Chemical Geology 413 (2015) 94–106

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Chemical Geology

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3
H/3He, 14C and (U–Th)/He groundwater ages in the St. Lawrence
Lowlands, Quebec, Eastern Canada
Geneviève Vautour a, Daniele L. Pinti a,⁎, Pauline Méjean a, Marion Saby a, Guillaume Meyzonnat a,
Marie Larocque a, M. Clara Castro b, Chris M. Hall b, Christine Boucher a,1, Emilie Roulleau c,2, Florent Barbecot a,
Naoto Takahata c, Yuji Sano c
a
GEOTOP and Département des sciences de la Terre et de l'atmosphère, Université du Quebec à Montreal, CP8888 succ. Centre-Ville, Montreal, QC, Canada
b
Dept. of Earth and Environmental Sciences, University of Michigan, 1100 N. University, Ann Arbor, MI 48109-1005, USA
c
Atmosphere and Ocean Research Institute, The University of Tokyo, Kashiwa, Chiba 277-8564, Japan

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

Article history: This study attempts to place constraints on groundwater residence times using helium isotopes and 14C of a
Received 8 February 2015 regional groundwater flow system – the Becancour River watershed – located midway between Montreal and
Received in revised form 27 July 2015 Quebec City (Quebec, Canada). This densely populated region is one of the main targets for shale gas exploitation
Accepted 5 August 2015
in Eastern Canada. For this reason, this watershed has been the focus of a detailed aquifer study to gain a better
Available online 1 September 2015
understanding of groundwater resources, both in terms of availability and quality. In the current study, noble
Keywords:
gases were sampled and analyzed in twenty-eight wells from a Quaternary granular aquifer and a regional
Helium isotopes bedrock aquifer of Ordovician age. Tritium (3H) and radiocarbon (A14C) activities were measured on selected
3
H/3He ages wells. Helium isotopic ratios 3He/4He (R) normalized to that of the atmosphere (Ra = 1.386 × 10−6) range
U–Th/4He ages from R/Ra = 0.039 ± 0.003 to 3.109 ± 0.065. The helium isotopic signatures point to the presence of three
14
C ages water bodies: 1) modern infiltration water with nearly atmospheric helium isotopic ratio and little post-bomb
St. Lawrence Lowlands tritium recharging the shallower granular aquifer; 2) mid-50s tritium-rich water slightly mineralized; and 3)
Quebec an older water component rich in terrigenic helium flowing in from the bedrock fractured aquifer. Uncorrected
14
C ages range from 15 ka to modern. 14C is affected by several dead carbon reservoirs related to carbonate dis-
solution, cations exchange, oxidation of organic matter and methanogenesis. Adjusted 14C ages calculated with
NETPATH range from 7 ka to modern. Older 14C ages correspond to the end of the regional re-organization of
the hydrological system following deglaciation and isostatic rebound. Noble gas recharge paleotemperatures
are 4–9 °C colder than the present temperatures, although no clear relation with ages has been found. The
relationship between the helium isotopic ratios and 14C ages suggests that the regional bedrock aquifer is affected
by mixing between these three water sources. Calculated (U–Th)/4He ages can be partially explained by in situ
production of 4He in the aquifer rock and the addition of a radiogenic helium source external to the aquifer.
Calculated minimum helium fluxes of 1.0 × 10−8 to 1.8 × 10−7 cm3 STP cm−2 yr−1 are tens to hundreds of
times lower than the average continental crust flux of 3.3 × 10−6 cm3 STP cm−2 yr−1, suggesting local sources,
possibly from production of radiogenic helium in the shale gas formations underlying the studied aquifers. The
occurrence of old groundwater in this aquifer system clearly limits the renewable resource and increases the
risk of overexploitation in the case of increased use or in the case of pollution from different sources.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction including recharge conditions and geological characteristics of the

Groundwater flow rates in most aquifers are difficult to estimate be-
cause they are dependent on multiple and highly variable parameters,
⁎ Corresponding author.
E-mail address: pinti.daniele@uqam.ca (D.L. Pinti).
1
Now at: Centre de Recherches Pétrographiques et Géochimiques (CRPG), Nancy
Université, BP 20, 54501 Vandoeuvre-lès-Nancy Cedex, France.
2
Now at: CEGA - Centro de Excelencia en Geotermia de Los Andes, Departamento de
Geologia, Plaza Ercilla 803, Santiago, Chile.
reservoirs (e.g., Carrera and Neuman, 1986; Harvey and Gorelick,
1995; Castro and Goblet, 2005). Cross-formational flow and water
mixing (e.g., Pinti and Marty, 1998; Ma et al., 2005, 2009) make the
estimation of groundwater flow rates even more complex. Using the
distribution of natural tracer concentrations in an aquifer may contrib-
ute to quantify groundwater age. They can be further used to constrain
groundwater flow, to identify recharge areas and estimate recharge
rates, as well as to understand groundwater susceptibility to contami-
nation (e.g., Solomon et al., 1993).

http://dx.doi.org/10.1016/j.chemgeo.2015.08.003
0009-2541/© 2015 Elsevier B.V. All rights reserved.
 G. Vautour et al. / Chemical Geology 413 (2015) 94–106 95

Estimation of groundwater ages can be challenging (e.g., Goode,
1996; Bethke and Johnson, 2008) and often calls upon the use of multi-
ple isotopic tracers such as stable isotopes, CFC, SF6 or noble gases
(e.g., Cook and Solomon, 1997). These tracers provide information on
water mixing displaying different residence times and distinct flow
paths (e.g., Castro and Goblet, 2003). Because they are inert and stable,
noble gases are suited to place constraints on groundwater flow rates
and flow direction (e.g., Phillips and Castro, 2003). In addition, a number
of noble gas isotopes are produced by radioactive decay of parent
elements with contrasting half-lives, facilitating the estimation of a
wide range of groundwater residence times, from modern water with
the use of the 3H/3He method (e.g., Takaoka and Mizutani, 1987),
to million years old water with the use of the U–Th/4He method
(e.g., Andrews, 1985; Torgersen and Clarke, 1985; Castro et al., 2000;
Kulongoski et al., 2005; Aggarwal et al., 2015).
This study uses noble gases to constrain groundwater flow and to es-
timate groundwater residence times in the regional groundwater flow
system of the Becancour watershed (Fig. 1). The studied area is located
midway between Montreal and Quebec City, in the Province of Quebec,
eastern Canada. This region, corresponding geographically to the St.

Fig. 1. Simplified map of the Becancour watershed with potenziometric head isolines for the regional fractured bedrock aquifer, groundwater sampling locations and major tectonic
accidents (A). Profile along a NW–SE direction showing the architecture of the sampled aquifers (B).
96 G. Vautour et al. / Chemical Geology 413 (2015) 94–106

Table 1
He, Ne and Ar isotopic compositions of groundwater in the Becancour basin together with chemical and physical data.

Sample name X coord. Y coord. Altitude Water Depth Casing T TDS δ18O δD 4
Hemeas ±1σ 20
Ne ±1σ 36
Ar

UTM NAD 83 asl chemistry m length, m °C g L−1 cm3 STP g−1

H2O

x 10−8 x 10−7 x 10−6

Quaternary granular aquifer

BEC 105 (M) −72.0012 46.3643 91.7 Ca-HCO3 7.0 – 9.4 0.213 −11.71 −81.95 9.23 0.14 2.195 0.029 1.52
BEC 106 (M) −72.2271 46.3680 58.6 Ca-HCO3 20.0 – 8.3 0.062 −12.42 −87.59 7.12 0.11 2.130 0.030
BEC 113 (M) −71.5788 46.3699 138.6 Ca-SO4 9.1 – 7.8 0.270 −12.57 −88.81 11.08 0.17 3.502 0.046
BEC 117 (M) −72.1083 46.5447 40.2 Ca-HCO3 15.2 – 7.4 0.084 −12.12 −84.01 5.36 0.08 1.898 0.025
BEC 118 (P) −72.1274 46.5265 41.7 Ca-HCO3 6.1 – 9.9 0.298 −12.43 −86.06 6.04 0.09 2.275 0.030 1.49
BEC 124 (P) −71.6002 46.2505 317.3 Ca-Cl 2.2 – 10.2 0.053 −13.22 −93.75 4.81 0.07 1.546 0.020

Ordovician fractured aquifer

BEC 009 (P) −72.0076 46.2512 94.8 Ca-HCO3 50.3 18.6 10.0 0.197 −11.75 −83.55 8.02 0.12 2.209 0.029
BEC 010_1 (P) −71.9328 46.2696 105.2 Ca-HCO3 37.0 4.9 10.6 0.192 −10.88 −76.28 52.54 0.79 2.137 0.028
BEC 010_2 (P) 71.25 1.07 2.222 0.029
BEC 021 (P) −71.9511 46.3237 113.1 Ca-HCO3 25.9 12.2 10.6 0.294 −11.48 −79.48 5.98 0.09 1.907 0.025
BEC 034 (P) −71.8509 46.2415 130.1 Ca,Na-HCO3 24.4 6.0 9.3 0.192 −11.58 −80.73 5.68 0.09 1.443 0.019
BEC 101 (P) −72.1687 46.2760 90.6 Na-HCO3,Cl 47.2 12.6 12.0 0.780 −11.93 −83.60 1169.41 17.54 3.163 0.041 2.01
BEC 102 (M) −72.0291 46.4898 60.1 Ca,Na-HCO3 21.6 20.0 8.9 0.427 −11.29 −77.26 7.95 0.12 1.725 0.022
BEC 103 (M) −72.3201 46.1482 81.7 Ca,Na-HCO3 43.6 7.6 9.6 0.501 −12.57 −88.81 63.35 0.95 4.803 0.062 2.15
BEC 107 (P) −72.2478 46.2156 82.0 Ca-HCO3 36.6 17.5 13.3 0.188 −11.52 −80.31 39.65 0.59 2.260 0.029 1.48
BEC 110 (P) −72.5012 46.1853 49.7 Ca,Na-HCO3 37.8 26.1 8.9 0.346 −11.19 −77.80 60.65 0.91 2.217 0.029 1.48
BEC 112 (M) −71.8732 46.4124 115.0 Ca,Na-HCO3 38.1 4.7 8.6 0.286 −11.90 −84.70 6.70 0.10 2.191 0.028 1.58
BEC 119 (P) −72.0529 46.5095 54.8 Na-HCO3 45.7 34.1 12.0 0.471 −11.51 −81.49 62.92 0.94 2.360 0.031 1.58
BEC 126_1 (P) −71.5454 46.3040 210.2 Ca,Na-HCO3 49.1 3.8 8.8 0.227 −11.77 −82.03 4482.00 67.23 2.819 0.037 2.15
BEC 126_2 (P) 3.8 2662.41 39.94 2.508 0.033 2.08
BEC 137 (P) −71.6311 46.3518 141.6 Na-HCO3 23.7 10.0 8.6 0.350 −11.68 −82.13 11.32 0.17 2.251 0.029 1.65
BEC 138 (P) −71.7041 46.3403 130.6 Ca-HCO3 32.0 3.9 8.9 0.216 −11.85 −82.25 7.72 0.12 2.612 0.034 1.72
BEC 147 (P) −71.8162 46.3475 122.9 Ca-SO4 32.0 6.1 9.6 0.157 −11.87 −83.56 7.51 0.11 2.382 0.031 1.63
BEC 148 (P) −71.7726 46.3266 120.2 Na-SO4 64.6 13.7 8.7 0.109 −11.61 −80.37 12.38 0.19 2.579 0.034 1.63
BEC 149 (P) −71.8032 46.2562 128.1 Ca-HCO3 54.9 8.3 9.5 0.286 −11.87 −81.59 97.94 1.47 2.223 0.029 1.59
F2 PACES −72.2125 46.2252 130.0 Na-SO4 42.0 – 7.2 0.131 −11.53 −79.92 21.22 0.32 2.149 0.028 1.72
F3 PACES −72.2022 46.3511 84.9 Na-Cl 78.3 47.9 7.2 2.175 −14.15 −99.26 45.14 0.68 1.722 0.022 0.52
F4 PACES −71.8462 46.3822 128.5 Na-HCO3 36.6 9 8.5 0.339 −11.67 −79.46 62.30 0.93 1.901 0.025 4.59
F5 PACES −71.9141 46.4507 103.0 Na-HCO3 47.2 17.44 8.0 0.529 −12.25 −83.74 12.77 0.19 1.937 0.025 1.35
F9 PACES −72.4686 46.3260 10.0 Na-HCO3,Cl 35.7 5.1 8.5 0.222 −10.92 −74.44 272.50 4.09 0.996 0.013 1.15
Air/ASW 4.72 1.860 1.31

F = fractured; G = granular; P = private well; M = municipal well; PACES = instrumented wells, drilled in the framework of the PACES project (see text for details).
Air Saturated Water (ASW) values are indicative and calculated for a freshwater with TDS = 0 mg L−1 and T = 10 °C using Smith and Kennedy (1983) equations.
Casing is the length of the casing in the unconsolidated granular aquifer section of wells tapping water in the fractured bedrock.
Granular aquifer's wells have casing all along to the bottomhole which are equipped with a short screen (1 m).
When casing length is not reported for wells in the fractured aquifer it means that the fractured bedrock arrives at the surface with little or no cover (ex. BEC126).

Lawrence Lowlands, is the third most densely populated region in
Canada (158 inhabitants per km2), with agriculture and industry
being the province's main economic drivers. The St. Lawrence Lowlands
is also one of the main regions targeted for shale gas exploitation in
Canada (Lavoie et al., 2013; Pinti et al., 2013; Moritz et al., 2015). For
these reasons, this watershed has been the focus of a detailed aquifer
characterization project funded by the Quebec Ministry of Environment
and by local municipalities (Larocque et al., 2013). Results from this pro-
ject include analyses for solute ion contents, trace elements and stable
isotopes of water (Larocque et al., 2013; Meyzonnat et al., in press).
The focus of the present study is to determine groundwater residence
times using noble gases, tritium (3H) and radiocarbon (14C). The overall
goal was to gain a better understanding of groundwater resources both
in terms of availability and quality, with an eye to future natural
resource exploitation.
2. Geological and hydrogeological background
2.1. Geology
The studied area is located in southwestern Quebec, Canada
(Fig. 1A). It covers 2859 km2 in the southern portion of the Becancour
River watershed and includes eight sub-watersheds that drain into the
St. Lawrence River (Fig. 1A). The northwestern part corresponds to the
St. Lawrence Lowlands, a flat area with elevations less than 150 masl,
while the southeastern part is located in the Appalachians, marked
by an irregular topography with maximum elevations of 500 masl
(Fig. 1B). The two regions correspond to the St. Lawrence Platform
and the Appalachian Mountains geological provinces, respectively. The
St. Lawrence Platform is a Cambrian–Lower Ordovician siliciclastic and
carbonate platform having a thickness of ca. 1200 m, overlain by ca.
1800 m of Middle–Late Ordovician foreland carbonate-clastic deposits
(Lavoie et al., 2013). The Ordovician geological units of the St. Lawrence
Platform outcropping in the study area are the Upper Ordovician
turbiditic Nicolet Fm. (Fig. 1) of the Lorraine Group and the Saint-
Sabine les Fonds Fm. of the Sainte-Rosalie Group. These two formations
are dominated by thick successions of mudstones with subordinate
alternating sandstone and siltstone. Another unit outcropping in the
St. Lawrence Platform is the Becancour Fm. of the Queenston Group
consisting of post-orogenic red shale, sandstone and conglomerate
(Globensky, 1987).
The terrains outcropping in the Appalachian Mountains correspond
to imbricated thrust sheets. In the Becancour watershed area we can
distinguish Cambrian green and red shales (Sillery Group); Ordovician
bedded black and yellowish-weathered shaly matrix containing chaotic
blocks of shales, cherts, sandstone forming the “wildflysch” of the
Etchemin River (Fig. 1); middle Ordovician dolomitic or calcitic schists
of the Sweetsburg and West Sutton Fm. of the Oak Hill Group (Fig. 1)
(Globensky, 1993).
Unconsolidated Quaternary sediments derived from multiple
glaciation–deglaciation cycles cover unconformably the Cambrian–
Ordovician sequence of the St. Lawrence Platform (Lamothe, 1989).
 G. Vautour et al. / Chemical Geology 413 (2015) 94–106 97

H
84 132 20
±1σ Kr ±1σ Xe ±1σ R/Ra ±1σ Ne/22Ne ±1σ 21
Ne/22Ne ±1σ 38
Ar/36Ar ±1σ 40
Ar/36Ar ±1σ

x 10−8 x 10−9

0.02 6.02 0.09 4.13 0.09 0.788 0.021 9.81 0.03 0.0282 0.0002 0.1875 0.0003 297.4 0.7
1.115 0.007
1.500 0.008
1.604 0.010
0.02 5.55 0.08 3.69 0.08 1.077 0.037 9.83 0.03 0.0283 0.0001 0.1873 0.0005 296.5 0.8
1.090 0.025

3.109 0.065
0.414 0.013
0.308 0.005
2.299 0.049
1.912 0.042
0.03 6.95 0.10 3.76 0.08 0.074 0.003 9.87 0.05 0.0288 0.0002 0.1907 0.0016 296.5 3.4
2.316 0.048
0.03 7.51 0.11 4.94 0.11 0.381 0.011 9.81 0.02 0.0285 0.0002 0.1875 0.0006 296.7 0.8
0.02 5.57 0.08 3.87 0.09 0.412 0.009 9.76 0.05 0.0288 0.0001 0.1879 0.0007 295.0 1.1
0.02 5.66 0.08 3.78 0.08 0.172 0.008 9.75 0.05 0.0287 0.0001 0.1876 0.0005 295.3 1.0
0.02 6.15 0.09 4.98 0.11 1.238 0.041 9.85 0.04 0.0282 0.0001 0.1873 0.0005 295.1 0.8
0.02 5.94 0.09 4.07 0.09 0.283 0.014 9.75 0.03 0.0291 0.0002 0.1868 0.0017 297.3 2.1
0.03 7.37 0.11 4.51 0.10 0.039 0.003 9.85 0.05 0.0290 0.0002 0.1874 0.0008 297.4 1.0
0.03 6.94 0.10 4.56 0.10 0.054 0.005 9.84 0.04 0.0293 0.0004 0.1829 0.0012 294.7 1.5
0.02 6.41 0.10 4.66 0.10 0.720 0.019 9.83 0.04 0.0285 0.0001 0.1880 0.0008 295.2 0.8
0.02 6.53 0.10 4.56 0.10 2.005 0.039 9.85 0.03 0.0286 0.0001 0.1878 0.0009 295.0 1.8
0.02 6.31 0.09 4.42 0.10 1.341 0.033 9.76 0.03 0.0285 0.0001 0.1881 0.0007 297.6 0.9
0.02 6.56 0.10 4.65 0.10 0.711 0.014 9.83 0.03 0.0286 0.0001 0.1878 0.0007 293.9 0.9
0.02 6.29 0.09 4.60 0.10 0.344 0.010 9.80 0.04 0.0287 0.0001 0.1884 0.0006 295.5 0.9
0.02 6.56 0.10 4.57 0.10 0.386 0.010 9.85 0.02 0.0277 0.0002 0.1884 0.0010 295.8 1.3
0.01 2.53 0.04 2.01 0.04 0.073 0.003 9.92 0.09 0.0279 0.0002 0.1871 0.0011 296.3 0.8
0.06 11.70 0.18 6.11 0.13 1.043 0.038 9.79 0.01 0.0284 0.0002 0.1864 0.0008 295.3 0.7
0.02 5.14 0.08 3.59 0.08 0.564 0.020 9.91 0.02 0.0273 0.0001 0.1874 0.0008 295.7 1.0
0.01 4.59 0.07 2.43 0.05 0.058 0.002 9.87 0.05 0.0273 0.0002 0.1866 0.0007 297.2 0.8
5.26 3.61 1.000 9.80 0.0290 0.1880 295.5

Quaternary deposits are also found in the Appalachian Mountains, in
the most heavily incised river valleys. A nearly continuous till sheet
(Gentilly till) covers most of the area between the overlain discontinu-
ous marine and lacustrine silt (Lampsilis Lake silts) and clay units of the
Champlain Sea (11.2 to 9.8 kyrs old) and the underlain discontinuous
patches of sand deposited during marine regressions (Vielles Forges
and Lotbinière sands; Lamothe, 1989) with an optical stimulated lumi-
nescence (IRLS) measured age of 44–50 ka (Godbout, 2013).
2.2. Hydrogeology and hydrogeochemistry
The regional aquifer is located in the fractured bedrock consisting
of the Cambrian–Ordovician schists and shales of the Appalachian
Mountains and St. Lawrence Platform. This aquifer is mainly unconfined
in the Appalachian Mountains and in the Appalachian piedmont,
progressively becoming semi-confined, northwesterly. In a 10 km
wide zone bordering the St. Lawrence River, the aquifer is confined by
thick marine clay of the Champlain Sea and receives limited recharge
(Larocque et al., 2013).
The hydraulic conductivities of the studied aquifer are low to
moderate (~10−9–10−6 m s−1) and porosities are variable, between 1
and 5% porosity equivalent for the Ordovician fractured regional
aquifer to effective porosities of 10–20% for the Quaternary granular
aquifer (Larocque et al., 2013). Wells in the fractured bedrock aquifer
yield enough water to supply single-family dwellings and, in a few
areas, small- to medium-size municipalities (1000–20,000 inhabitants).
Only one medium- to high-yield aquifer exists in Quaternary
glaciofluvial coarse-grained surficial sediments, the “Vielles Forges”
aquifer (Lamothe, 1989), but spatial extent remains undefined
(Lamothe, 1989; Godbout, 2013). The granular Quaternary aquifer is
separated from the fractured bedrock aquifer by a basal till aquitard
unit (Becancour till; Lamothe, 1989). Regional groundwater flow is
SE–NW and usually follows the topography, with recharge occurring
mainly in the Appalachian Mountains and discharge in the main
tributaries of the St. Lawrence River (Fig. 1B). Local recharge areas are
also found in the plain, along a band located just northwest of the
Appalachian piedmont, where the Champlain Sea clays are absent
(Larocque et al., 2013).
Groundwater in the Becancour watershed is characterized by low-
salinity with Total Dissolved Solids (TDS) ranging from 0.5 to 2.2 g L−1
(Table 1). Water types are dominated by Ca-HCO3 and Na-HCO3 with
a few samples showing Na-SO4 and Na-Cl chemistry (Meyzonnat
et al., in press). Freshwater in the Appalachian recharge acquires
Ca–Mg-HCO3 and Ca–Na-SO4 chemistry through interactions with
limestone units of the St. Lawrence Platform. This water evolves toward
a Na-HCO3 type by Ca2+–Na+ ion exchange, where Ca2+ water exchanges
with Na+ mineral (Cloutier et al., 2006, 2010) in semi-confined aquifers. Fi-
nally, close to the St. Lawrence River, groundwater evolves into a Na-Cl
type with salinity likely derived from exchange of freshwater with pore
seawater trapped in the Champlain Sea clays or the fractured rock
aquifers, in particular in areas confined by thick marine clay with
limited recharge.
98 G. Vautour et al. / Chemical Geology 413 (2015) 94–106
The stable isotope (δ18O, δD) composition of the groundwater is
shown in Fig. 2. With the exception of F3 and BEC124, water samples
yield a relatively narrow δ18O range value with a mean of − 11.6 ±
0.6‰ (Fig. 2). This value is similar to the δ18O annual mean of
− 11.15‰ calculated from forty-one precipitation data measured
at two local stations of Lemieux and Saint Ferdinand (Quebec)
(Meyzonnat, 2012). The sampled groundwater δ2Η and δ18O values
fall slightly below the LMWL (Local Meteoric Water Line) established
on the data collected from these two stations, indicating a slight enrich-
ment in 18O due to evaporation. No significant variations are found in
the δ18O values between groundwater from the granular and fractured
aquifers. This uniformity in δ18O values might point to modern
precipitation as a common origin for groundwater in both aquifers.
Alternatively, uniform δ18O values might result from well-mixed
groundwater sources in these aquifers. F3 and BEC124 deviate from
this trend with more depleted δ18O values than the average. F3 is
located in the plain and taps a confined aquifer (Larocque et al., 2013).
Groundwater chemistry is of Na-Cl type and yields a TDS value of
2.2 g L−1, which is 10 times the median value for all sampled groundwa-
ter in Becancour (0.284 g L−1; Table 1). Thus, one cannot exclude the
possibility that part of the water might be fossil and recharged during
a colder period. Well BEC124 is drilled in an unconfined aquifer located
in the Appalachians and is weakly mineralized (TDS = 0.053 g L−1). It is
possible that groundwater recharge in this well is dominated by spring
snowmelt rather than summer rainfall, which would explain the more
depleted δ18O value (Fig. 2).
3. Sampling and analytical methods
Twenty-eight groundwater samples (two duplicates: BEC010 and
BEC126) were collected at depths ranging between 2.2 and 78.3 m
(Fig. 1; Table 1). Twenty-three samples were collected from municipal
and domestic wells, while five (F2, F3, F4, F5 and F9; Table 1) are from
instrumented wells drilled by our research group for monitoring
purposes. Six wells are tubular wells with screen at their bottom
to tap groundwater from shallower Quaternary granular aquifers.
Twenty-two wells tap water from the fractured bedrock aquifer.
These latter are equipped with casing in the section crossing the uncon-
solidated Quaternary granular aquifers (casing length; Table 1) and
down 1–2 m into the bedrock. In the remaining bedrock section, they
are open boreholes. When information on the casing length was not
available from the owners, the length of the Quaternary deposits was
calculated rather precisely from detailed maps of the Quaternary
deposits (Larocque et al., 2013). With the exception of wells BEC101,
BEC110 and F5, which are drilled in a confined section of the fractured
bedrock aquifer, all the other wells are drilled in unconfined or semi-
confined aquifers.
Groundwater was collected for noble gas measurements at the
instrumented piezometers using a Waterra® Inertial Pump System
which consists of a foot valve fixed at the bottom of a high-density
polyethylene tube with a variable diameter of 5/8 in. to 2 in. and an elec-
tric actuator pump Hydrolift-2®. In municipal wells, water was
collected directly at the wellhead. In domestic wells water was collected
at the closest water faucet, taking precautions to avoid intermediate
reservoirs where the water could undergo degassing. Water was purged
from wells and piezometers until measurement of chemo-physical
parameters (conductivity, pH, Eh, temperature) stabilized. Water was
subsequently allowed to flow through armored PVC tubes connected
to 3/8-inch diameter, refrigeration-type copper tubes. After a few mi-
nutes, two steel clamps were closed and the sealed tube was recovered.
All stable noble gases (He, Ne, Ar, Kr, Xe) were measured in twenty
groundwater samples (BEC126 as duplicate) at the Noble Gas Laborato-
ry at the University of Michigan (Table 1). The remaining eleven
samples (BEC010 as duplicate) were analyzed only for helium isotopic
composition and Ne concentrations at the University of Tokyo
(Table 1). At the University of Michigan, water samples were attached
to a vacuum extraction system and noble gases were quantitatively
extracted for inletting into a MAP-215 mass spectrometer. Extracted
gases were passed over to a Ti sponge getter to remove reactive gases,
and sequentially allowed to enter the MAP-215 mass spectrometer
using a cryo-separator. The cryo-separator temperatures were set at
35, 65, 200, 215, and 270 K for analysis of He, Ne, Ar, Kr and Xe, respec-
tively. The 4He, 20Ne, 22Ne, 36Ar and 40Ar were measured using a Faraday
detector while 38Ar and all other isotopes were measured using an
electron multiplier in ion counting mode. During neon isotope analysis
a liquid N2 cold trap was applied to minimize peak interferences and
appropriate mass peaks were monitored to correct for interferences
of 40Ar++ and H18 +
2 O on
20
Ne and CO++
2 on 22Ne. The interference cor-
20 22
rections for Ne and Ne were typically ~1.1% and 0.17%, respectively.
Prior to each sample analysis, a calibrated amount of air standard was
analyzed following a procedure similar to that of the sample measure-
ment and blank correction was applied. Isotopic abundances for each
sample are normalized to the air standard after blank correction.
Elemental abundances of 4He, 22Ne, 36Ar, 84Kr, and 132Xe have typical
uncertainties of 1.5, 1.3, 1.3, 1.5 and 2.2%, respectively and all uncer-
tainties are at ±1 σ level. Additional details on the noble gas analytical
procedures can be found in Castro et al. (2009).
At the Atmospheric and Ocean Research Institute (AORI) of the
University of Tokyo, samples were degassed offline using a dedicated
line and recovered gas was collected in a lead-rich glass ampoule. The
ampoule was connected to a stainless steel line for purification on a
Ti-getter and cryogenic separation of He from other noble gases. The
helium aliquot was then analyzed for the 3He/4He isotopic ratio using
a Helix SFT calibrated against the HESJ standard (Helium standard of
Japan; Matsuda et al., 2002). Precision on the 3He/4He ratio of HESJ is
typically ± 0.2% (2σ) (Sano et al., 2008). Prior to being cryogenically
adsorbed, the amount of 20Ne was measured on a Balzers QMS Prisma
80 connected to the preparation line.
Water samples for tritium analysis were collected using 1 L
Nalgene® bottle filled up and sealed before shipment to the Environ-
mental Isotope Laboratory at the University (EIL) of Waterloo. Liquid
scintillation counting (LSC) is the technique used by EIL for quantifica-
tion of tritium. Samples analyzed for tritium are enriched 15 times by
electrolysis and subsequently counted. The detection limit for enriched
samples is 0.8 TU (Table 3). EIL uses a scintillation cocktail having a high
Fig. 2. D vs. δ 18 O plot for the Becancour groundwater, plotted against the Local
Meteoric Water Line (LMWL), calculated from data recorded at Lemieux and Saint
Ferdinand (Quebec) stations (Meyzonnat, 2012). Stars represent the mean δD vs.
δ 18 O of local rainfall during summer and winter seasons, measured from data of
Lemieux and Saint Ferdinand stations. Black dots are groundwater from the regional
fractured Ordovician aquifer while white dots represent groundwater from the
granular Quaternary aquifer.
Table 2
3
H–3He, 14C and (U–Th)/He groundwater ages of Becancour.
3 3 3
Well name H activity TU ± He tritiogenic × ± H/3He ± A14C ± δ13C DIC 14
C age A0 = 100 14
C age adjusted 4
Heeq 4
Heea 4
Heterr (U–Th)/4He
10−14 cm3 age yrs activity measured NETPATH yrs F&G NETPATH yrs −8
x 10 3
cm STP g−1 age
STP g−1
H2O measured ‰ VPDB (±0.5%) (±20‰) H2O

pMC % in situ yrs

Quaternary granular aquifer

BEC 105 – – – – – – 104.83 0.27 −13.8 208 −1133 4.70 0.98 3.55 6745
BEC 106 16.09 0.94 3.20 1.47 10.44 0.46 – – – – – 4.75 0.87 1.50 2846
BEC 113 7.62 0.94 9.00 2.39 31.06 1.81 – – – – – 4.75 5.22 1.11 2118
BEC 117 13.59 1.07 5.20 1.43 16.54 0.85 – – – – – 4.76 0.87 −0.27 −514

G. Vautour et al. / Chemical Geology 413 (2015) 94–106

BEC 118 17.17 0.98 0.71 1.22 2.72 0.14 119.64 0.28 −17.0 −1482 0 4.66 1.42 Modern
BEC124 10.72 0.85 0.81 0.97 4.70 0.33 – – – – – 4.71 0.10 182

Ordovician fractured aquifer

BEC 009 8.45 1.30 25.84 3.74 45.98 2.53 – – – – – 4.71 1.23 2.08 677
BEC 010_1 8.73 1.49 8.53 1.86 28.34 2.41 – – – – – 4.70 1.03 46.81 15,208
BEC 010_2 9.40 1.60 7.35 1.79 25.26 2.30 – – – – – 4.70 1.30 65.25 21,197
BEC 021 9.53 0.88 11.94 2.10 31.93 1.36 – – – – – 4.70 0.30 0.98 317
BEC 034 6.81 1.07 8.34 1.68 31.60 2.32 – – – – – 4.73 0.96 311
BEC 101 – – – – – – 21.77 0.14 −7.3 15,426 6696 4.73 4.35 1160.33 376,960
BEC 102 9.37 0.86 18.12 2.73 38.59 1.45 – – – – – 4.73 3.22 1046
BEC 103 – – – – – – 69.60 0.21 −13.7 4258 470 4.77 9.19 49.39 16,046
BEC 107 – – – – – – 89.85 0.26 −15.6 891 −3883 4.65 1.34 33.67 10,937
BEC 110 – – – – – – 54.78 0.19 −16.2 5081 147 4.67 1.19 54.80 17,803
BEC 112 – – – – – – 67.18 0.21 −12.7 3288 −685 4.75 0.80 1.16 378
BEC 119 0.72 0.36 3.22 1.36 52.24 8.42 34.15 0.16 −10.6 11,214 4551 4.71 1.54 56.67 18,411
BEC 126a 4.41 0.63 31.05 5.51 60.03 2.45 43.21 0.18 −17.9 7978 2535 4.79 2.90–1.88 4474–2656 1.45–0.86 Ma
BEC 137 – – – – – – 41.14 0.17 −13.0 7342 2029 4.79 1.01 5.57 1808
BEC 138 – – – – – – 64.77 0.22 −14.9 3590 −676 4.75 2.20 0.77 250
BEC 147 8.58 0.73 5.14 1.46 21.79 1.07 65.95 0.20 −12.8 4933 1027 4.74 1.50 1.28 416
BEC 148 1.73 0.37 2.47 1.41 33.85 3.18 43.17 0.17 −15.6 6953 1653 4.72 2.04 5.60 1819
BEC 149 6.95 0.64 11.78 1.99 36.53 1.43 – – – – – 4.74 0.94 92.27 29,974
F2 PACES 0.85 0.57 2.68 1.28 46.45 10.98 – – – – – 4.73 0.66 15.78 5128
F3 PACES – – – – – – – – – – – 4.78 −4.28 45.14 14,664
F4 PACES 9.09 1.04 7.31 8.16 25.64 1.56 – – – – – 4.29 54.53 3.19 1035
F5 PACES 0.76 0.38 2.67 1.26 48.31 8.30 – – – – – 4.58 0.43 7.75 2517
F9 PACES 4.55 0.85 −0.36 0.92 −6.75 1.54 – – – – – 4.59 −2.36 270.30 87,814
F9b – – 11.20 1.99 (42.51) (3.03) – – – – – 4.56 – – –
a
Helium ages are calculated for samples (1) and (2) respectively. 3H/3He age if from data of sample BEC126_2.
b
Because of the choice of Rterr, it was not possible to calculate a 3H/3He age. Assuming a Rterr of 0.012Ra (Pinti et al., 2011) a minimum age of 42.5 ± 3.0 yrs is obtained.

99
100 G. Vautour et al. / Chemical Geology 413 (2015) 94–106

carrying capacity for water with high efficiency and low background Table 3
(Heemskerk and Johnson, 1998). Noble gas temperatures (NGT) in selected groundwater samples of the Becancour
watershed.
Carbon species (TDIC) were converted into CO2 by direct acidifica-
tion, and the 13C content in the purified CO2 fractions was measured Sample name NGT ± χ2 Excess air ± ΔNe
by mass spectrometry (SIRA) at the IDES Laboratory (University of (°C) (cm3) (%)

Paris Sud, France). 13C content is reported using conventional δ (‰) Quaternary granular aquifer
notation as a deviation from the V-PDB (Vienna-Belemnite from the BEC 105 5.36 0.34 1.90 0.0019 0.0002 14.01
BEC 118 8.29 0.86 11.51 0.0027 0.0005 19.47
Pee Dee formation, North Carolina, USA) (Table 2). Graphite targets
for 14C analyses were prepared from pure CO2 fractions at the IDES Ordovician fractured aquifer
Laboratory, and sources were measured by accelerator mass spectrom- BEC 101 4.32 3.56 205.02 0.0083 0.0026 41.61
BEC 103 2.77 0.54 3.75 0.0175 0.0005 59.66
etry (ARTEMIS accelerator of the UMS LMC14 of INSU-CNRS, Gif-sur-
BEC 107 7.74 0.50 3.89 0.0026 0.0003 18.51
Yvette, France). 14C content is expressed as a percentage of modern BEC 110 7.65 0.66 6.95 0.0023 0.0003 16.69
carbon (pMC) (Table 2). BEC 112 3.15 1.11 23.17 0.0015 0.0006 11.43
In order to calculate the production rate of radiogenic 4He in ground- BEC 119 5.86 0.73 9.04 0.0029 0.0004 20.39
water, the parent elements U and Th were measured from rock cores BEC 126_1 −0.40 3.02 189.49 0.0055 0.0023 31.36
BEC 126_2 −0.11 2.95 186.969 0.0036 0.0020 22.89
recovered from wells of the Becancour watershed (Table 4). U, Th and
BEC 137 2.53 0.54 5.62 0.0019 0.0003 14.07
K concentrations were measured by neutron activation at the Slowpoke BEC 138 2.88 0.69 8.52 0.0042 0.0005 26.33
Laboratory at the University of Montreal. BEC 147 3.68 0.50 4.63 0.0029 0.0003 19.70
BEC 148 3.25 0.34 0.85 0.0039 0.0002 24.95
BEC 149 3.25 0.34 2.23 0.0018 0.0002 13.30
4. Results
F2 PACES 1.68 1.13 26.36 0.0013 0.0007 9.50
F4 PACES 9.75 1.09 2.72 0.1041 0.0016 90.48
In Table 1 He, Ne and Ar, Kr and Xe concentrations and He, Ne and Ar F5 PACES 9.70 0.47 3.48 0.0008 0.0002 6.91
isotopic ratios are reported for the wells analyzed at the University of F9 PACES 14.42 3.20 171.90 −0.0045 0.0008 −73.16
Michigan. He and Ne concentrations and He isotopic ratios are reported
for samples analyzed at the University of Tokyo. Well location, depth
and altitude together with water chemistry type, temperature, Total ΔNe (%), given as ([Ne]measured/[Ne]atmospheric equilibrium − 1 ×100;
Dissolved Solids (TDS) and δ18O and δD are also given in Table 1. Table 2) reflects the total amount of excess air (e.g., Aeschbach-Hertig
Helium concentrations vary over several orders of magnitude, et al., 2001).
from atmospheric (ASW or Air Saturated Water at 10 °C;
4.59 × 10 − 8 cm 3 STP g− 1
rock ) values to 4.48 × 10
−5
cm 3 STP g − 1
rock 5. Discussion
(BEC126_1; Table 1), pointing to significant accumulations of
terrigenic 4 He. BEC010 was sampled twice in 2012 and 2013. The 5.1. 3H/3He ages
4
He concentration in 2012 is 5.25 × 10− 7 cm3 STP g− 1
rock, 35% lower
−7
than the amount measured in 2013 (7.13 × 10 cm 3 STP g − 1
rock ). Helium in groundwater is the sum of several components: the
BEC126 was also sampled twice, showing very large differences above-mentioned Heeq and Heea, together with terrigenic helium
in the amounts measured, from 4.48 × 10− 5 cm 3 STP g − 1
rock to (Heterr) produced by U–Th decay in the crust and/or mantle-derived
−5 3 −1
2.65 × 10 cm STP grock (Table 1). These variations could be due helium, and helium from decay of tritium (3Hetri). The proportions of
to the natural variability over short and long sampling time intervals. tritiogenic and terrigenic helium in the sampled groundwater can be
Indeed, natural concentration variability in other groundwater flow visualized in a Weise-type plot (Fig. 3; Weise and Moser, 1987). In
systems where degassing has not taken place has been previously this plot, the excess-air-corrected helium isotopic ratio (3Hetot–3Heea)/
observed (e.g., Warrier et al., 2012). (4Hetot–4Heea) is plotted versus the inverse of the normalized excess-
3
He/4He (R) values, normalized to that of the atmosphere (Ra = air-corrected helium concentration 4Heeq/(4Hetot–4Heea). An addition
1.386 × 10−6; Clarke et al., 1976), range from R/Ra = 0.039 ± 0.003
(BEC126_21) to 3.109 ± 0.065 (BEC009; Table 1). These ratios point
to the presence of tritiogenic 3He and terrigenic He. Ne isotopic ratios
(20Ne/22Ne from 9.75 to 9.92; 21Ne/22Ne from 0.0273 to 0.0293)
and Ar isotopic ratios (38Ar/36Ar from 0.1829 to 0.1907; 40Ar/36Ar
from 293.9 to 297.6) are all also atmospheric within uncertainties
(Table 1).
Table 2 reports calculated 3H/3He ages and 14C uncorrected and
corrected ages using complex inversion technique models from
NETPATH (Plummer et al., 1994). Tritium was measured in 19 water
samples to calculate 3H/3He ages (Table 2). Measured tritium values
range from the detection limit of 0.8 TU (BEC119 and F5) to 19.3 TU
(BEC118) (Table 2). The uncorrected 14C (A14C) activity ranges from
21.8 ± 0.1 pMC for BEC101 to 119.6 ± 0.3 pMC for BEC118, while
δ13C values range from −17.9‰ to −7.3‰ (Table 2).
The measurements of all noble gases dissolved in groundwater were
used to calculate the recharge noble gas temperatures (NGT) using
the unfractionated air (UA) model (Stute and Schlosser, 1993), imple-
mented in the inverse model of Ballentine and Hall (1999). Resulting
temperatures ranges from −0.4 ± 3.0 °C (BEC126_1) to 14.4 ± 3.1 °C Fig. 3. Weise-type plot of helium measured in Becancour groundwater. The lowermost
line represents the mixing between water at the recharge (Air Saturated Water or ASW
(F9) (Table 3). The model allows one to estimate the helium in solubility
with Req of 0.983Ra) and water enriched in radiogenic 4He (Rterr = 0.012Ra). Dashed
equilibrium with the atmosphere (Air Saturated Water He or Heeq) and lines interpolated through samples represent the addition of 3, 11, 21, 34, 51, 81 and
the excess air helium (Heea) which results from air bubbles entering the 104 TU helium, mixed with the terrigenic components having variable Rterr. Gray stars
water table and dissolved in groundwater (Heaton and Vogel, 1981). represent the ASW and terrigenic helium end-members. Symbols are the same as Fig. 2.

of only 3Hetri will move the points up, along the right-hand side Y-axis
from an initial ASW isotopic composition (Req = Ra × 0.983; Benson
and Krause, 1980). Addition of 3Heterr produced by nucleogenic
reactions with Li (Morrison and Pine, 1955), 4Heterr from α-decay of U
and Th in crustal rocks or both 3He and 4He from addition of a mantle
component will shift points on the left side of the plot to the local Rterr
value. Rterr corresponds to the time-integrated ratio from 3He and 4He
radiogenic production and/or mantle He addition.
Mixing between the different end-members will be represented by a
straight line of equation Y = mX + b (Weise and Moser, 1987):

 !
3
Hetot −3 Heea 3
Hetri

 ¼ Req −Rterr þ 4
4
Hetot − Heea 4 Heeq
|fflfflfflfflfflfflfflfflfflfflfflfflfflffl{zfflfflfflfflfflfflfflfflfflfflfflfflfflffl} |fflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflffl{zfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflffl} |fflfflfflfflfflfflfflfflfflfflffl{zfflfflfflfflfflfflfflfflfflfflffl}
m X
Y
In a Weise-type plot, samples align on several straight lines
representing the mixing between groundwater accumulating 3Hetri
decayed from a constant amount of tritium and terrigenic helium
(Fig. 3). From the slope “m” and the Y-intercept “b” of each mixing
line it is possible to calculate the Rterr and the initial 3H amount. Water
samples plot on mixing lines corresponding to the decay of 3 to 104
TU 3H and with Rterr ranging between 5.99 × 10−8 and 2.95 × 10−7. As-
suming a typical crustal Rterr of the St. Lawrence Platform fractured bed-
rock is 1.66 × 10−8 (Pinti et al., 2011), then the calculated Rterr from
each mixing line suggest the addition of 0.4 to 2.5% of mantle helium
(Fig. 3). Although small, the mantle component is nevertheless non-
negligible. Interestingly, a mantle helium of ~2–3% was also identified
in deeper brines residing at the base of the Ordovician geological forma-
tions of the St. Lawrence Platform near the Becancour municipality
(Pinti et al., 2011), in the same watershed (Fig. 1).
To calculate the 3H/3He ages, 3Hetri was estimated following the
equation (Schlosser et al., 1989):
 
3
Hetrit ¼ 4 Hetot  ðRtot −Rterr Þ−4 Heeq  Req −Rterr
!
4
He 
− 20  20 Netot −20 Neeq Þ  ðRea −Rterr Þ
Ne
ea
where Rtot is the measured 3He/4He ratio; Req = α*Ratm with α
representing a fractionation factor of 0.983 (Benson and Krause,
1980). Ratm and (4He/20Ne)ea are generally assumed to be atmospheric
(Ratm = 1.386 × 10−6; [4He/20Ne]exc = 0.3185; Ozima and Podosek,
1983). 4Hetot and 20Netot is the measured amount of 4He and 20Ne in
the groundwater sample (Table 1). 4Heeq and 4Heea are calculated
from the recharge temperatures (NGT; Table 3). 20Neeq is calculated as
20
Neeq = 20Netot − 4Heeq/(4He/20Ne)ea = air. For samples BEC09, 010,
021, 034, 102, 106, 113, 117 and 124, only the 20Ne amount has been
measured. In this case, the 4Heeq (and 20Neeq) is calculated using
solubility data from Smith and Kennedy (1983) on the basis of the
present day temperature measured in the well (Table 1). Because the
He and Ne solubility variability is relatively small at the expected
recharge temperatures of 0–15 °C (Table 3), this approximation can be
considered acceptable. Uncertainty in the calculated 3Hetri is the propa-
gated error taking into account all uncertainties on each variable of
Eq. (2).
Calculated 3H/3He apparent ages are reported in Table 2. The youn-
gest 3H/3He apparent age of 2.7 ± 0.1 yrs is from the shallowest water
sample (BEC118) from the granular Quaternary aquifer (Fig. 1). The
oldest 3H/3He age is 60.0 ± 2.5 yrs and was measured in sample
BEC126_2 from the fractured bedrock aquifer, in the Appalachian
recharge area (Fig. 1). To evaluate the validity of 3H/3He groundwater
ages, the initial amount of 3Hinit = 3H + 3Hetri prior to decay was
compared with the 3H in precipitation at the Ottawa GNIP station
(IAEA/WMO, 2004; Fig. 4). The curve that fits the measured 3H at the
GNIP station represents the yearly average.
G. Vautour et al. / Chemical Geology 413 (2015) 94–106 101
4
Heeq
4 þ Rterr : ð1Þ
Hetot −4 Heea |ffl{zffl}
b
Fig. 4. Initial tritium content (3H + 3Hetri) of groundwater compared with 3H in precipita-
tion as recorded at the GNIP station of Ottawa (IAEA/WMO, 2004). The curve that fits the
measured 3H at the GNIP station represents the yearly average. Symbols are the same as
Fig. 2.
The majority of samples fall within the calculated yearly-averaged
Ottawa tritium input curve. Samples BEC148, BEC119, F2 and F5
fall below the line, suggesting a dilution of the initial 3H input by pre-
bomb water (Aeschbach-Hertig et al., 1998), which is virtually free of tri-
tium. The dashed curve represents a two-component mixture containing
25% of water recharged at the time and 75% of pre-bomb water, and can
explain the low 3Hinit recorded in BEC148. The dashed and double dotted
curve represents a two-component mixture containing 2% of water
recharged during the observed period and 98% of pre-bomb water, and
can explain the low 3Hinit calculated for BEC119, F2 and F5.
ð2Þ 5.2. 14C ages
Uncorrected 14C activities (A14C) show a rough inverse trend with
the HCO− 13
3 content (Fig. 5a), as well as with the δ C value of the TDIC
(Fig. 5b). These correlations suggest an evolution of groundwater with
age, with post-bomb freshwater (represented by sample BEC118)
dissolving biogenic soil CO2 (A14C = 120 pMC, Levin et al., 1992;
δ13C = − 20‰, Taupin, 1990; HCO− 3 ~ 0), which evolves with time
and accumulates dead carbon from carbonate dissolution (A14C = 0
pMC; δ13C = 0‰; HCO− 3 ≫ 0; Le Gal Lasalle et al., 2001; sample
BEC101). Uncorrected A14C vs. δ13C suggests the occurrence of a third
source of carbon in the watershed (Fig. 5b). This reservoir is also
enriched in dead carbon (A14C ~ 0 pMC; Fig. 4) but it displays a δ13C of
less than −20‰, indicating an organic origin.
This third dead carbon reservoir could be related to thermogenic
methane. Groundwater from the regional fractured aquifer of the St.
Lawrence Lowlands contains methane with measured concentrations
in the Becancour wells ranging from 0.0008 to 32.7 mg L−1 (BEC101)
with a median value for the watershed of 0.133 mg L−1 (Moritz et al.,
2015). Measured δ13C ranges from − 103.6 to − 24.8‰ indicating the
mixing between biogenic methane produced by methanogenesis and
thermogenic methane produced in the Ordovician age Utica and
Lorraine shales. These reservoirs contain methane with a δ13C varying
between −30‰ and −40‰ (Moritz et al., 2015). The sample that devi-
ates most from a simple binary mixing between a dead carbon reservoir
(Ordovician limestone) and biogenic CO2 from soil respiration is
BEC126 (Fig. 5b) which has a methane concentration (2.4 mg L− 1),
well above the expected natural background level of 0.133 mg L−1.
BEC126 also displays a δ13C(CH4) value of −59.4‰, suggesting a mixed
source of methane (Moritz et al., 2015).
During methanogenesis, CO2 reduction is accompanied by strong
carbon fractionation of the DIC. For an initial organic substratum with
102 G. Vautour et al. / Chemical Geology 413 (2015) 94–106
Fig. 5. Inverse trends between the measured 14C activity (A14C) and HCO−
3 concentrations
(in mg L−1) of groundwater (a); and the measured δ13C of the TDC (b). Dead carbon
14
reservoir isotopic composition and C activities are taken from Taupin (1990) (soil
CO2); Le Gal Lasalle et al. (2001) (carbonates); and Moritz et al. (2015) (thermogenic
methane δ13C for Utica and Lorraine shale).
δ13C = − 25‰, methane and DIC products would have δ13C values of
− 60‰ and + 10‰ respectively (e.g., Whiticar, 1999). This is not
observed here (Fig. 5b). However, Moritz et al. (2015) have shown
that most of the methane in St. Lawrence Lowlands has been affected
by oxidation. During methane oxidation, strong fractionation of meth-
ane is not associated with that of DIC (ε 13CCO2–CH4 = 5‰; Whiticar,
1999). This process could explain why this old carbon reservoir
(A14C ~ 0 pMC) has an unfractionated δ13C of less than −20‰ (Fig. 5b).
The initial 14C activities (A14
o C) of Becancour groundwater have been
modified by the numerous water–rock interactions affecting the studied
aquifers, including calcite and dolomite dissolution and Ca/Na ion
exchange (Meyzonnat et al., in press), as well as isotope exchange
between soil CO2, calcite and DIC during recharge, and methanogenesis
(Geyh and Künzl, 1981).
There are several well-known methods for calculating A0 and thus
14
C ages (see e.g., Fontes, 1992; Plummer and Glynn, 2013 for a review).
The method of Fontes and Garnier (1979) takes into account the disso-
lution of carbonates and Ca/Na exchange but it is limited to inorganic
carbon dissolution (DIC) reactions (Plummer and Glynn, 2013). For
more complex aquifers in which carbonate systems undergo complex
geochemical reactions, such as oxidation of organic carbon and
methanogenesis, adjusted radiocarbon ages are best estimated by
inverse geochemical modeling techniques such as those implemented
in the software NETPATH (Plummer et al., 1994; Aravena et al., 1995).
Here we use NETPATH-WIN® software (El-Kadi et al., 2011) to calcu-
late uncorrected and adjusted 14C ages (Table 2). NETPATH uses water
chemistry and δ13C ratios to correct 14C activity by accounting for
mass transfers of carbon that occur along a flow path between an initial
water location, where the initial 14C activity (A0) is fixed, and a final
water composition, where the 14C activity has been measured (Aobs).
NETPATH calculates the term AND, which is the 14C activity at the final
well, adjusted for all inorganic and organic chemical reactions, but not
radioactive decay (El-Kadi et al., 2011). The adjusted 14C age (14CADt)
will be the age increment between initial and final wells calculated as
follows (El-Kadi et al., 2011):
 
14 5730 AND
CAD t ¼ ln : ð3Þ
ln2 Aobs
Ideally, young but tritium-free pre-bomb water should be used as
the initial water where the 14C activity A0 is fixed. Based on the trends
exhibited in Fig. 5a–b, BEC118 is assumed to represent the initial
water even though it contains a small amount of post-bomb tritium
and post-bomb 14C (Tables 2, 3). Indeed, no entirely tritium free pre-
bomb samples are available. Further, the initial and final water chemical
compositions are expected to represent the water chemical/isotopic
evolution along a flow path from the recharge to discharge area. Our
end-members (BEC118, BEC101, BEC126; Fig. 5) represent the shallow
and deep compositions in the down-gradient portion of the basin.
Uncorrected 14C ages obtained with NETPATH range from 15,426 yrs
for BEC101 to 208 yrs for BEC105. Uncertainties on the 14C uncorrected
ages are estimated to be ±0.5% of the value and related to the analytical
uncertainties of the measured A14C (Table 2). Adjusted 14C between
BEC118 and individual wells, using the F & G model implemented in
NETPATH, range from 6696 yrs for BEC101 to 147 yrs for BEC110. Neg-
ative 14C ages for BEC105, 107, 112 and 137 suggest groundwater infil-
trated since the mid-1950s (Table 2). Uncertainties in the adjusted ages
depend essentially on the assumed δ13C of soil CO2, as calculated with
the thermodynamics model 3 (dissolved CO2 is in isotopic equilibrium
with the soil gas) and model 4 (recharge water evolved under open sys-
tem conditions) proposed in NETPATH, which is the most realistic
(Plummer and Glynn, 2013). The average uncertainty on the adjusted
ages has been evaluated to be ±20% of the value (Table 2).
Uncorrected 14C values are in the range of those calculated by
Beaudry (2013) in the same Ordovician regional fractured aquifer of
the St. Lawrence Lowlands in the eastern portion of the Monteregie
region (14C from 13,800 to 910 yrs; Beaudry, 2013), located approxi-
mately 100 km SW of the Becancour watershed. Uncorrected older 14C
ages of 15 to 13 kyrs (this study; Beaudry, 2013) are roughly coincident
with the end of the glaciation and the ice retreat of the 3 km thick
Laurentide Ice sheet in the region. This was followed by a glacio-
isostatic marine transgression, known as the Champlain Sea, which
invaded the area at 12.8–12.3 kyrs (Parent et al., 1985). Between 10.6
and 6.7 kyrs, the main phase of isostatic rebound lowered the St.
Lawrence River base level from + 60 masl to approximately 16 masl,
followed by some fluctuations until 1000 yrs ago (Lamarche et al.,
2007). At 6.7 kyrs, the hydrographic network of the St. Lawrence Valley
reached a configuration close to the present one. It is expected that dur-
ing this accelerated isostatic rebound period, new emerging recharge
areas and increased potentiometric heads favored a large meltwater in-
vasion into the Quaternary shallower aquifers, and the confined aquifers
of the St. Lawrence Basin. Most of the groundwater samples from the
fractured bedrock aquifer of Becancour show 14C uncorrected ages
within this period of regional re-organization of the hydrological system
(Table 2). Calculated noble gas recharge paleotemperatures (NGT;
Table 3) do not show a clear trend with the uncorrected 14C or the
adjusted 14C ages. The majority of the groundwater samples from the
fractured bedrock aquifer show NGTs from − 0.40 ± 3.02 to 5.86 ±
0.73 (Table 3), 4 to 9 °C below the present-day recharge temperature
of 8–10 °C, suggesting that this groundwater recharged in a cooler
 G. Vautour et al. / Chemical Geology 413 (2015) 94–106
period, possibly at temperature approaching 1 °C. NGT measured in
shallower aquifers in the Michigan Basin have already revealed a
ground temperature of 1 °C toward the end of the Last Glacial Maximum
suggesting that groundwater recharge occurred under the Laurentide
Ice Sheet cover (Ma et al., 2004).
Calculated 14C groundwater ages for samples BEC119, BEC148 and
BEC126 are much older than the calculated 3H/3He ages for the same
wells (Table 2). This apparent contradiction in age could result from
mixing of old groundwater with modern water, as suggested by the de-
viation of the 3Hinit composition from the yearly-averaged Ottawa-GNIP
tritium input curve for samples BEC148 and BEC119 (Fig. 4). This mixing
could take place along the well casing or within the fractured aquifer.
Mixing of groundwater from the granular aquifer with fossil water
from the fractured aquifer within the well is unlikely, because the well
casing prevents groundwater from the granular deposits. Thus we can
assume that this mixing is produced within the fractured regional
aquifer as in situ groundwater mixes with recharge water.
The relation between uncorrected 14C ages and the 3He/4He ratios
(Fig. 6) highlights the mixing between young and old groundwater.
One trend corresponds to the mixing between freshwater from the
Quaternary shallower aquifer (BEC118) showing a nearly atmospheric
3
He/4He ratio of 1.077 ± 0.037 Ra and modern 14C ages (Fig. 6) and
fossil water from the fractured bedrock aquifer (BEC126/2) enriched
in radiogenic 4He (3He/4He = 0.054 ± 0.005) and with an uncorrected
14
C age of ~ 7980 yrs. A second trend corresponds to the mixing of a
more evolved tritiated groundwater (3He/4He ≥ 1.5Ra; Fig. 6)
recharging the fractured bedrock aquifer in the Appalachian recharge
area (BEC138; see Fig. 1A for location) which mixes with a fossil
groundwater (14C uncorrected ages of 15 kyrs) contained in the frac-
tured bedrock aquifer and enriched in 4Heterr (BEC101; 3He/4He =
0.074 ± 0.003 Ra; Fig. 6).
Similarly to Fig. 5, it is worth noting that these trends do not repre-
sent the chemical/isotopic evolution of groundwater along a flow-path
from the recharge to the discharge, but rather reflect local flow direc-
tions. This could be partially caused by the fact that recharge of the
deeper regional fractured aquifer is not uniform but is produced
through direct infiltration in the main Appalachian recharge area and
in the St. Lawrence plain through unconfined or semi-confined portions
of the Quaternary granular aquifers (Larocque et al., 2013). Thus, the
trend between BEC118 (located downgradient and in the granular aqui-
fer) and BEC126 (located upgradient in the fractured aquifer) should be
interpreted as a direct infiltration of modern precipitation (mid-1950s
Fig. 6. Helium isotopic ratios 3He/4He plotted against the uncorrected 14C ages of ground-
water. The two trends indicate mixing between modern precipitation and groundwater
infiltrated in the mid-50s with a “fossil” water infiltrated the system since the end of
deglaciation. The increase in ages and in radiogenic 4He (as indicated by the decrease in
the 3He/4He ratio) corresponds to a chemical evolution of groundwater from freshwater
dissolving carbonates to groundwater affected by cation exchange and NaCl dissolution.
103
and younger) into the fractured reservoir. This is not surprising for
BEC126, which is located in the main recharge area (Fig. 1) with the
fractured aquifer directly exposed to precipitation, with little or no
Quaternary cover. Direct infiltration of modern precipitation would
also explain why BEC126, which contains the highest amount of radio-
genic 4He measured in Becancour (4.48–2.65 × 10−5 cm3 STP g−1;
Table 1) which requires a long accumulation (residence) time in the
aquifer, also shows an appreciable amount of tritium (4.2 TU; Table 2).
5.3. Radiogenic 4He in the aquifers: the old water component
The relation between the 14C uncorrected ages and the 3He/4He
ratios (Fig. 6) supports the hypothesis of an increasing contribution of
radiogenic 4He to groundwater during its journey in the fractured
regional bedrock aquifer. The two end-members, BEC101 and BEC101,
are the two samples contain the highest radiogenic 4He content, from
1.17 to 4.48 × 10−5 cm3 STP g−1 (Table 1). This means that groundwa-
ter in these locations resided in the aquifer long enough to accumulate
significant amounts of radiogenic 4He produced from decay of U and
Th contained in the aquifer rocks (Andrews and Kay, 1982) or from a
sustained crustal flux from underneath the aquifer (e.g., Torgersen and
Clarke, 1985).
Assuming that the measured radiogenic 4He is produced from U
and Th decay contained in the aquifer rocks (in situ production), the
U–Th/4He groundwater residence times can be calculated as follows
(Torgersen and Clarke, 1985):
h i
4
Heterr
t¼   ð4Þ
1−ϕ
P4 He  Λ 4 He  ρ
ϕ
where [4Heterr] is the measured radiogenic 4He concentration in
groundwater (cm3 STP g− 1
water; Table 2); P4He is the radiogenic He
4
production rate in the fractured bedrock (cm3 STP g− 1
rock ); Λ4He is the
He retention factor (4Hereleased/4Heproduced) taken as 1 (Torgersen,
1980; Sano et al., 2008); (1 − ϕ/ϕ) is the void ratio where ϕ is the frac-
tional effective porosity; and ρ is the aquifer matrix density (assumed to
be 2.72 g cm−3 for a dominant carbonate matrix and 2.65 g cm−3 for a
sand matrix). Effective porosities of the Ordovician silty-carbonate-
shale facies of the regional fractured aquifer from 1 to 5% have been
estimated from pumping well tests (Larocque et al., 2013) and
measured on core samples (Tran Ngoc et al., 2014). Effective porosities
of the Quaternary granular aquifers range between 10 and 20%
(Larocque et al., 2013). 4He production rate (P4He) were estimated on
the basis of U and Th amounts measured by neutron activation and
ICP-MS analyses on eight aquifer cores sampled from domestic wells
(BEC101, BEC105 and BEC107) and from monitoring wells (F1, F2, F5,
F7 and F10) in the study area (Table 4). U contents range from 0.85
to 2.98 ppm and those of Th range from 1.3 to 12.9 ppm. Calculated
P4He assumes secular equilibrium among the U and Th descendants
(see Ballentine and Burnard, 2002), and range between 1.39 and
6.84 cm3 STP g−1 rock yr
−1
with a geometric mean and average deviation
of 3.5 ± 1.4 × 10−13 cm3 STP g−1 rock yr
−1
. This P4He production rate is
−13
close to that of 3.27 × 10 cm STP g−
3 1
rock yr
−1
calculated by Pinti
et al. (2011) for limestone facies of the St. Lawrence Lowlands.
Average in situ U–Th/4He water ages were calculated using a mean
porosity value of 3% for the fractured bedrock aquifer (and a density of
2.72 g cm− 3) and of 15% for the granular aquifer (and a density of
2.65 g cm−3). Taking into account uncertainties in the variables used
in Eq. (4), particularly the P4He (40%) and effective porosities (50%), it
is assumed here that the calculated U–Th/4He groundwater ages have
a total uncertainty of at least 50%, as generally assumed in these age
models (e.g., Torgersen and Clarke, 1985; Marty et al., 1993).
Calculated in situ U–Th/4He groundwater ages (Table 2) range from
311 yrs for BEC034 to 1.45 Ma for BEC126 (Table 2). U–Th/4He ages have
104 G. Vautour et al. / Chemical Geology 413 (2015) 94–106

Table 4 line (Fig. 7). The first group of samples requires very low helium
U and Th contents measured in core rock from selected wells. production rates P4He from 2.5 to 9 × 10−14 cm3 STP g− 1
rock yr
−1
with
−14 3 −1 −1
Rock type Weight U Th P4He x 10−13 cm3 an average of 5.8 × 10 cm STP grock yr (Fig. 7b). If the corrected
(g) (ppm) (ppm) STP g−1 yr−1 F&G 14C are valid (Table 2), then the P4He required to explain the mea-
BEC 101 2.345 1.19 5.36 2.96 sured helium amounts are from 1.4 to 3.85 × 10−13 cm3 STP g−1 rock yr
−1
,
BEC 105 2.488 2.98 8.91 6.11 again within the range of expected production rates in the fractured
BEC 107 2.203 2.63 12.90 6.84 bedrock (Table 4).
F1 2.058 1.11 6.48 3.19
The second group of water samples that plot above the 1:1 reference
F2 2.635 1.16 5.24 2.89
F5 2.082 1.36 5.89 3.31 line (Fig. 7a) points to an additional helium source in the Becancour
F7 2.290 2.00 6.67 4.30 aquifers capable of explaining the large 4Heterr amounts measured and
F10 2.362 0.85 1.30 1.39 the U–Th/4He ages higher than the equivalent 14C ages. This additional
Average 1.515 5.670 3.50 ± 1.41 helium source can be ascribed to a helium flux entering the base of
the aquifer, following the model of Torgersen and Clarke (1985). In
this case, Eq. (3) should be expressed as (e.g., Kulongoski and Hilton,
been plotted against uncorrected 14C ages (Fig. 7a). The dashed line is 2011):
the 1:1 reference line (Kulongoski et al., 2003). If the U–Th/4He and
14
C ages are concordant, all points should plot on this line. Only 4

Heterr
BEC119 plots close to the 1:1 line suggesting that radiogenic production t¼   ð5Þ
100−ϕ J0
of 4He in the aquifer rocks could be sufficient to explain the measured P4He  Λ 4 He   ρrock þ
4 ϕ zx ϕρwater
Heterr amounts (Fig. 7a). To accumulate the measured radiogenic 4He
amount of 5.67 × 10−7 cm3 STP g−1 H2O in 11.2 ka (uncorrected
14
C age;
Table 2) it requires a P4He of 5.7 × 10−13 cm3 STP g−1 rock yr −1
, within where ρwater is assumed to be equal to 1 g cm−3 and zx is the distance
the expected range of helium production rates reported in Table 4. from the base of the aquifer, where the external flux enters, to the
The remaining samples show two distinct trends (Fig. 7). A first well screen. Because the wells have no casing along the fractured
group of samples (BEC112, BEC137, BEC138, BEC147 and BEC148) bedrock aquifer section, zx is here assumed as the half-distance between
have calculated U–Th/4He water ages that are younger than the calcu- the bottom-hole and the top of the fractured bedrock aquifer.
lated 14C ages and thus plot below the 1:1 reference line. A second Data from Table 1 indicate that the fractured bedrock aquifer has an
group of water samples (BEC101, BEC103, BEC105, BEC107, BEC110, average thickness of 28 m, thus a mean zx of 14 m is here assumed.
BEC119, BEC126) show calculated U–Th/4He water ages higher than J0 is the 4Heterr flux entering the aquifer across the bottom boundary
the corresponding 14C ages and thus they plot above the 1:1 reference (in cm3 STP cm−2 yr−1).

Fig. 7. Plots of corrected U–Th/4He groundwater residence times (porosity ϕ = 3%) vs. 14C uncorrected ages for in situ production (helium production rate of 3.50 × 10−13 cm3 STP g−1
rock yr
−1
) (a);
in situ production and helium production rate of 5.8 × 10−14 cm3 STP g−1
rock yr
−1
(b); and for two crustal fluxes J0 of 1.0 × 10−8 cm3 STP cm−2 yr−1 (c) and of 18 × 10−7 cm3 STP cm−2 yr−1 (d).
 G. Vautour et al. / Chemical Geology 413 (2015) 94–106
The best fit between U–Th/4He and 14C ages for samples BEC103,
BEC107, BEC110 and BEC101 is obtained by adding a helium flux J0 of
1.0 × 10− 8 cm3 STP cm−2 yr−1 (Fig. 7c) To explain the high 4Heterr
amounts of BEC101 and BEC126 (Table 2), a helium flux J0 of
1.8 × 10−7 cm3 STP cm−2 yr−1 is required (Fig. 7d). These again are
minimum estimates because they are based on uncorrected 14C ages.
If the corrected 14C ages are assumed to be valid, then the minimum
and maximum flux entering the bedrock aquifer would range from to
9.0 × 10−8 to 5.9 × 10−7 cm3 STP cm−2 yr−1.
Calculated minimum 4Heterr fluxes J0 are 18 to 330 times lower
than the average helium continental crustal flux of 3.3 ×
10−6 cm3 STP cm− 2 yr−1 (O'Nions and Oxburgh, 1983) and even
lower (32–583 times) than the helium flux calculated for the Canadian
Precambrian Shield (5.83 × 10−6 cm3 STP cm−2 yr−1; Torgersen, 2010).
Assuming a P4He of 3.5 × 10−13 cm3 STP g−1 rock yr
−1
and a rock density of
−3 4 Aeschbach-Hertig, W., Schlosser, P., Stute, M., Simpson, H.J., Ludin, A., Clark, J.F., 1998. A
2.72 g cm , the minimum Heterr fluxes J0 can be sustained by the total
4
He radiogenic production in a sedimentary layer of 100 to 1900 m,
much less of the total thickness of the Cambro-Ordovician St. Lawrence
Platform sedimentary sequence which is evaluated to 2900 m (Lavoie
et al., 2013). Maximum 4Heterr fluxes J0 are equivalent to the radiogenic
production of a layer of 950–6200 m, which implies an additional pro-
duction from a 2 km-thick section in the Grenvillian crystalline base-
ment rocks (P4He of 6.4 × 10−13 cm3 STP g−1 rock yr
−1
; Pinti et al., 2011).
These helium fluxes suggest that local sources rather than crustal
fluxes can explain the few anomalous helium amounts measured in
Becancour groundwater. A possible source of radiogenic helium could
be the organic-rich (0.5–2% TOC; Lavoie et al., 2013), 400 m-thick
Lorraine Shale that partially releases methane in the aquifers of the
region (Moritz et al., 2015) or the 100 m thick Utica Shale. Gas analyses
in shale gas wells showed that helium occurs together with shale gas
methane at concentrations between 0.01 and 0.05 mol%. Local fractur-
ing could enhance the release of helium into groundwater (together
with methane), creating anomalous concentrations of helium in
groundwater. Methane and helium surveys in groundwater from the
Becancour and surrounding area's fractured aquifers have shown that
both methane (Moritz et al., 2015) and helium (Pinti et al., 2013) con-
centrations in groundwater increase linearly toward the major faults
present in the region. Interestingly, the two samples with the highest
4
Heterr concentrations, i.e BEC126 and BEC101 are close to two major
tectonic features, the Foulon Fault and the Logan Fault (Fig. 1) and
groundwater from these samples contains methane concentrations
from 2.4 to 32 mg L−1 (Moritz et al., 2015). Pinti et al. (2013) found
that anomalous areas of radiogenic helium dissolved in groundwater
in the St. Lawrence Lowlands aquifers are also rich in methane, suggest-
ing a common source.
6. Conclusions
Results from this study showed a complicated flow system in the
Becancour watershed with three isotopically distinct water masses
mixing together in the regional bedrock aquifer. The mixing between
modern water that infiltrated since the mid-50s and fossil water, possi-
bly recharged at the end of the deglaciation period in the region, has
been revealed by 3H/3H and14C ages and helium isotopes. The calculated
ages are compatible with the chemical evolution of the waters, yet the
observed isotopic mixings do not correspond to an evolution along the
flow path. This is probably caused 1) by a bias related to the sampling
density and 2) by local recharge areas which complicate, isotopically
and chemically, the deconvolution of groundwater flow paths. The
regional fractured bedrock aquifer of the St. Lawrence Lowlands is the
main local water resource for drinking, agricultural and industrial
purposes, including the extraction of fluids for hydraulic fracturing in
shale gas exploitation. The occurrence of old groundwater in this aquifer
system clearly limits the renewable resource and increases the risk of
overexploitation in the case of increased uses or in the case of pollution
from different sources.
105
Acknowledgments
The authors thank the Quebec Ministry of Environment (Ministère
du Développement durable, de l'Environnement, des Parcs et de la
Lutte contre les Changements climatiques), the Quebec Research Fund
(“Fonds de recherche du Quebec - Nature et Technologies”), the
Becancour River Watershed Organization (“organisme de bassin versant
GROBEC”) and the municipalities that contributed with funds to this re-
search. The authors thank the UMR GEOPS, the INSU and the Artemis of
LMC14 for 14C analyses. DLP thanks Tokyo University and Mombusho
for supporting his sabbatical stay at AORI.
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