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Procedia Earth and Planetary Science 17 (2017) 634 – 637

15th Water-Rock Interaction International Symposium, WRI-15

Geochemistry and environmental isotopes as natural tracers of

groundwater flow in shallow aquifer systems within Lisbon
Volcanic Complex (Portugal)
Paula M. Carreiraa,1, Maria O. Nevesb, Paula Figueiredoc, José M. Marquesb, Dina
Nunesa, João C.M. Reic, Artur J.E. Carachoc
a
Centro de Ciências e Tecnologias Nucleares, CTN/IST, Universidade de Lisboa, Estrada Nacional nº 10, 2695-066 Bobadela LRS, Portugal
b
CERENA, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais 1049-001, Portugal
c
Academia Militar, Rua Gomes Freire, 1169-203 Lisboa

Abstract

Under the scope of a R&D Project for the use of GSHP systems in a Military facility near Lisbon, groundwater samples were
collected for chemical and isotopic characterization since these shallow aquifers could represent the basis for this Project viability
(i.e. the source of heat transfer – using groundwater from local dug wells). An isotopic difference around 1‰ in 18O and around
10 ‰ in 2H and deuterium excess d = 10 ‰, was found in the shallow groundwater samples, collected in an area of about 3 km2,
where the pH values range from 7 to 10. The differences in the isotopic and chemical signatures could be ascribed to different
recharge altitudes and/or different flow paths in the Lisbon Volcanic Complex, and to the existence of organic layers or linked to
residues from old anthropogenic activities (δ13C measured in the total dissolved carbon vary from -23.5 to -14 ‰).
© 2017
2017TheTheAuthors.
Authors. Published
Published by by Elsevier
Elsevier B.V.B.V.
This is an open access article under the CC BY-NC-ND license
Peer-review under responsibility of the organizing committee of WRI-15.
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the organizing committee of WRI-15
Keywords:Shallow aquifers; environmental isotopes; GSHP systems; Lisbon Volcanic Complex; Portugal

1. Introduction

Groundwater is a renewable source of energy, with constant temperature below a certain depth, and can easily
supply enough energy throughout the year to heat and cool a suburban residential housing, as in the winter or in the
summer the soil temperature is higher and lower, respectively, than the average air temperature, making it possible

* Corresponding author. Tel.:+ 351-219946179; fax: + 351-219946185.

E-mail address: carreira@ctn.tecnico.ulisboa.pt

1878-5220 © 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/).
Peer-review under responsibility of the organizing committee of WRI-15
doi:10.1016/j.proeps.2016.12.170
 Paula M. Carreira et al. / Procedia Earth and Planetary Science 17 (2017) 634 – 637 635

touse Ground Source Heat Pumps (GSHP) systems. This work was carried on within Amadora Quartering, near
Lisbon (Fig.1) under the scope of a R&D Project in which the main objective was looking for natural energy sources
either for heating or cooling using a GHP system. The study and characterization of the shallow aquifer systems in
the area of influence represents a huge importance because of the negative environmental impacts that may cause on
the level of water resources. Ecological aspects in respect to the protection of ground and groundwater are of
paramount importance in any shallow low geothermal heating project and some issues should be considered even
drilling shallow aquifers such as the prevention of connect aquifers to the surface or either with aquifers at different
depth with each other.
The objective of the hydrogeochemical and environmental isotope (2H, 3H, 13C and 18O) approach in this research
was to demonstrate not only the feasibility of using GHPS systems in this military facility, but also to contribute to
the characterization of the shallow aquifer systems that will be used as the base of this Project viability, through the
estimation of groundwater mean residence time, identification of active recharge and find out possible hydraulic
influences between local dug wells (Fig.1). The studied shallow aquifer systems ascribed to the Lisbon Volcanic
Complex (LVC), present a variable depth and groundwater temperatures between 17 and 21ºC, liable to supply
water-air- or water-water-type GSHP systems. In this region the geothermal gradient is 31 ºC/km, the heat flow
density is around 91 mW/m1, and the temperatures at 500 m depth could reach 34ºC1.

Fig. 1 –(a) Location of the research area in the Iberian Peninsula.; (b) Location of the sampled dug wells (●), within Amadora Quartering
(adapted from Google Earth 2016)

2. Methodology

Environmental stable and radioactive isotopic, geochemical and hydrogeological studies were carried out to
characterize the shallow aquifer systems at Amadora Quartering. Two fieldwork campaigns were performed.
Groundwater samples were collected from 5 dug wells where T (ºC), pH, Eh (mV) and electrical conductivity (EC
in µS/cm) were measured in situ. Major and minor chemical species dissolved in the water samples were analyzed at
Laboratory of Mineralogy and Petrology (LAMPIST, IST-Portugal) by ion chromatography for anions using
DIONEX ICS-900 equipment, and at ActLabs Ltd, Canada by inductively coupled plasma optical emission
spectrometry (ICP-OES) for cations. The δ2H and δ18O measurements (vs. V-SMOW reported in ‰) were
performed by Laser Spectroscopic (LGR 24d) at C2TN/IST - Portugal. The 3H water content (reported in Tritium
Units, TU) was also determined at C2TN, using electrolytic enrichment followed by liquid scintillation counting
(PACARKD TRI-CARB 2000 CA/LL); the standard deviation varies between ±0.5 and ±0.6 TU. The δ 13C
determinations were performed in the Total Dissolved Inorganic Carbon (TDIC), precipitated in the field by addition
of BaCl2 to the water sample, under a pH environment higher than 10, and after measured at C 2TN Light Isotopes
Laboratory, using Geo SerCon 20-20 mass spectrometer. The δ13C values are reported in ‰ vs. V-PDB, with an
accuracy of ±0.1‰.
636 Paula M. Carreira et al. / Procedia Earth and Planetary Science 17 (2017) 634 – 637

3. Results

3.1. Hydrochemistry

The area under research is located in the Neo-cretaceous Lisbon Volcanic Complex (LVC), composed by a set of
basaltic lava flows interlayered with pyroclastic beds. Given the geological nature of the LVC, most probably
regional groundwater flow paths will be mainly ascribed to the basis of this geological formation (at the Upper
Cretaceous limestones), where groundwater circulates through main alteration zones and basalt diaclases and issue
along regional deep faults. Previous studies2 carried out in the region mention the absence of significant water
resources ascribed to the LVC, but refer importance of this geological unit as a source of recharge for the deeper
aquifer systems. The groundwater sampling was carried out only in shallow aquifer systems (dug wells). Although
these five dug wells are located in a rather narrow area, around 3 km 2 (Fig. 1b), different hydrochemical facies were
identified (Fig. 2), with a special emphasis on the differentiation between sample P3 - Poço das Escadas and all the
remaining water samples.

Fig. 2- (a) DurovDiagram; (b) SchollerDiagram. Thesymbolsin thediagramsstands for: (○) P1- Poço Branco; (□) P2- Poço da Barbearia; (U) P3 -
Poço das Escadas; ( ) P4 - Poço Bar dos Alunos; (š) P5 - Poço Praça de Armas (Poço stands for “dugwell”).

The sampled groundwater (P1, P2, P4 and P5) is alkaline with a pH values between 7.4 and 7.8, with low
mineralization (Dry Residuum < 500 mg/L) and electrical conductivity < 690 μS/cm, presenting a Ca/Na-HCO3
facies. On the other hand, sample P3-Poço das Escadas is an Āoutlierā from this group, presenting higher pH
values (pH ≈10), the smallest mineralization (EC Ĭ 350 µS/cm) and a Ca/Na-SO4 facies (Fig. 2).
The predominant hydrochemical facies (Ca/Na-HCO3) is a consequence of the water-rock interaction process
occurring between the precipitation water recharging the LVC shallow aquifers while P3 composition might be
related to the remaining contribution of the waste leaching from local old anthropogenic activities. In fact,
groundwater movement through old dumps tend to leach the remaining wastes (organic or not), and acquire higher
ions concentration, as for example SO4, K, Mn, Fe, S and Zn, nevertheless the NO3 content is similar in all sampled
points with a mean value of 15 mg/L.

3.2. Isotope Hydrology

Tritium determination was carried out in all samples with mean concentrations around 2 TU, indicating an active
recharge of the shallow aquifer systems. As mention before, although these shallow groundwater sampling sites are
located in a narrow area, an isotopic difference of about 1 ă was obtained in the δ18O and about 10 ă in δ2H values
(Fig. 3). All samples do not present any indication of fractionation due to evaporation (deuterium excess Ĭ 10 ă)
that could explain the different isotopic signatures. The groundwater samples are plotted along the Global Meteoric
Water Line (G-MWL), define by3. The isotopic differences observed within this group of water samples can be
ascribed to different recharge altitudes (isotopic fractionation associated to the “altitude effect”). From the
 Paula M. Carreira et al. / Procedia Earth and Planetary Science 17 (2017) 634 – 637 637

hydrodynamic results (pumping tests), a link between P1 and P5 was identified, although, from the isotopic point of
view the samples from these two dug wells present distinct isotopic composition.
Carbon-13 determinations were carried out on the TDIC. Once more, sample P3 – Poço das Escadas have a
distinct δ13C content, presenting the most depleted composition (δ13C = -23.5 ‰ vs. V-PDB) of the sampled waters.
The 13C concentration is probably due to the presence of natural peats at depth or to the occurrence of organic
residues due to anthropogenic activities. Either sources can be responsible for the low Eh (P3 ≈ 25 mV) and isotopic
depletion (δ13C).
General 13C/12C variation in natural components like land plants C3 type varies between -30 to -20 ‰ while for
peat formations is around -30 to -23 ‰, both origins can support the δ13C values found at P3.

Fig. 3 – (a) δ2H vs. δ18O; (b) δ13C vs. δ18O; (c) δ13C vs. pH; (d) δ13C vs. Total Alkalinity; (e) δ13C vs. SO42-and (f) δ13C vs. K+. Thesymbols stand
for: (○) P1 – Poço Branco; (□) P2 – Poço da Barbearia; (Δ) P3 – Poço das Escadas; (°) P4 – Poço Bar dos Alunos and (š) Poço Praça de Armas.

4. Final Remarks

This R&D Project is at an initial stage. Future data regarding the 3H content (residence time information) and
13
δ C data will contribute to a better knowledge on the hydrogeological systems within the Lisbon Volcanic
Complex. A significant range of values were observed in the electrical conductivity and in the pH. The isotopic and
physico-chemical differences can be ascribed to different recharge altitudes or mixture between different water
systems with diverse flow paths reflecting the heterogeneities of the aquifer matrix. Although an interconnection
between well 1 and 5 has been recognized in situ from the hydraulic point of view, no relation was identified from
the isotopic composition. The results obtained so far seem to indicate that in a near future it will be possible to
incorporate techniques and methodologies in the fields of Geosciences and Energy Management.

Acknowledgements

This research was developed under the scope of the GHAMA Project, funded by Estado Maior do Exército
(Portugal). C2TN/IST authors gratefully acknowledge the FCT support through the UID/Multi/04349/2013 Project
and CERENA/IST acknowledges the FCT support through the UID/ECI/04028/2013 Project.

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