 30.78 45.89
Mean 14.34 7.11 2339 240.08 606.18 79.47 352.06 42.95 16.88 22.97 41.38
Median 14.10 7.19 2360 240.32 597.61 79.31 353.61 38.08 15.88 20.28 40.09
PIC 31 hdw_Arcos Minimum 14.40 6.32 4440 65.88 1218.58 157.40 623.28 73.75 30.85 35.03 24.16 588.00 424.00 -4.28 -21.8 0.708755 38.40
Maximum 17.30 7.81 5420 163.48 1615.25 212.86 786.18 100.98 49.60 59.83 29.14
Mean 15.93 7.08 4928 87.43 1445.05 176.12 712.19 85.82 37.14 44.56 27.77
Median 16.10 7.12 5010 70.45 1470.58 170.99 701.28 83.08 34.97 38.26 28.42
32 hdw_Lajido Minimum 14.30 6.27 3760 133.60 1038.37 130.46 535.70 61.50 26.08 32.94 37.69 n.d. n.d. -4.39 -21.9 n.d. n.d.
Maximum 16.80 7.25 4370 168.36 1281.55 157.70 695.90 91.16 36.26 56.54 46.03
Mean 15.48 6.75 4073 151.49 1160.72 144.38 605.95 77.62 32.38 43.32 40.88
Median 15.45 6.71 4165 150.98 1164.35 143.02 610.81 78.05 33.06 38.89 40.75
33 hdw_Cachorro Minimum 13.50 6.74 4120 201.90 1159.94 154.96 595.13 75.83 29.60 34.70 45.96 n.d. n.d. -4.54 -22.9 n.d. n.d.
Maximum 17.60 7.17 4890 248.30 1434.20 191.42 743.23 111.63 36.75 58.88 53.00
Mean 14.95 6.90 4612 222.44 1316.71 172.81 686.56 93.97 33.64 44.72 48.78
Median 14.70 6.87 4625 221.11 1312.01 171.71 700.46 95.83 33.85 39.52 48.27
34 hdw_Mourato Minimum 13.80 6.42 6680 258.54 2162.93 113.35 1103.05 143.15 51.95 48.55 42.23 n.d. n.d. -2.2 -17.2 n.d. n.d.
Maximum 15.80 7.18 8690 274.50 2712.28 363.41 1410.55 188.35 72.55 114.90 50.44
Mean 14.62 6.87 8087 266.45 2484.16 277.77 1284.34 164.67 61.52 78.08 47.37
Median 14.50 6.93 8305 265.66 2542.16 313.14 1336.35 164.53 60.68 67.95 47.75
35 hdw_Aço Minimum 15.70 6.88 4680 222.04 1146.62 154.61 619.45 91.38 32.95 27.98 36.22 n.d. n.d. -4.52 -21.6 n.d. n.d.
Maximum 17.00 7.67 4880 445.30 1405.72 187.55 764.40 127.60 42.45 44.45 43.96
Mean 16.30 7.35 4788 371.80 1295.15 173.19 710.66 108.24 37.38 34.42 42.40
Median 16.15 7.52 4800 392.84 1316.70 175.64 731.84 107.08 37.07 30.81 43.75
36 hdw_Ana Clara Minimum 14.30 6.62 373 182.39 1009.55 136.03 430.54 74.94 20.54 34.90 42.83 n.d. n.d. -4.69 -22.4 n.d. n.d.
Maximum 16.20 7.56 4420 218.99 1275.09 175.43 697.00 126.04 38.54 58.72 52.10
Mean 15.13 7.16 3287 199.37 1107.64 155.39 553.46 104.22 32.67 43.72 45.33
(continued on next page)
Journal of Hydrology: Regional Studies 12 (2017) 69–87
 Table 2 (continued)

Island Refª Name Statistics T pH Cond. HCO3 Cl SO4 Na Mg K Ca SiO2 Sr B δ18O (‰) δ2H (‰) δ87Sr δ11B (‰)

°C μS/cm mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L μg/L μg/L
J.V. Cruz, C. Andrade

Median 15.25 7.22 3715 199.17 1086.48 150.27 564.36 105.03 36.02 39.82 44.15
37 hdw_Guindaste Minimum 13.60 6.45 4330 53.68 1233.80 157.23 672.63 79.50 28.08 29.95 32.20 n.d. n.d. -4.37 -20.5 n.d. n.d.
Maximum 15.80 7.55 5680 67.71 1728.85 239.19 801.50 103.80 43.15 67.28 44.74
Mean 14.42 6.94 5062 61.10 1481.34 188.27 747.61 90.09 35.97 44.70 37.69
Median 14.25 6.91 5160 62.22 1503.93 180.81 761.76 90.38 36.33 37.57 37.26
PIC 38 hdw_Silveira Minimum 13.90 5.76 1688 287.92 324.48 42.09 193.19 42.27 17.25 21.59 50.55 n.d. n.d. -2.24 -16.8 n.d. n.d.
Maximum 16.50 6.43 1806 330.60 440.20 58.11 279.70 65.89 26.08 32.75 64.18
Mean 15.72 6.20 1758 301.21 381.14 49.14 237.25 55.22 20.16 25.66 54.81
Median 16.00 6.23 1784 295.85 387.95 46.43 243.67 59.39 19.03 22.11 52.97
39 hdw_Furna Minimum 14.20 6.24 6890 56.12 1926.89 255.67 1052.65 117.65 46.50 54.10 20.92 n.d. n.d. -3.79 -18.7 n.d. n.d.
Maximum 17.00 6.89 8400 67.70 2580.85 364.38 1228.85 149.80 58.85 109.10 35.14
Mean 15.90 6.51 7522 63.80 2288.58 304.12 1145.92 131.10 51.47 74.35 26.24
Median 16.40 6.43 7380 65.88 2416.01 296.58 1160.10 128.45 50.45 58.35 25.01
40 hdw_Gingal Minimum 14.90 6.47 7520 66.49 2389.55 305.29 1339.15 146.20 56.00 68.90 17.10 1200.00 778.00 -3.76 -18.6 0.708864 39.20
Maximum 18.10 7.76 10130 78.08 3163.05 383.28 1535.15 184.00 68.75 120.20 24.80
Mean 16.14 7.10 8876 71.00 2786.18 341.59 1436.49 161.38 60.31 89.56 22.16
Median 15.90 7.09 8830 70.76 2869.90 336.09 1462.60 162.60 57.55 73.05 24.19
41 hdw_Cabrito Minimum 15.00 6.48 7670 59.78 2080.02 270.17 1166.20 134.95 5.24 59.90 19.87 n.d. n.d. -3.86 -19.5 n.d. n.d.
Maximum 18.10 8.02 10500 79.30 3344.10 330.94 1469.55 180.15 73.75 114.50 28.89
Mean 17.02 7.14 8596 72.83 2511.77 302.32 1312.66 159.28 27.55 80.83 23.19
Median 17.60 7.24 8530 75.03 2341.75 297.84 1315.95 162.75 6.28 64.15 22.11
42 hdw_Frades Minimum 13.60 6.74 6250 148.84 1906.38 150.81 838.00 105.10 38.25 38.30 33.19 635.00 595.00 -4.22 -20.8 0.708819 37.90

76
Maximum 16.70 8.01 6930 214.72 2059.00 306.68 1164.90 162.00 69.45 76.45 42.68
Mean 15.62 7.16 6704 182.02 1984.28 237.19 1055.62 138.05 53.71 52.35 36.44
Median 16.50 7.04 6800 183.00 1988.30 248.00 1056.10 139.10 53.40 44.50 35.42
43 hdw_João Lima Minimum 15.20 7.17 4300 274.50 1125.14 119.11 600.63 69.95 29.48 36.50 28.01 n.d. n.d. -1.89 -16.6 n.d. n.d.
Maximum 17.10 7.72 5750 355.63 1675.60 248.03 912.68 115.93 43.45 63.48 35.31
Mean 16.24 7.45 5198 326.60 1421.14 173.70 793.38 102.85 37.22 44.71 32.97
Median 16.50 7.41 5310 336.72 1486.68 170.59 827.60 112.15 36.88 39.90 33.80
44 hdw_Café Concerto Minimum 15.00 6.91 4850 281.80 1249.95 142.17 683.00 84.55 30.30 37.65 29.08 n.d. n.d. -4.55 -22.5 n.d. n.d.
Maximum 17.20 8.17 5500 346.48 1551.35 193.93 844.23 112.73 42.98 58.60 40.10
Mean 15.98 7.51 5088 330.98 1385.28 170.97 778.93 103.28 36.77 46.17 32.50
Median 16.00 7.30 5000 343.43 1341.51 175.22 837.10 104.58 37.65 40.18 29.17
45 hdw_Madalena Minimum 14.40 6.29 5250 166.50 1413.38 181.21 792.55 74.43 32.18 31.65 37.35 n.d. n.d. -4.33 -21.5 n.d. n.d.
Maximum 17.10 7.70 5870 179.34 1778.31 227.42 951.08 121.80 44.00 55.18 46.32
Mean 15.78 7.10 5594 174.45 1634.28 198.01 880.01 108.85 40.57 41.43 39.79
Median 15.80 7.16 5610 174.46 1653.19 193.08 908.70 118.43 42.20 34.83 38.16
46 hdw_Porto Calhau Minimum 15.00 4.49 8650 180.56 2382.78 252.64 1372.25 165.35 67.05 73.50 31.19 n.d. n.d. -1.13 -12.8 n.d. n.d.
Maximum 17.10 7.45 10620 214.72 3269.55 423.05 1698.65 194.05 74.15 113.65 40.58
Mean 16.38 6.63 9732 202.21 2912.99 346.54 1553.80 179.84 70.93 94.60 34.71
Median 16.70 7.29 9830 206.78 2999.81 355.23 1572.15 179.98 71.25 95.63 33.54
Journal of Hydrology: Regional Studies 12 (2017) 69–87
J.V. Cruz, C. Andrade Journal of Hydrology: Regional Studies 12 (2017) 69–87

Fig. 2. Major-ion relative composition represented by means of a Piper diagram: A − Graciosa and Pico islands; B − drilled wells from other islands (STM − Santa
Maria; SMG − São Miguel; TER − Terceira; FAI − Faial; SJG − São Jorge).

Scandinavian, Sweden) by MC-ICP-MS using internal standardization, and external calibration with bracketing isotope SRMs.

4. Results and discussion

4.1. Major-ion composition

The major-ion composition descriptive statistics (minimum; maximum; mean; median) for Graciosa and Pico islands samples are
shown in Table 2. In Pico island, charge-balance errors (CBE) are within the ± 5% (88.6% of the samples) and ± 10% (8.6%)
intervals, while one sample presents a CBE equal to 10.2%. In Graciosa, 36.7% of the samples have CBE in the range ± 5% and 36.7%
in the interval ± 10%, while the remaining samples present a CBE in the interval 10–12% (27.3% of the samples). Results from
samples collected in the other islands are reported in Table E1 (electronic supplementary material), being 51% and 22% of the
samples respectively within the ± 5% and ± 10% charge-balance intervals. Isotopic composition (δ18O; δ2H; δ87Sr; δ11B) is also
shown on Tables 1 and E1.
In Graciosa island, drilled wells present Na-Cl and Na-Mg-Cl type waters, while the hand-dug wells are from the Na-Mg-Cl, Mg-Na-
Cl and Na-Mg-HCO3 types (Fig. 2A). Groundwater from drilled wells in Pico is mainly from the Na-Cl to Na-HCO3 types, despite a few
samples that present higher relative alkali earth metals content (Ca + Mg) (Fig. 2A). In this island, samples from coastal hand-dug
wells are mainly from the Na-Cl type. In the other islands of the Azores, groundwater from drilled wells is mainly from the Na-Cl and
Na-HCO3 types, despite some samples that are plotted in the Na-Mg and Mg-Na fields over the cationic triangle (Fig. 2B).
The mean groundwater temperature in Graciosa range between 17.9 °C (well 2) and 25.8 °C (well 6) (median = 19.5 °C), being a
total of four samples classified as thermal waters according to the criteria proposed by Schoeller (1962), thus presenting a
temperature of about 4 °C higher than the average mean air temperature (17.5 °C): wells 4 (25.3 °C), 5 (24.1 °C), 6 (25.8 °C) and 7
(24.3 °C). In Pico island, water temperature range between 13.5 °C (well 22) and 17.0 °C (well 41) (median = 15.5 °C). In the

77
J.V. Cruz, C. Andrade Journal of Hydrology: Regional Studies 12 (2017) 69–87

remaining islands, water temperature is in the range of 14.3 °C (well 67) and 51.2 °C (well 66), being four samples classified as
thermal waters: wells 66, 70 (26.1 °C), 79 (24.1 °C) and 86 (22.7 °C).
Mean EC values in Graciosa range between 308 μS/cm (well 9) and 3462 μS/cm (well 4) (median = 1205 μS/cm), and only two
samples present measurements higher than 2000 μS/cm: well 4 and 6 (2202 μS/cm).
Generally the hand-dug wells in Pico are highly mineralized (1758–9732 μS/cm; median = 5074 μS/cm), while for drilled wells
EC measurements are in the range of 186 μS/cm (well 21) to 5625 μS/cm (well 29), being the median value about five times lower
(1037 μS/cm). Nevertheless, considering only the drilled wells in this island, wells 16, 18, 25, 29 and 30 present a mean EC higher
than 2000 μS/cm. Samples collected in the other islands present a mean EC ranging between 133 μS/cm (well 57) and 4710 μS/cm
(well 55) (median = 359 μS/cm), and only two samples having values higher than 2000 μS/cm (wells 55 and 66–4060 μS/cm).
The mean pH range in both Graciosa and Pico islands is similar, respectively equal to 6.59 (well 1) − 7.21 (well 4) and 6.16 (well
19) − 7.80 (well 26), with their median values rather close to neutrality (6.97; 6.96). In the other islands, the range is wider, between
5.14 (well 70) and 8.28 (well 53), with a similar median value (6.91).
The overall mineralization of groundwater is mainly controlled by Cl and Na, which account respectively for 10.4%-46.9% and
22.1%-39.7% in Pico and 18.9%-41.6% and 16%-36.4% in Graciosa of the relative major-ion content. For the group of wells
presenting EC higher than 2000 μS/cm, the relative Cl and Na contribution is even higher, respectively in the range of 30.7%-46.9%
and 24.8%-37.2% in Pico and 37.8%-41.6% and 24.9%-27.4% in Graciosa islands. In the other islands, Cl and Na account
respectively for 14.2%-49.3% and 16.2%-40.8% of the major-ion content.
From the plots in Fig. 3, two major groups of wells can be identified according to the electrical conductivity (EC) measurements.
The first are the wells with mean EC higher than 2000 μS/cm, to which drilled wells 4 and 6 in Graciosa and hand-dug wells 31–37
and 39–46 and drilled wells 16, 18, 25, 29 and 30 in Pico island belong. The other group of samples have a mean EC lower than
2000 μS/cm, to which the remaining wells from Graciosa and Pico, as well as the majority of the samples collected on the other
islands, belong. Wells 55 (Santa Maria) and 66 (São Miguel) also belong to the former group.
The highest correlation coefficients between EC and the major-ion species content is computed for Cl (r = 0.994; Fig. 3E), Na
(r = 0.988; Fig. 3A), SO4 (r = 0.966; Fig. 3F) and Mg (r = 0.929; Fig. 3C). A high correlation coefficient is also depicted for K
(r = 0.896; Fig. 3B). These results suggests the influence of a groundwater salinization process due to mixture with seawater, which is
also consistent with the lower correlation coefficients being computed for HCO3 (r = 0.317; Fig. 3G) and SiO2 (r = −0.041; Fig. 3H).
The influence of a seawater component on the groundwater chemistry also explains the close relationship between Na and Cl
(r = 0.991) and between Cl and SO4 (r = 0.973). The marine source is also shown by the fact that samples are plotted close to the
seawater ratio line. Considering a binary mixing process, and using Cl as conservative ion, seawater fraction ranges between 0.1%
(well 9) and 5.80% (well 4) (median = 1.33%) in Graciosa island. In Pico, the range for drilled wells is 0.03% (well 21) − 9.52%
(well 29) (median = 0.96%) while for hand-dug wells values are much higher being in the range 1.62% (well 38) − 17.23% (well
41) (median = 7.71%). For the other islands, values are in the range between 0.02% (well 57) and 6.88% (well 55)
(median = 0.23%), with a very high fraction (4.84%) observed in well 66.
Bicarbonate accounts for 1.8%–27% and 0.7%–38% of the major-ion content respectively in Graciosa and Pico islands, being the
highest values computed for wells 9 and 11 in the latter and in wells 21 and 22 in the former. They correspond to waters that depict
some of the lowest EC mean values (308.3–428 μS/cm) among the studied samples. The rCl/rHCO3 ratio ranges between 0.41 (well
11) and 13.22 (well 4) in Graciosa and between 0.16 (well 22) and 39.24 (well 40) in Pico island and the higher values are associated
to the marine signature as Cl is practically unavailable for dissolution during water percolation (Join et al., 1997).
The most important type of hydrogeochemical reaction in volcanic aquifers is silicate leaching, which releases alkali metals or
alkali-earth metals while neutralizing fluid acidity and releasing HCO3 (Evans et al., 2002). Therefore, the HCO3 enrichment
originates from CO2 in the soil and from the associated HCO3 enrichment due to fluid acidity neutralization through rock leaching,
which is enhanced by water temperature as in the case of well 66 (mean temperature = 51.2 °C). Nevertheless, factors such as the
saturation state of primary minerals, the precipitation of secondary minerals, the aqueous chemistry of each element and the acidic
character of the environment controls the dissolution of primary minerals on the volcanic rocks (Aiuppa et al., 2000). SiO2 solubility
is being controlled by the oversaturation of the majority of the samples for chalcedony and quartz as determined using PHREEQC
software (Parkhurst and Appelo, 1999). The influence of silicate leaching is also depicted by the SiO2 content of well 66 (113.4 mg
SiO2/L), the sample that most represents this trend.
The relationship between alkali and alkali earth metals show that samples with higher overall mineralization depict an
enrichment in Na + K as this group of samples is clearly plotted under the Na + K = Ca + Mg line (Fig. 4). Generally, the rMg/rCa
ratio is higher than 1 due to groundwater that flow through basaltic rocks (Custodio and Llamas 1983). In Graciosa, the mean value
for rMg/rCa ranges between 0.58 (well 2) and 3.94 (well 1), with higher values again for wells 8 (3.78) and 3 (3.24). In Pico, values
range between 0.75 and 6.74, with the lowest values observed in wells 14 (0.75) and 19 (0.95) and the highest values in wells 35
(6.74), 45 (6.17), 42 (6.07) and 25 (5.81).
Studies about the groundwater chemistry on perched water bodies in the Azores have shown that Na-HCO3 is the dominant water
type (Cruz and Amaral 2004; Cruz and Andrade 2015). A clear host-rock signature resulting from the contribution of weathering was
identified in these more pristine aquifers, depicting differences between groundwater that flows through aquifers of basaltic nature,
more enriched in alkali-earth metals, compared to more evolved volcanic rocks. Springs in Graciosa and Pico follow the first trend
(Cruz and Amaral 2004). Therefore, the overall enrichment in sodium observed in the studied wells of Graciosa and Pico islands is
controlled by the marine contribution. In Graciosa, the rNa/rCa ratio ranges between 0.75 (well 11) and 9.43 (well 2), being the
lowest values observed in hand-dug wells and the highest in drilled wells. In Pico, the rNa/rCa values are generally higher, in the
range between 1.37 (well 14) and 25.03 (well 45). There is also a group of wells that present ratios higher than 20 (wells 25, 26, 35,

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Fig. 3. Relationship between electrical conductivity (in μS/cm) and major-ion species (in meq/L) and SiO2 (in mmol/L) (linear regression lines are also shown in the
plots).

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Fig. 4. Relationship between Na + K (in meq/L) and Ca + Mg (in meq/L).

42, 45). The fact that rNa/rCa ratio is generally higher than 1 is associated to the Na-enrichment resulting from mixture with
seawater.

4.2. Factor analysis

Factor analysis with varimax rotation was applied to a dataset made of all samples collected along the present study using the
SPSS Statistics vs. 22. Previously, the Kaiser-Meyer-Olkin measure of sampling adequacy and the Bartlett sphericity tests were
performed, in both cases with results that show the applicability of factor analysis. The Kaiser-Meyer-Olkin statistic equals 0.774,
while the chi-square value for the Bartlett test (2029.69) allows to reject the null hypothesis (uncorrelated variables) at a significance
level α < 0.005.
The sum of the percentage of variance explained by both factors is equal to 79% (factor 1: 58.71%; factor 2: 20.63%). The factor 1
variables as EC, Cl, Na, SO4, Mg, K and Ca depict high positive loadings, therefore suggesting that this factor represents the
salinization process through mixing with seawater (Fig. 5A). The fact that Ca also depicts a high score along factor 1 represents the
influence of ion exchange processes of alkali metals by alkali earth metals.
The cation exchange of Na + K for Ca + Mg is also suggested using the methodology proposed by Appelo and Geinaert (1991), as
samples with a significant seawater fraction higher than 2% are plotted well above the conservative binary mixing line between fresh
water and seawater drawn on the upper part of the Piper diagram (Fig. 6), being the location of each sample on the mixing line
computed from the expression proposed by Appelo and Postma (1993).
Instead, along factor 2 temperature, HCO3 and SiO2 depict high positive scores, while pH has a high negative load (Fig. 5B). This
factor represents the contribution to groundwater chemistry from silicate weathering as well as the volcanic influence through
temperature increase and CO2 release. The fact that pH depicts an inverse relationship along factor 2 for HCO3 suggest a control
through CO2 dissolution that imbalances the expected pH increase through weathering of silicate minerals.
Samples that are most enriched in chloride, as well as those that present an overall higher mineralization as expressed by EC,
depict higher positive loads along factor 1 (wells 34, 39–46), a trend that expresses the effect of seawater mixture (Fig. 7). Well 66
depict the highest load along factor 2 representing the influence of silicate weathering. This well is plotted in an intermediate position
between both axes, which results from the cumulative influence of mixture with seawater.

4.3. Isotopic composition

The 18O and 2H stable isotope content in Graciosa island ranges from −1.61 to −4.62‰ for δ18O and from −15.2 to −23.6‰ for
δ2H, with the exception of drilled well 5, which presents an heavier isotopic composition (δ18O = 1.52‰; δ2H = −7.9‰) (Table 2).
The data for wells in Pico island show a δ18O content range from −1.13 to −4.78‰ and from −14.2 to −23.9‰ for δ2H.
The stable isotope composition of the samples collected in drilled wells spread over the other islands range between −1.02‰
(well 90) and −4.94‰ (well 76) for δ18O and between −11.4‰ (well 95) and −22.1‰ (wells 75 and 76) for δ2H. Well 67 presents
the most heavy isotopic composition (δ18O = −0.1‰; δ2H = −4.4‰).
Data on δ87Sr range between 0.705064 (well 7) and 0.705217 (well 6) in Graciosa Island and between 0.706222 (well 15) and

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Fig. 5. Scores of variables along factor 1 (A) and factor 2 (B).

0.708864 (well 40) in Pico Island, corresponding to an elemental content respectively in the range of 132–1090 μg/L and
56.2–1200 μg/L. The δ11B values range between 27.6‰ (well 10) to 39.9‰ (well 6) for Graciosa island and from 37.1‰ (well 17) to
39.2‰ (well 40) in Pico, while the elemental content is respectively in the range between 64.7–135 μg/L and 40.7–778 μg/L.
The majority of the samples are plotted near the global meteoric water line (Craig 1961; δ2H = 8.13 δ18O + 10.8), which
suggests that groundwater is from meteoric origin (Fig. 8). The same effect is observed considering the regional meteoric water line
proposed by Rodrigues (1995; δ2H = 8δ18O + 15). However, a group of samples shows observations under the local meteoric water
line suggesting the influence of other processes, namely mixture with seawater and evaporative isotopic enrichment, both causing
less negative 8δ18O and δ2H values (Fig. 8). Similar isotopic enrichment mechanism was identified based on the δ18O vs. δ2H plot
(Jorgensen and Banoeng-Yakubo, 2001; Faye et al., 2005; Cary et al., 2015).
The majority of the samples from Graciosa and Pico fall near the computed mixing line between fresh water and seawater on the
Cl vs. δ18O plot, nevertheless with a small fraction of seawater (Fig. 9). Samples from hand-dug wells in Pico island that depict the
high mean values for EC and Cl content reflect the higher seawater fraction and are plotted along the mixing line.
The same samples that showed an evaporative signature are scattered over the mixing line presenting a large range of Cl values: a
group of samples (A) present a Cl content lower than 100 mg/L, suggesting that the isotopic enrichment is independent of the
chloride enrichment, and that it therefore can be attributed to seawater spraying. Seawater spraying has been already identified as a
source of Cl in shallow groundwater in the Azores archipelago (Cruz and Amaral 2004; Cruz et al., 2013; Cruz and Andrade 2015) and
controls rain water chemistry in islands and continental coastal regions (Berner and Berner, 1996). A second group of samples in
Fig. 9 (group B) depict an evaporative effect over the 8δ18O vs. δ2H plot but present much higher Cl content (higher than 1000 mg Cl/
L as for samples 29, 34, 43, 46) suggesting the coupled effect of mixing with seawater and evaporation. A similar pattern is depicted
in the Cl vs δ2H plot (Fig. E3 − electronic supplementary material).
By plotting the 87Sr/86Sr isotope ratio against the reciprocal of Sr, it is possible to shown the effect of a mixture process between
two end-members as represented by a straight line, besides their usefulness to assess other processes besides mixing (Shand et al.,

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Fig. 6. Upper part of the Piper diagram represented for samples with a seawater fraction higher than 2% (samples 16, 18, 25, 29, 30, 31–46 in Pico; 2, 4, 5, 6, 8 in Graciosa;
55, 66, 86 in the other islands). Tails on each plot points directly toward the position of the same sample over the mixing line considering only a mixture process and are
determined from the theoretical composition. Seawater (sw) and freshwater (fw) chemistry data from respectively Cruz (1997) and Cruz and Amaral (2004).

2009). Applying this procedure, a trend representing mixture between freshwater and seawater is depicted by samples from wells 15,
17, 29, 30, 31, 40, 42 (Fig. 10A), that have δ87Sr values in the range from 0.706222 to 0.708864. The higher δ87Sr values were
measured in hand-dug wells 31, 40 and 42, which correspond to samples where mean EC and Cl values are very high (Table 2), and
the mean seawater fraction is respectively equal to 7.41%, 14.34% and 10.2% (Fig. 10A). In the same plot, another trend is depicted
for the wells in Graciosa island (wells 4–7, 10) with lower δ87Sr values, in the range from 0.705064 to 0.705155. This latter trend is
suggested to represent the influence of water-rock interaction besides seawater spraying, but for wells 4, 5, 6 and 7 a cumulative
effect from mixture with seawater is also expected to occur. Nevertheless, the 87Sr/86Sr isotope ratio in groundwater is much higher
than in the whole rock (Graciosa: 0.70336-0.70390; Larrea et al., 2014; Pico: 0.703540-0.703883; França et al., 2006) and the
residual lithologic signature over the isotopic composition suggests a slight influence of water-rock interaction over water
composition, consistent in an hydrogeological environment characterized by high groundwater flow velocities that imply a high
water-rock ratio (Langmuir, 1997). Similar trends are shown by plotting Cl content vs δ87Sr (Fig. 10B).
A mixture between freshwater and seawater trend is also depicted by the δ11B data (Fig. 11A and B). Nowadays water in open sea
environments has a δ11B content of about 40‰, while the natural water range is −16‰ to 60‰ (Vengosh et al., 1991; 1994), and

Fig. 7. Factor analysis results represented as function of scores of samples along factors 1 and 2.

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Fig. 8. Relationship between δ18O (‰) and δ2H (‰). Global meteoric water line from Craig (1961) and seawater data from Cruz (1997).

the measurements made in Graciosa and Pico islands suggest a marine boron source. The plot of well 10 (Graciosa island) suggests
that other processes besides groundwater mixture with seawater are influencing the δ11B composition such as water-rock interaction.
Nevertheless, δ11B values for groundwater are much higher comparing to rock values as determined for Pico island (−3.3 to −4.1‰;
Genske et al., 2014), suggesting that water-rock contribution is limited as is also confirmed for the δ87Sr data. For example, a set of
samples of mineral waters collected in São Miguel island present values in the range of −6.2‰ to 3.3‰ (Morell et al., 2008b), close
to the overall range determined in the Azores by Genske et al. (2014 and Turner et al. (2007, constraining the water-rock end-
member.

5. Conclusions

The protection of groundwater resources in the Azores is a corner stone of the water policies developed in the archipelago, as
98.3% of the total water appropriation (47.5 × 106 m3/a) is abstracted from groundwater sources, such as springs and drilled wells
(AHA/DRA, 2015).
Groundwater salinization due to seawater intrusion in Graciosa and Pico is one of the major processes controlling water chemistry

Fig. 9. Relationship between Cl content (in mg/L) and δ18O (‰). Mixing line computed for 5% increments of the seawater end member. Freshwater data from
Coutinho et al. (1996) and seawater data from Cruz (1997).

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Fig. 10. Relationship between the elemental composition on 1/Sr (A) and Cl (B) vs. the δ87Sr content. Freshwater data from Louvat and Allègre (1998) and the range of
the isotopic content of rocks in Graciosa and Pico are respectively from Larrea et al. (2014) and França et al. (2006). Seawater data from Clark (2015).

in both islands, as shown in the present study through the characterization of major-ion and the stable and radiogenic isotopic
content. This process, constrains severely water supply in these islands due to both natural factors, such as the small thickness of
freshwater lenses over salt water in the coastal aquifers due to the high permeability of lava flows, the tidal fluctuation of the
groundwater level due to tides (Cruz and Silva 2001; Cruz et al., 2011), and an anthropogenic factor. The latter factor results from
technical problems during wells completion and from water resources management, ranging from very high pumping rates to the
drilling strategy itself (Cruz et al., 2011).
The impact of groundwater salinization on the water availability for human consumption supply in Graciosa and Pico islands is
shown by the comparison with EC and chloride reference values from the Decree-Law n.° 236/98, that establishes water quality
guidance values to be observed for any groundwater source to be abstracted for water supply.
In Graciosa and Pico, respectively 72.7% and 71.4% of the wells exceed the 200 mg Cl/L reference value, while considering the
reference value for conductivity (1000 μS/cm) the exceedance percentage is equal to 72.7% and 77.1% respectively. Also, 72.7% of
the wells in Graciosa exceeds the groundwater threshold values derived from the same reference values (Cl = 121,9 mg/L;
EC = 649.1 μS/cm; Cruz et al., 2015), while in Pico the exceedances are equal to 82.9% and 88.6% respectively.
For the remaining islands, 7.8% of the wells exceed the reference values for chloride content and EC, and about 23.5% and 25.5%
of the wells exceed the referred groundwater threshold values, which suggest that the impact of seawater intrusion on water quality is
less important than for Graciosa and Pico islands. Moreover, water supply in Graciosa and Pico island is almost entirely dependent on
groundwater exploitation in drilled wells, while in the remaining islands the contribution from springs discharging from perched-
water bodies in altitude is dominant.
Results shown that groundwater abstraction should be carefully managed in the Azores archipelago, and mainly in Graciosa and
Pico, with the establishment of sustainable well discharges and the development of a monitoring programme in order to allow
measurements of the main variables (such as well discharge, groundwater level, coupled with conservative hydrogeochemical tracers,
as chloride).

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Fig. 11. Relationship between the elemental composition on 1/B (A) and Cl (B) vs. the δ11B. The range of the isotopic content of rocks in Pico is from Genske et al.
(2014) and seawater data from Clark (2015).

Acknowledgments

The authors are grateful to the Azores Directorate-Regional for Environment for the funding of the present project and for the
permission to handle the data for this paper, as well as to the Editor and the anonymous reviewers for the contribution to the
manuscript improvement.

Appendix A. Supplementary data

Supplementary data associated with this article can be found, in the online version, at http://dx.doi.org/10.1016/j.ejrh.2017.04.
003.

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