See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/341498750

Past hot fluid flows in limestones detected by Δ47–(U-Pb) and not recorded by
other geothermometers

Article  in  Geology · May 2020

DOI: 10.1130/G47358.1

CITATIONS READS
11 733

7 authors, including:

Benjamin Brigaud Magali Bonifacie

Université Paris-Saclay Institut de Physique du Globe de Paris
83 PUBLICATIONS   1,537 CITATIONS    95 PUBLICATIONS   2,045 CITATIONS   

SEE PROFILE SEE PROFILE

Maurice Pagel Thomas Blaise

Université Paris-Sud 11 Université Paris-Sud 11
183 PUBLICATIONS   4,502 CITATIONS    32 PUBLICATIONS   228 CITATIONS   

SEE PROFILE SEE PROFILE

Some of the authors of this publication are also working on these related projects:

RECA : reconstructing the influence of climate change on laterite formation. View project

Dynamics of lanthanides and actinides in the Critical Zone View project

All content following this page was uploaded by Benjamin Brigaud on 05 September 2020.

The user has requested enhancement of the downloaded file.

 https://doi.org/10.1130/G47358.1

Manuscript received 27 December 2019

Revised manuscript received 1 April 2020
Manuscript accepted 7 April 2020

© 2020 Geological Society of America. For permission to copy, contact editing@geosociety.org.

Published online 19 May 2020

Past hot fluid flows in limestones detected by Δ47–(U-Pb) and

not recorded by other geothermometers
Benjamin Brigaud1, Magali Bonifacie2, Maurice Pagel1, Thomas Blaise1, Damien Calmels1,2, Frédéric Haurine1 and
Philippe Landrein3
1
 eosciences Paris Sud (GEOPS), Université Paris-Saclay, CNRS, 91405 Orsay, France
G
2
Institut de Physique du Globe de Paris, Université de Paris, CNRS, 75005 Paris, France
3
Andra, Route Départementale 960, 55290 Bure, France

ABSTRACT such as fluid inclusions, apatite fission tracks,

Geothermometers are commonly used to reconstruct the diagenetic and thermal history of Rock-Eval organic matter pyrolysis, or vitrinite
rocks. However, characterizing the timing, origin, and temperature of paleofluid flow remains reflectance. In favorable cases, such unexpected
challenging because it must be assessed indirectly through the analysis of microscopic cements hot fluid flows can be directly dated by coupling
that precipitate and fill intergranular spaces during fluid circulation. Here, we measure both calcite U-Pb geochronology with Δ47 (Mangenot
the clumped isotope (Δ47) temperature and in situ U-Pb age of individual diagenetic calcite et al., 2018b).
cements within a sedimentary section of the Paris Basin (France), whose thermal history This study investigates whether carbonate
has been previously inferred to be <60 °C. We show that cementation occurred during two cements in the Paris Basin (Fig. 1) did indeed
stages associated with major events at the western European lithospheric scale: (1) the Bay precipitate under the thermal conditions pre-
of Biscay rifting (Late Jurassic–Early Cretaceous), and (2) north-south Pyrenean compres- dicted by conventional geothermometers in
sion (Eocene) followed by east-west extension during the European Cenozoic rift system shallow-buried basins (<1 km and 60 °C). Here,
event (Oligocene). Related to both events, we report unexpectedly hot fluids, up to 110 °C, we combine (1) petrography, (2) stable oxygen
contrasting with the lower temperatures inferred from other geothermometers (e.g., fluid isotope composition, (3) Δ47 thermometry, and
inclusions, clay minerals, apatite fission tracks, maturity of organic matter by Rock-Eval (4) U-Pb geochronology by laser ablation (LA)
pyrolysis, or vitrinite reflectance). These high temperatures (>70 °C) have been measured for combined with high-resolution inductively cou-
calcite cements containing single-phase aqueous fluid inclusions, challenging the commonly pled plasma mass spectrometry (HR-ICP-MS;
accepted assertion that the absence of nucleation of a vapor phase indicates crystallization at Roberts et al., 2017; Pagel et al., 2018; Parrish
low temperature (∼<70 °C). We suggest that the kinetics of mineralization events prevented et al., 2018).
the recording of short-lived hot fluid flows by other geothermometers.
DIAGENETIC, THERMAL, AND
INTRODUCTION (δ18Ocalcite) and its formation temperature. It has TECTONO-SEDIMENTARY CONTEXT
Fluid flows in the upper continental crust long been difficult to identify the origin of flu- Previous studies have usefully characterized
greatly modify the properties of rocks through ids in shallow-buried sedimentary basins due the limestone petrography, geochemistry, and
dissolution-recrystallization processes and play to lack of reliable crystallization temperatures paragenesis, which guided our sampling strat-
a key role in dissipating heat at the Earth’s sur- (Swart et al., 2016). egy of the main blocky calcite cements (Brigaud
face (e.g., Vasseur and Demongodin, 1995; Application of the clumped isotope (Δ47) ther- et al., 2009). We identified two types of calcite
Swart, 2015). Diagenetic cements may provide mometer in diagenetic carbonates unlocks this cement, Cal1 and Cal2. Calcite cement Cal1
important insights into paleofluid circulation limitation and provides accurate δ18Owater values exhibits two subzones, a first crystal growth sub-
and potential thermal anomalies in sedimentary (e.g., Mangenot et al., 2018a; Pagel et al., 2018; zone composed of a thin (<50 μm) bright orange
rocks, but age and temperature determinations Dassié et al., 2018). In the Paris Basin depocen- subzone under cathodoluminescence (CL), and
commonly remain uncertain (e.g., Vincent et al., ter (France) Δ47 temperatures coupled to U-Pb a second broad (200 μm to a few millimeters)
2007; Swart et al., 2016). The oxygen isotope ages mostly match the known thermal history, dull brown subzone (Table 1; see the Supple-
composition of the water from which an oxygen- except for one cement highlighting a thermal mental Material1 and Fig. S1 therein). Calcite
bearing crystal precipitated (δ18Owater) may indi- anomaly during the Aptian–Albian (Mangenot cement Cal2, mainly occurring in fractures, con-
cate the origin of paleofluids, but robust δ18Owater et al., 2018b). This challenges the identification sists of dark brown CL spars. In the two calcite
estimates rely on accurate measurements of both of thermal events with Δ47–(U-Pb) that have not cements, fluid inclusions are small (<10 µm)
the oxygen isotope composition of the crystal been detected by conventional g­ eothermometers and ­contain a single aqueous liquid phase, sug-

1
Supplemental Material. Supplemental text, Tables S1 and S2, and Figures S1–S3 (petrographical descriptions, clumped Δ47 and U-Pb methods); and Table S3
(detailed laser ablation–inductively coupled plasma–mass spectrometry U-Pb data). Please visit https://doi​.org/10.1130/GEOL.S.12275738 to access the supplemental
material, and contact editing@geosociety.org with any questions.

CITATION: Brigaud, B., et al., 2020, Past hot fluid flows in limestones detected by ∆47–(U-Pb) and not recorded by other geothermometers: Geology, v. 48,
p. 851–856, https://doi.org/10.1130/G47358.1

Geological Society of America  | GEOLOGY |  Volume 48  |  Number 9  | www.gsapubs.org 851

Downloaded from https://pubs.geoscienceworld.org/gsa/geology/article-pdf/48/9/851/5135190/851.pdf

by CNRS_INSU user
 A
B C

Figure 1.  (A) Geological section of the Paris Basin (France) from borehole EST433 and location of samples. (B) Thermal and depth history of
each stratigraphic unit (Neo.—Neogene; Paleog.—Paleogene; O—Oligocene; Eo.—Eocene; P.—Paleocene; L.—Late; M.—Middle). (C) Geo-
logical map of the Paris Basin and location of the study area. (D) Fault and well locations. (E) Geological cross section from Gély and Hanot
(2014), with location of wells studied here and wells studied by Mangenot et al. (2018a, 2018b) in the depocenter.

gesting c­ rystallization temperatures <70 °C
(Roedder, 1984). The thermal history deduced
from geothermometers such as fluid inclusions
in quartz overgrowths, apatite fission tracks (in
Triassic sandstones), Tmax, or vitrinite reflectance
points to a maximum temperature during burial
of 60 °C at the base of the Middle Jurassic lime-
stones (Fig. 1; Blaise et al., 2014). Considering
this temperature estimate and δ18Ocalcite from
−5‰ to −10‰ (relative to Vienna Peedee bel-
emnite, VPDB), cold (<50 °C) meteoric water
influx has been invoked to explain extensive
cementation (Vincent et al., 2007; Carpentier
et al., 2014). A major Late Jurassic fluid event in
western France is interpreted as the consequence
of the deflection of the western European lith-
osphere induced by the Arctic–North Atlantic
rifting, the decrease in Tethyan accretion, and
by the shoulder of the Bay of Biscay rift (Cathe-
lineau et al., 2012; Gigoux et al., 2015). Calcite
Cal1 has been interpreted as precipitating during
this event, and Cal2 during the Cenozoic (Vin-
cent et al., 2007; Carpentier et al., 2014). For
this study, samples were collected from bore-
holes HTM102, EST210, EST205, EST433, and
EST443, drilled by Andra (e.g. Landrein et al.,
2013), located 2, 4, 5, 11, and 19 km from the
Gondrecourt faults, respectively (Fig. 1). The
Gondrecourt faults formed during the Eocene
(43–42 Ma; Pagel et al., 2018). The Vittel and
Marne faults are ancient Variscan structures
that were reactivated during the Meso-Ceno-
zoic period (Bergerat et al., 2007). The closest
borehole (HTM102) to the Vittel fault is located
20 km away.
SAMPLE SELECTION AND METHODS
Nine calcite cements and one bivalve were
sampled in the five wells in the ­Bajocian–
Oxfordian stratigraphic interval between
375 m and 885 m depth (Table 1; Fig. 1). A
representative sampling was carried out on the
two main blocky calcite types, previously ana-
lyzed for petrography, δ18O, δ13C, and 87Sr/86Sr
(see the Supplemental Material and Table S1;
Brigaud et al., 2009). Calcite Δ47 compositions
were determined at the Institut de Physique du
Globe de Paris following the data acquisition
and processing methods detailed in Bonifacie
et al. (2017) and summarized in the Supplemen-
tal Material. Δ47 data were converted into tem-
peratures (T) using the Δ47-T calibration from
Bonifacie et al. (2017). To calculate δ18Owater
from Δ47 temperature and δ18Ocalcite, we used
the oxygen isotope fractionation between cal-
cite and water from Watkins et al. (2013). All
δ18Owater data are expressed relative to Vienna
standard mean ocean water (VSMOW) in per
mil (‰), while δ18Ocalcite data are relative to
VPDB in per mil (‰).
Calcite cements were U-Pb dated using an
LA 193 nm Teledyne Photon Machines laser
coupled to a Thermo Scientific Element XR HR-
ICP-MS at the University Paris-Saclay (France)
following standard methods described elsewhere
(Ring and Gerdes, 2016; Nuriel et al., 2017;
Roberts et al., 2017). Analytical protocols are
detailed in the Supplemental Material and Fig-
ure S3 and Table S2.
RESULTS
The Δ47 temperature of calcite cements varies
between 30 and 109 °C. The six Cal1 cements
have Δ47 crystallization temperatures ranging
from 54 °C to 109 °C (average of 77 °C) and
δ18Owater values from −0.2‰ to +7.5‰ (average
of 3.2‰; Table 1). Despite small variations in
their δ18Ocalcite values, from −6.7‰ to −5.8‰, the
Cal1 cements exhibit relatively large variability
in terms of temperature and thus in terms of
δ18Owater values. The Cal2 cement sampled within
a fracture (borehole HTM102, sample HTM4,
2 km from the Gondrecourt fault system) from
the top of the Middle Jurassic carbonate yields

|  Volume 48  |  Number 9  | GEOLOGY |  Geological Society of America

852 www.gsapubs.org 

Downloaded from https://pubs.geoscienceworld.org/gsa/geology/article-pdf/48/9/851/5135190/851.pdf

by CNRS_INSU user
by CNRS_INSU user
TABLE 1.  LOCATION, CATHODOLUMINESCENCE (CL) RESPONSE, STABLE ISOTOPIC COMPOSITIONS (δ18O, δ13C, AND CLUMPED ISOTOPES
[Δ47]), Δ47 TEMPERATURE [T(Δ47)], AND U-PB AGE OF MEASURED CARBONATES, EASTERN PARIS BASIN
Sample Carbonate Stratigraphic Sedimentary Borehole Depth Latitude (°N) Longitude CL response δ13Ccalcite δ18Ocalcite n Δ47 T(Δ47) δ 18Owater Age Tera
name stage stage / formation (m) (°E) (‰, VPDB) (‰, VPDB) (‰, CDES25) (°C) (‰, VSMOW) Wasserburg
ammonite zone (Ma)
ET7 Bivalve Early Bajocian / Coral EST210 750 48.48331593 5.35989676 Nonluminescent 3.07 ± 0.12 −1.22 ± 0.03 3 0.676 ± 0.009 27 ± 3 −0.2 N.D.†
humphriesianum Limestones
E011 Cal1 Early Bathonian Chaumont EST210 584.5 48.48331593 5.35989676 Bright orange 2.36 ± 0.02 −6.16 ± 0.11 3 0.601 ± 0.019 54 ± 8 −0.2 ± 1.3 147.7 ± 4.7
/ zigzag Limestones
G8 / Cal1 Late Bajocian / Longwy EST443 885 48.58875429 5.23089466 Bright orange to 2.45 ± 0.05 −6.65 ± 0.08 2 0.577 ± 0.009 65 ± 4 1.0 ± 0.7 147.8 ± 3.8*
EST29185 Niortense Marls dull brown
E076B Cal1 Late Bajocian / Lower EST210 689.3 48.48331593 5.35989676 Bright orange to 1.89 ± 0.02 −6.28 ± 0.07 3 0.556 ± 0.016 75 ± 7 2.9 ± 1.2 161 ± 8.6
Garantiana miliaire dull brown
Oolite
E107 Cal1 Late Bajocian / Longwy EST210 716.9 48.48331593 5.35989676 Bright orange to 1.35 ± 0.01 −6.25 ± 0.03 3 0.497 ± 0.009 109 ± 6 7.5 ± 0.6 157.7 ± 7.7
Niortense Marls dull brown
E115 Cal1 Late Bajocian / Longwy EST210 722.9 48.48331593 5.35989676 Bright orange to 0.85 ± 0.01 −6.02 ± 0.14 3 0.556 ± 0.009 75 ± 5 3.2 ± 0.6 N.D.†
Niortense Marls dull brown
E160 Cal1 Early Bajocian / Coral EST210 763.9 48.48331593 5.35989676 Dull brown 2.34 ± 0.04 −5.77 ± 0.06 2 0.536 ± 0.011 85 ± 6 4.9 ± 0.5 N.D.†
humphriesianum Limestones
HTM4 Cal2 Late Bathonian Fréville HTM102 484.5 48.46137766 5.36836303 Dark brown 1.37 ± 0.02 −10.66 ± 0.06 3 0.527 ± 0.009 90 ± 5 0.6 ± 0.7 41.5 ± 4.8
/ discus Oolite
EST30573 Cal2 Early Oxfordian Chaille EST433 548 48.55003099 5.30586007 Dark brown, 2.90 ± 0.01 −8.68 ± 0.06 2 0.666 ± 0.019 30 ± 6 −7.0 ± 1.1 N.D.†
/ cordatum Marls concentric
zoned
G4 / Cal2 Middle Mésangère EST205 375 48.48528723 5.35591418 Dark brown, 0.53 ± 0.01 −9.31 ± 0.01 2 0.592 ± 0.009 58 ± 4 −2.8 ± 0.5 33.5 ± 2.8*
EST07057 Oxfordian / Formation concentric

Downloaded from https://pubs.geoscienceworld.org/gsa/geology/article-pdf/48/9/851/5135190/851.pdf

transversarium zoned
Note: Stable isotopic compositions are reported in per mil (‰); δ13Ccalcite and δ18Ocalcite are reported relative to Vienna Peedee belemnite (VPDB), δ18Owater is reported relative to Vienna standard mean ocean water (VSMOW), and Δ47 values
are reported in the carbon dioxide equilibrated scale for a 25 °C acid digestion frame (CDES25). Δ47 temperatures are calculated from the Δ47-T calibration from Bonifacie et al. (2017): Δ47(CDES25) = 42 200/T2 + 0.2082. δ18O values of the
mineralizing waters (δ18Owater) have been calculated using T(Δ47) and δ18Ocalcite according to the equation for fractionation of oxygen isotopes between calcite and water from Watkins et al. (2013): 1000lnαcalcite-H2O = (17 747/T) - 29.777. n is the
number of replicate isotopic measurements of the same carbonate powder. Reported uncertainties on Δ47(CDES25) are one standard deviation (S.D.) for replicate measurements of the same carbonate powder. Uncertainties on T(∆47) are
one standard error (S.E.) = S.D. / √n. When the S.D. of the sample was lower than the long-term standard deviation of the homogeneous standards (average of ±0.016‰, n = 27 in this study), S.D. of the standards were used to calculate
S.E. for the samples. U-Pb ages are also reported. See Tables S2 and Table S3 (see text footnote 1) for detailed laser ablation–inductively couple plasma mass spectrometry (LA-ICPMS) U-Pb data.

Geological Society of America  | GEOLOGY |  Volume 48  |  Number 9  | www.gsapubs.org

*Age from Pisapia et al. (2018).
†
N.D. = not determined
of −0.2‰.

FLUID FLOW
(Fig. 2; Table 1).

LATE JURASSIC AND EARLY

CRETACEOUS HYDROTHERMAL
compositions ranging from 0.82 to 0.92 and

The temperatures of the fluids from which

established temperature-time path of the studied

area, which indicates that rocks did not reach
precipitation might change through solid-state
mean square weighted deviation (MSWD)
of the Oxfordian strata in boreholes EST205 and

(e.g., 100 m.y. at 80–100 °C following Passey

ing experienced prolonged high temperatures
Wasserburg space have been interpreted as an

through solid-state reordering (see Fig. S2 and

and Henkes [2012]). However, according to the
reordering of isotopes in carbonates heated
2014). The calculated δ18Owater values for Cal1
isochron (i.e., all calcites sampled in each spot
associated with a δ18Owater value of 0.6‰. The

853
80–100 °C for a long period (Blaise et al., 2014),

(aqueous) fluid inclusions that did not nucleate

no change in Δ47 values of calcites is predicted
This process typically occurs in carbonate hav-
that the initial Δ47 value acquired at the time of
formed at different times, from different fluids,
features and δ18Ocalcite values, Cal1 cements
Late Jurassic at 161 ± 8.6 Ma, 157.7 ± 7.7 Ma,
are the same age), with common initial 207Pb/206Pb
Fig. 2). One bivalve Trichites shell indicates a
of 58 ± 4 °C and 30 ± 6 °C, and c­ rystallized from

temperature of 27 ± 3 °C and a δ18Owater value

meteoric waters (δ18Owater = −7‰ and −2.8‰;
EST433 (5 km and 11 km from the Gondrecourt

contains small (<10 µm) single-phase liquid

to +7.5‰). Hence, despite similar petrographic
to Kimmeridgian), are positive (from +2.9‰
cements, sampled in Bajocian strata and dated
to 0‰, which is compatible with connate sea-
respectively (Tithonian to Berriasian), are close
(54 ± 8 °C) and 147.8 ± 3.8 Ma (65 ± 4 °C)
from Bajocian strata, dated at 147.7 ± 4.7 Ma
than temperatures recorded by other geother-

discussions in the Supplemental Material). Cal1

at 161 ± 8.6 Ma and 157.7 ± 7.7 Ma (Bathonian
waters. The parent δ18Owater values of other Cal1
mometers (40–50 °C; Figs. 1 and 3; Blaise et al.,
values ranging from 0.78 to 1.5 (Fig. 2). The
two Cal2 cements sampled from the lower part
a relatively high Δ47 temperature of 90 ± 5 °C

The U and Pb isotopic data spreads in Tera-

over long periods (Passey and Henkes, 2012).

and (2) 41.5 ± 4.8 Ma and 33.5 ± 2.8 for Cal2
147.7 ± 4.7 Ma, and 147.8 ± 3.8 Ma for Cal1,
calculated U-Pb ages reveal two periods, (1)

samples E011 from Bathonian strata and G8

a vapor phase. This may be explained by the flat

faults, respectively) exhibit lower temperatures,

during the Late Jurassic are unexpectedly higher

Cal1 cements precipitated (averaging 77 °C)

and at different temperatures. It is noteworthy

 A B C

Figure 2.  (A) Paragenetic

sequence for the eastern
Paris Basin, France. (B)
D Clumped isotope (Δ 47)
temperature versus δ18O of
calcites (δ18Ocalcite; VPDB—
Vienna Peedee belemnite).
Dashed lines indicate
δ18O of mineralizing water
(δ18Owater; VSMOW—Vienna
standard mean ocean
water) using equation of
Watkins et al. (2013). For
error bars, refer to Table 1.
(C) Cross-plot of temper-
ature versus δ18Owater (‰).
Red arrow shows the fluid
evolution path. (D) Tera-
Wasserburg diagrams
displaying 207 Pb/ 206 Pb
versus 238U/206Pb; num-
bers along the blue curve
(concordia) correspond
to ages in Ma (MSWD—
mean square weighted
deviation).

shape of those inclusions and their small size,
favoring a metastable liquid (Roedder, 1984;
Goldstein and Reynolds, 1994; Krüger et al.,
2007). The nucleation of the vapor phase may
well be inhibited by nucleation kinetics and
surface energy effects. In this case, the liquid
within the inclusion remains in a superheated
state and is under tension (overexpanded). This
phenomenon is commonly observed during
microthermometric measurements in aque-
ous fluid inclusions, when the nucleation of a
vapor phase occurs at a temperature below the
homogenization temperature (Alvarenga et al.,
1993; Tarantola and Caumon, 2015). To force
the vapor bubble to nucleate, cooling-heating
cycles and prolonged cooling were attempted
on similar calcite cement samples (same strata
in the same locality), but were unsuccessful
(Blaise et al., 2015). Mangenot et al. (2017)
were, however, able to obtain homogenization
temperatures from some fluid inclusions in low-
temperature calcite cements (<100 °C) from the
Middle Jurassic limestones in the depocenter
of the Paris Basin, using similar techniques to
nucleate the vapor bubble. However, as men-
tioned by those authors, most inclusions were
metastable liquid (Mangenot et al., 2017, their
figure 3F).
The age uncertainties of ±3.8 to ±8.6 m.y.
are too large for a duration of the mineralizing
events to be suggested. However, the ranges of
temperature of Cal1 and Cal2 and the fact that
geothermometers did not record this hot fluid
circulation suggest very brief flows (probably
<1 m.y.), too short to be recorded by organic
matter or apatite fission tracks.

|  Volume 48  |  Number 9  | GEOLOGY |  Geological Society of America

854 www.gsapubs.org 

Downloaded from https://pubs.geoscienceworld.org/gsa/geology/article-pdf/48/9/851/5135190/851.pdf

by CNRS_INSU user
 the clay ­formation and infiltrated a large part
of the Upper Jurassic reservoir located in the
vicinity of the faulted zone. This last stage is
clearly related to the north-south Pyrenean
compression phase of late Eocene age (ca.
45 Ma) followed by east-west extension during
the European Cenozoic rift system event (Guil-
locheau et al., 2000; Pisapia et al., 2018; Pagel
et al., 2018). Volcanic activity in Burgundy,
180 km south of the study area, occurred during
the Eocene in relation to diffuse melting zones
in the upper part of the mantle (Bellon et al.,
1974). This volcanic activity may be further
evidence of the thermal anomaly at the litho-
spheric scale during this period.

CONCLUSION
The coupling of Δ47 temperatures and U-Pb
ages shows that the temperatures recorded in
calcite cements from the well-known eastern
Paris Basin reflect local hydrothermal events that
were probably too short-lived to be recorded by
organic matter, clay minerals, or apatite fission
tracks. More broadly, applying the Δ47–(U-Pb)
thermochronometer can thus reveal short-
Figure 3.  Thermal history of Middle and Late Jurassic limestones and marls in the eastern Paris
Basin, France. Time-temperature path of rocks is derived from Blaise et al. (2014). Δ47 tempera- lived hydrothermal events, and may challenge
tures and U-Pb ages are plotted in accordance with Cal1 and Cal2 calcite cement stages in the assumptions about the history of paleofluid cir-
eastern Paris Basin (circles), and with calcite cements Cal1 and Cal2 and dolomite cements culation in sedimentary basins. Unexpectedly,
Dol1 and Dol2 in the Paris Basin depocenter (squares; Mangenot et al., 2018b). Ages in the this study also suggests that fluid inclusions in
geologic time scale are marked in Ma (Bajo.—Bajocian; Batho.—Bathonian; Callov.—Callo-
calcite precipitated at >100 °C may not nucle-
vian). The two sets of thermal gradient values correspond to surface temperatures of 10 °C
and 15 °C. For error bars, refer to Table 1. ate a vapor bubble, challenging the commonly
accepted assumption that single-phase aqueous
inclusions indicate low crystallization tempera-
The Δ47 temperatures of Cal1 reveal hydro- of the eastern Paris Basin indicates tempera- tures. Our study reveals that marked temperature
thermal fluids, and the δ18Owater values sug- tures between 40 and 50 °C at the Eocene-Oli- anomalies (>60 °C) can punctuate the history of
gest that the waters from which these cements gocene boundary (Blaise et al., 2014), i.e., as intracratonic sedimentary basins during periods
­precipitated were enriched in 18O relative to much as 20–40 °C lower than the maximum of rifting or ocean accretion and play a key role
seawater, which disagrees with previous sug- Δ47 temperature (Fig. 3). This variability can in the evolution of sedimentary rock properties
gestions of meteoric waters (Carpentier et al., be explained by the distance from the source of (i.e., porosity destruction).
2014). Such 18O-rich fluids could have resulted the hot brines that interacted with the basement
from prolonged or extensive water-rock interac- (90 °C and δ18O of 0.6‰ in borehole HTM102 ACKNOWLEDGMENTS
This work is the result of collaborative project
tions within the crystalline basement or detrital located 2 km from the Gondrecourt faults). At
063559SGE “Thermal History of Paris Basin Car-
Triassic units. A topography-driven flow could 5 km from the faults (borehole EST205) and bonates” between the Université de Paris, Andra
have induced downflows of meteoric water from above the thick (∼140 m) Callovian–Oxford- (the French national radioactive waste management
the Ardennes massif to the basin during a period ian clay formation, the temperature of Cal2 is agency), and Université Paris-Saclay. This study has
of uplift and erosion and/or weathering (Late 58 °C. The temperature of Cal2 (30 °C) 11 km benefitted greatly from Andra funding. We also thank
Cathy Hollis (University of Manchester, UK), Peter
Jurassic and/or Early Cretaceous; Barbarand from the faults (borehole EST433) and also Swart (University of Miami, Florida, USA), and two
et al., 2018). After heating, this hydrothermal above the clay formation is in agreement with anonymous reviewers for their helpful reviews that
brine would have been driven by quick ascend- temperatures predicted by geothermometers improved the quality of the manuscript.
ing flows, possibly along faults (e.g., Vittel or in the host strata. These three Cal2 tempera-
Marne faults), resulting in anomalously hot and tures suggest that the fluids cool by ∼6 °C/km REFERENCES CITED
Alvarenga, A.D., Grimsditch, M., and Bodnar,
18
O-enriched waters. A mechanism of convective away from their potential source. The δ18Owater R.J., 1993, Elastic properties of water under
cells in the upper part of the continental crust of −7‰ suggests meteoric water within the negative pressures: The Journal of Chemi-
could have occurred (<5 km). range of the modern water isotopic composi- cal Physics, v. 98, p. 8392–8396, https://doi​
tion in this aquifer (Rebeix et al., 2011). The .org/10.1063/1.464497.
Barbarand, J., Bour, I., Pagel, M., Quesnel, F., Del-
IMPLICATIONS FOR THERMAL FLUID calcites of the Gondrecourt fault zone reveal
cambre, B., Dupuis, C., and Yans, J., 2018, Post-
FLOW DURING THE EOCENE AND meteoric fluids (−4.5‰) and Δ47 temperature Paleozoic evolution of the northern Ardenne
OLIGOCENE of 44 °C for ages ranging from 43 Ma to 35 Ma Massif constrained by apatite fission-track ther-
The final stage of calcite cement Cal2 is (Pagel et al., 2018). The temperature of 58 °C mochronology and geological data: Earth Sci-
not voluminous and records fluid temperatures in Cal2 sampled in Oxfordian limestones con- ence Bulletin, v. 189, 16, https://doi.​ org/10.1051/
bsgf/2018015.
either higher than those predicted by geother- firms that occasionally large volumes of hot Bellon, H., Gillot, P.Y., and Nativel, P., 1974, Eocene
mometers (58 and 90 °C) or in agreement with fluids from underlying reservoirs may have volcanic activity in Bourgogne, Charollais,
predictions (30 °C; Fig. 3). The thermal history migrated along the Gondrecourt faults across Massif Central (France): Earth and Planetary

Geological Society of America  | GEOLOGY |  Volume 48  |  Number 9  | www.gsapubs.org 855

Downloaded from https://pubs.geoscienceworld.org/gsa/geology/article-pdf/48/9/851/5135190/851.pdf

by CNRS_INSU user
 Science Letters, v. 23, p. 53–58, https://doi​
.org/10.1016/0012-821X(74)90029-6.
Bergerat, F., et al., 2007, 3D multiscale structural
analysis of the eastern Paris basin: The ANDRA
contribution, in Lebon, P., ed., A Multi-Disci-
plinary Approach to the Eastern Jurassic Bor-
der of the Paris Basin (Meuse / Haute-Marne):
Mémoire de la Société Géologique de France,
v. 178, p. 15–35.
Blaise, T., et al., 2014, Reconstruction of low tem-
perature (<100 °C) burial in sedimentary basins:
A comparison of geothermometer in the intrac-
ontinental Paris Basin: Marine and Petroleum
Geology, v. 53, p. 71–87, https://doi​.org/10.1016/​
j.marpetgeo.2013.08.019.
Blaise, T., Tarantola, A., Cathelineau, M., Boulvais,
P., Techer, I., Rigaudier, T., Boiron, M.-C., Pier-
ron, O., and Landrein, P., 2015, Evolution of
porewater composition through time in lime-
stone aquifers: Salinity and D/H of fluid inclu-
sion water in authigenic minerals (Jurassic of the
eastern Paris Basin, France): Chemical Geology,
v. 417, p. 210–227, https://doi​.org/10.1016/​
j.chemgeo.2015.10.014.
Bonifacie, M., et al., 2017, Calibration of the dolomite
clumped isotope thermometer from 25 to 350 °C,
and implications for a universal calibration for
all (Ca, Mg, Fe)CO3 carbonates: Geochimica et
Cosmochimica Acta, v. 200, p. 255–279, https://
doi​.org/10.1016/​j.gca.2016.11.028.
Brigaud, B., Durlet, C., Deconinck, J.-F., Vincent, B.,
Thierry, J., and Trouiller, A., 2009, The origin
and timing of multiphase cementation in car-
bonates: Impact of regional scale geodynamic
events on the Middle Jurassic Limestones dia-
genesis (Paris Basin, France): Sedimentary Geol-
ogy, v. 222, p. 161–180, https://doi​.org/10.1016/​
j.sedgeo.2009.09.002.
Carpentier, C., et al., 2014, Impact of basin burial
and exhumation on Jurassic carbonates diagen-
esis on both sides of a thick clay barrier (Paris
Basin, NE France): Marine and Petroleum Geol-
ogy, v. 53, p. 44–70, https://doi​.org/10.1016/​
j.marpetgeo.2014.01.011.
Cathelineau, M., Boiron, M.-C., Fourcade, S., Ruf-
fet, G., Clauer, N., Belcourt, O., Coulibaly,
Y., Banks, D.A., and Guillocheau, F., 2012,
A major Late Jurassic fluid event at the basin/
basement unconformity in western France:
40
Ar/39Ar and K-Ar dating, fluid chemistry, and
related geodynamic context: Chemical Geology,
v. 322–323, p. 99–120, https://doi​.org/10.1016/​
j.chemgeo.2012.06.008.
Dassié, E.P., et al., 2018, A newly designed analytical
line to examine fluid inclusion isotopic composi-
tions in a variety of carbonate samples: Geochem-
istry Geophysics Geosystems, v. 19, p. 1107–
1122, https://doi​.org/10.1002/2017GC007289.
Gély, J.-P., and Hanot, F., 2014, Coupe géologique
du Bassin parisien et du Fossé rhénan: Bulletin
d’Information des Géologues du Bassin de Paris,
Mémoire hors-série no. 9, 1 planche.
Gigoux, M., Delpech, G., Guerrot, C., Pagel, M.,
Augé, T., Négrel, P., and Brigaud, B., 2015,
Evidence for an Early Cretaceous mineralizing
|  Volume 48  |  Number 9  | GEOLOGY |  Geological Society of America
856 www.gsapubs.org 
Downloaded fromView
https://pubs.geoscienceworld.org/gsa/geology/article-pdf/48/9/851/5135190/851.pdf
publication stats
by CNRS_INSU user
event above the basement/sediment unconfor-
mity in the intracratonic Paris Basin: Paragenetic
sequence and Sm-Nd dating of the world-class
Pierre-Perthuis stratabound fluorite deposit: Min-
eralium Deposita, v. 50, p. 455–463, https://doi​
.org/10.1007/s00126-015-0592-1.
Goldstein, R.H., and Reynolds, T.J., 1994, Systematics
of fluid inclusions in diagenetic minerals: SEPM
(Society for Sedimentary Geology) Short Course
31, 199 p., https://doi​.org/10.2110/scn.94.31.
Guillocheau, F., et al., 2000, Meso-Cenozoic geody-
namic evolution of the Paris Basin: 3D strati-
graphic constraints: Geodinamica Acta, v. 13,
p. 189–245, https://doi​.org/10.1080/09853111.
2000.11105372.
Krüger, Y., Stoller, P., Rička, J., and Frenz, M., 2007,
Femtosecond lasers in fluid-inclusion analysis:
Overcoming metastable phase states: European
Journal of Mineralogy, v. 19, p. 693–706, https://
doi​.org/10.1127/0935-1221/2007/0019-1762.
Landrein, P., Vigneron, G., Delay, J., Lebon, P., and
Pagel, M., 2013, Lithologie, hydrodynamisme
et thermicite dans le systeme sedimentaire mul-
ticouche recoupé par les forages Andra de Mon-
tiers-sur-Saulx (Meuse): Bulletin de la Societe
Geologique de France, v. 184, p. 519–543,
https://doi​.org/10.2113/gssgfbull.184.6.519.
Mangenot, X., Bonifacie, M., Gasparrini, M., Götz, A.,
Chaduteau, C., Ader, M., and Rouchon, V., 2017,
Coupling Δ47 and fluid inclusion thermometry on
carbonate cements to precisely reconstruct the
temperature, salinity and δ18O of paleo-ground-
water in sedimentary basins: Chemical Geol-
ogy, v. 472, p. 44–57, https://doi​.org/10.1016/​
j.chemgeo.2017.10.011.
Mangenot, X., Gasparrini, M., Rouchon, V., and Boni-
facie, M., 2018a, Basin-scale thermal and fluid
flow histories revealed by carbonate clumped iso-
topes (Δ 47)— Middle Jurassic carbonates of the
Paris Basin depocentre: Sedimentology, v. 65,
p. 123–150, https://doi​.org/10.1111/sed.12427.
Mangenot, X., Gasparrini, M., Gerdes, A., Bonifacie,
M., and Rouchon, V., 2018b, An emerging ther-
mochronometer for carbonate-bearing rocks: Δ47/
(U-Pb): Geology, v. 46, p. 1067–1070, https://doi​
.org/10.1130/G45196.1.
Nuriel, P., Weinberger, R., Kylander-Clark, A.R.C.,
Hacker, B.R., and Craddock, J.P., 2017, The
onset of the Dead Sea transform based on calcite
age-strain analyses: Geology, v. 45, p. 587–590,
https://doi​.org/10.1130/G38903.1.
Pagel, M., et al., 2018, Improving paleohydrological
and diagenetic reconstructions in calcite veins
and breccia of a sedimentary basin by combining
Δ47 temperature, δ18Owater and U-Pb age: Chemical
Geology, v. 481, p. 1–17, https://doi​.org/10.1016/​
j.chemgeo.2017.12.026.
Parrish, R.R., Parrish, C.M., and Lasalle, S., 2018,
Vein calcite dating reveals Pyrenean orogen as
cause of Paleogene deformation in southern Eng-
land: Journal of the Geological Society, v. 175,
p. 425–442, https://doi.​ org/10.1144/jgs2017-107.
Passey, B.H., and Henkes, G.A., 2012, Carbonate
clumped isotope bond reordering and geospeed-
ometry: Earth and Planetary Science Letters,
v. 351–352, p. 223–236, https://doi​.org/10.1016/​
j.epsl.2012.07.021.
Pisapia, C., Deschamps, P., Battani, A., Buschaert, S.,
Guihou, A., Hamelin, B., and Brulhet, J., 2018,
U/Pb dating of geodic calcite: New insights on
Western Europe major tectonic events and associ-
ated diagenetic fluids: Journal of the Geological
Society, v. 175, p. 60–70, https://doi​.org/10.1144/
jgs2017-067.
Rebeix, R., Le Gal La Salle, C., Michelot, J.-L., Ver-
doux, P., Noret, A., Monvoisin, G., Gianesinni,
S., Lancelot, J., and Simler, R., 2011, Tracing
the origin of water and solute transfers in deep
groundwater from Oxfordian, Dogger and Trias
formations in the east of the Paris Basin—France:
Physics and Chemistry of the Earth, Parts A/B/C,
v. 36, p. 1496–1510, https://doi​.org/10.1016/​
j.pce.2011.07.015.
Ring, U., and Gerdes, A., 2016, Kinematics of the
Alpenrhein-Bodensee graben system in the
Central Alps: Oligocene/Miocene transten-
sion due to formation of the Western Alps arc:
Tectonics, v. 35, p. 1367–1391, https://doi​
.org/10.1002/2015TC004085.
Roberts, N.M.W., Rasbury, E.T., Parrish, R.R., Smith,
C.J., Horstwood, M.S.A., and Condon, D.J.,
2017, A calcite reference material for LA-ICP-
MS U-Pb geochronology: Geochemistry Geo-
physics Geosystems, v. 18, p. 2807–2814, https://
doi​.org/10.1002/2016GC006784.
Roedder, E., 1984, Fluid Inclusions: Mineralogical Soci-
ety of America Reviews in Mineralogy 12, 644 p.
Swart, P.K., 2015, The geochemistry of carbonate dia-
genesis: The past, present and future: Sedimentol-
ogy, v. 62, p. 1233–1304, https://doi​.org/10.1111/
sed.12205.
Swart, P.K., Cantrell, D.L., Arienzo, M.M., and Mur-
ray, S.T., 2016, Evidence for high temperature
and 18O-enriched fluids in the Arab-D of the Gha-
war Field, Saudi Arabia: Sedimentology, v. 63,
p. 1739–1752, https://doi.​ org/10.1111/sed.12286.
Tarantola, A., and Caumon, M.-C., 2015, Raman spec-
tra of water in fluid inclusions: II. Effect of nega-
tive pressure on salinity measurement: Journal of
Raman Spectroscopy, v. 46, p. 977–982, https://
doi​.org/10.1002/jrs.4668.
Vasseur, G., and Demongodin, L., 1995, Convec-
tive and conductive heat transfer in sedimentary
basins: Basin Research, v. 7, p. 67–79, https://doi​
.org/10.1111/​j.1365-2117.1995.tb00096.x.
Vincent, B., Emmanuel, L., Houel, P., and Loreau,
J.-P., 2007, Geodynamic control on carbonate
diagenesis: Petrographic and isotopic investi-
gation of the Upper Jurassic formations of the
Paris Basin (France): Sedimentary Geology,
v. 197, p. 267–289, https://doi​.org/10.1016/​
j.sedgeo.2006.10.008.
Watkins, J.M., Nielsen, L.C., Ryerson, F.J., and
DePaolo, D.J., 2013, The influence of kinetics
on the oxygen isotope composition of calcium
carbonate: Earth and Planetary Science Letters,
v. 375, p. 349–360, https://doi​.org/10.1016/​
j.epsl.2013.05.054.
Printed in USA