Marine and Petroleum Geology 73 (2016) 228e248

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Marine and Petroleum Geology

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

Research paper

Hydrogeochemical characterization of oileld waters from southeast

Maracaibo Basin (Venezuela): Diagenetic effects on chemical and
isotopic composition

squez b,
Tiziano Boschetti a, *, Beatriz Angulo b, Frank Cabrera b, Jhaisson Va
c

n Luis Montero
Ramo
a
b
c

Department of Physics and Earth Sciences Macedonio Melloni, University of Parma, Parco Area delle Scienze 157/A, 43124, Parma, Italy

leos de Venezuela S.A. e PDVSA Intevep Strategic Research in Exploration, Los Teques, Venezuela
Petro
Universidad Central de Venezuela e Facultad de Ciencias, Instituto de Ciencias de la Terra e Apartado 3895, Caracas, 1010-A, Venezuela

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 30 September 2015
Received in revised form
7 January 2016
Accepted 10 February 2016
Available online 26 February 2016

Free water and water in emulsion with oil from hydrocarbon wells onshoreeoffshore Lake Maracaibo
were extracted and analyzed. The use of classical and new chemical diagrams evidenced that NaeHCO3
and NaeCl are the main chemical facies, whereas NaeSO4 facies was rare and revealed only in faulted
areas in which shallow groundwater was involved in deep circulation. Cretaceous CaeCl waters were not
revealed, but their imprint on some samples was traced and evidenced by LangeliereLudwig, BrineDifferentiation and Caexcess vs. Nadecit diagrams. These square plots, allowing a discrimination between the water contributions from the different source rocks, should be more exploited as hydrogeochemical tools in hydrocarbon exploration. Original data on monocarboxylic anions showed acetate
concentration higher than ten times that of formate at sampling conditions, but speciation under deep
conditions indicated a reversed activity dominance. Calculation of saturation indexes and kinetic
modeling showed an active precipitation of chalcedony, kaolinite and clays, especially where the temperature was lower (T < 100
C). Formation waters and lake water showed quite similar chloride concentration and hydrogen isotope composition. However, thermodynamic calculations at the oileld P-T
conditions revealed chlorite and illite, produced during previous diagenetic stages of Misoa sandstones,
recrystallization to smectite and vermiculite in present-day stage. The diagenetic water produced in
these reactions could have enriched the d18O isotopic composition of approximately 2. This isotope
diagenetic effect was more evident in NaeHCO3 waters, which also showed a decrease in chloride at
constant boron concentration as a consequence of clay dewatering. In this regard, a new boron geothermometer useful for formation waters is also proposed:

Keywords:
Lake Maracaibo
Diagenesis
Formation waters
Maracaibo basin

T
C

5:1364ln1=Bmg=1 5:7280:180
0:1640:012

1. Introduction
The literature on the oileld waters of Maracaibo Basin (MB) is
scarce and, when published, data are shown only in summary form.
One of the rst papers on the Venezuelan oileld waters dates back
to the rst half of the 20th century (Smith, 1931). In that pioneering
study, the content of naphthenic acids in oileld waters was i)
directly proportional to the alkalinity of the water and ii) related to

* Corresponding author.
E-mail addresses: tiziano.boschetti@unipr.it, work@tizianoboschetti.com (T. Boschetti).
http://dx.doi.org/10.1016/j.marpetgeo.2016.02.020
0264-8172/ 2016 Elsevier Ltd. All rights reserved.

2016 Elsevier Ltd. All rights reserved.

the length of time in contact with oil. Smith (1931) concluded that
iii) waters associated with oil contain few or no sulfates due to
reduction to suldes and that iv) water of meteoric origin with high
sulfate, when completely altered by contact with oil, had all of its
sulfate replaced by (bi)carbonate and/or naphthenic acids, resulting
in high total alkalinity.
Soto and Puche (1982) classied four water groups in the MB
distinguished by formation age: i) Cretaceous with Ca-chloride
(CaeCl) composition and a mean salinity of 60 g/l, ii) Lower
Eocene with Na-chloride (NaeCl) composition and a salinity of
10.7 g/l, iii) Upper Eocene/Oligocene with Na-bicarbonate

T. Boschetti et al. / Marine and Petroleum Geology 73 (2016) 228e248

(NaeHCO3) composition and 5.5 g/l salinity, and iv) Miocene with
NaeHCO3 composition and 4.8 g/l salinity. Bockmeulen et al. (1983)
conrmed both salinity and chemistry ranges, specifying that waters associated with the degraded oils are typically meteoric in
chemical composition with considerable bicarbonate content.
Nelson et al. (2000) and Porras et al. (2007) resumed the water
chemistry study of the NW elds of Lake Maracaibo, distinguishing
two types of CaeCl waters, one chemically homogeneous from preJurassic crystalline metamorphic basement and one more heterogeneous from Cretaceous carbonates; the latter was two times
more saline than modern seawater. Waters from the Paleocene and
Eocene formations were also distinguished by Nelson et al. (2000),
which also underlined a chemical variation during production, with
a peak in the area uplifted during the Eocene.
More recently, Rachinsky and Kerimov (2015) tabled the minimum and maximum chemical concentration data of the MB waters,
subdivided into three main classes: a) oileld waters, b) regional
background waters and c) inltration waters. These three classes
were further subdivided into ve subgroups (a regional stratigraphic scheme of the MB is available at the PDVSA webpage,
PDVSA, 2011): i) Cretaceous complex produced from Lower and
Upper Cretaceous carbonates and sandstones and mainly characterized by CaeCl with salinity up to 43.0e61.4 g/l (this subgroup
was not mentioned in the inltration waters); ii) Paleocene complex with sodium-bicarbonate waters (NaeHCO3) and salinity up to
15.1e16.8 g/l; iii) Eocene complex with NaeHCO3 waters, salinity
up to 11.8e12.9 g/l, diffused all over the region, and increased
salinity up to 20.0e22.9 g/l in the hydrocarbon production areas;
iv) Oligocene complex, NaeHCO3 waters with a salinity of
12.9e14.3 g/l that jumps to 16.6e20.6 g/l in productive areas; and
v) Miocene complex with alkaline waters and a salinity up to
10.4e11.8 g/l that jumps to 14.4e17.0 g/l where waters are in contact with hydrocarbons. Moreover, these authors noted that the
high sulfate concentration in Cenozoic water complexes was
recorded only within the productive fault-blocks; in which case, the
water usually has salinity similar to the waters from the Cretaceous
series.
Above contributions notwithstanding, the questions regarding
origin of the deep oil-bearing formation waters and their connection with shallow groundwater still left unanswered. This also due
to the lack of isotope analyses and absence of a hydrogeological
model of the area.
In this study, the results concerning main chemical constituents
from 30 years of monitoring the oilelds in the southeast MB are
shown and compared with the composition of shallow groundwater. Moreover, organic anion concentrations and isotope data are
also presented. From a general point of view, several reactions are
proposed to explain sandstone-shale mass transfer in sedimentary
basins (e.g. Milliken, 2014), but these are rarely thermodynamically
checked. Moreover, despite of suspected contribution of water from
dehydration reactions during diagenesis (Hanor, 1987), it is rarely
taken into account in d18O-d2H diagrams (e.g. Sharp, 2007).
Therefore, in this work attention was also focused to: i) calculation
of minerals saturation indexes of the formation water samples; ii)
checking of reactions directions comparing aqueous species activities and solubility products (masseaction relations) at specic P-T
conditions; iii) role of dehydration reactions on isotope composition and comparison with other fractionation processes dealing
with sedimentary basins.
2. Geological outline
The actual MB is a foreland basin located inside a triangular
tectonic block in northwest Venezuela (Fig. 1A). The tectonic block

fault in the Me

rida Andes, the Santa
is bounded by the Bocono

229

Range
Marta-Bucaramanga system faults located west of the Perija

n faults system
in Colombia, and the EeW striking Oca-Anco
running parallel to the boundary with the Caribbean plate (Fig. 1A).
The MB occupies an area of approximately 50,000 km2 and is
known to be a hydrocarbon-rich region that has produced over 30
billion oil barrels, with an estimated 44 billion yet to be recovered
(Escalona and Mann, 2006). It is bounded in the northwest by the

Range, in the southwest by the Santander massif of Colombia,
Perija
and in the southeast by the Venezuelan Andes. The northeastern
boundary of the basin is formed by the zone of the western foothills

n Basin
of the Trujillo Range, which separates it from the Falco
(Fig. 1B). Lake Maracaibo covers about one-third of the total area
and receives water drained from the Perij

a Range, the Venezuelan

rida Andes) and the Trujillo Ranges. In the north, Lake
Andes (Me
Maracaibo is connected to the Gulf of Venezuela (Caribbean Sea)
through the Maracaibo Strait. The geologic history of the MB
changed through time as it evolved from a passive continental
margin setting in Cretaceous-Eocene time to a foreland basin
setting in post-Eocene time (Talukdar and Marcano, 1994). The
development of the basin is related to interactions among the Pacic, Caribbean, and South American plates. The top of the basement is mainly composed of continental sedimentary and
siliciclastic volcanic rocks of Triassic-Jurassic age and some Paleozoic igneous and metamorphic rocks (Talukdar and Marcano, 1994).
Sedimentation of the Cretaceous rocks on the Maracaibo platform
started with the deposition of coarse continental clastics, followed
by a marine transgression deposited thick, shallow-water platform
carbonates and associated sedimentary rocks (Cogollo Group). At
maximum marine transgression (Cenomanian-Turonian age), the
organic material was deposited under anoxic conditions in a shelfslope setting represented by dark-gray limestone and calcareous
shale of the La Luna Formation (the source rock for 98% of the total
oil reserves in the MB). A tectonic uplift of the Western and Central
Colombia ranges was responsible for an increase in subsidence that

n Forresulted in the deposition of thick marine shale of the Colo
mation (Maastrichtian age; Lugo and Mann, 1995; Parnaud et al.,
1995). The oblique convergence between the Caribbean plate and
the northwestern margin of South America produced a complex
foreland basin (Late Paleocene - early to middle Eocene age),
characterized by an approximately 5-km thick Eocene wedge of
uvial-deltaic sedimentation where the most prolic hydrocarbon
reservoirs of the MB are concentrated (Misoa Formation, Eocene;
Fig. 1C). Isostatic rebound affected the central and eastern parts of
the MB and produced a widespread unconformity during the
Eocene that exposed and subaerially eroded the central and
northeastern parts of the basin until the end of the Oligocene
(Escalona and Mann, 2006). The marine shale and coarse sandstones sequence of Pauj Formations represents the main seal above
the Eocene reservoirs (Fig. 1C), but it is locally breached by faulting
(Fig. 1D), allowing the upward ascent of hydrocarbons into Miocene
reservoirs at the basin edges (Mann et al., 2006).
The study area is 60 km2 wide and located in the southeast of
Lake Maracaibo, near the border between Trujillo and Zulia states
(Fig. 1B). The exploited Misoa Formation is currently under hydrostatic (500 bar) or sub-hydrostatic pressure (200 bar) due to
extensive oil production (Bigelow, 1994; Chapman, 1994; Perez,
2003). However pressure of the unexploited reservoir was higher
than hydrostatic (~750 bar; Bernys, 1997). From a hydrological
point of view, the Quaternary cover in the surroundings of Lake
Maracaibo are characterized by shallow groundwater owing from
Coastal and Andean units (Fig. 1A) which is used from domestic and
farming activities (Montero, 2006). In particular, some springs of
the Trujillo Range are thermal or show high content of sulfate
(Fig. 1A, Quibor aquifer in Mella, 1982; thermal waters in

ndez and Sa

nchez, 2004 and Moreno et al., 2007). From the
Herna

230

T. Boschetti et al. / Marine and Petroleum Geology 73 (2016) 228e248

Fig. 1. A: Location of the Maracaibo Basin within the triangular tectonic block, as dened by Bueno (1996); numbers are the main hydrological provinces of shallow non-oileld
groundwater (after DeCarli, 2011; the border between the provinces 3 and 4 coincides with Orinoco River); of these waters, chemical data from south-west (Montero, 2006;

ndez and S
anchez, 2004; Moreno et al., 2007) were used for comparison with oilMontero et al., 2008), east (Quibor aquifer; Mella, 1982) and Trujillo thermal waters (Herna
eld waters in this study. B: Location of oil and gas elds in the Maracaibo Basin (modied after Bernys, 1997 and Talukdar and Marcano, 1994). Square depicts the studied area. Well
coordinates and locations are proprietary information of Petroleos De Venezuela (PDVSA). C: Simplied stratigraphic scheme of the studied area (modied from Laya 2013): oileld
waters of this study come from B1eB4 productive levels. D: East-West section at the middle of Maracaibo Basin (modied from Yoris and Ostos, 1997).

T. Boschetti et al. / Marine and Petroleum Geology 73 (2016) 228e248

231

Table 1
Chemical and isotopic composition of the waters sampled in this study (second monitoring, 2012e2013). ON: onshore wells; OF: offshore wells. Chemical classication was
done by relative prevalence of cation and anion constituents on ternary diagrams (Fig. 2). ON4 and ON3 are classiable as NaeCl or NaeHCO3 if cAlk (cAlk < Cl) or tAlk
(tAlk > Cl) were considered, respectively.
Well code

Misoa
Depth meters
formation
subunit

Pressurea Chemical classication

bar

Emulsionb

Temperature


C

pH L.C. pHc

Densityd
g/cm3

E.C. mS/cm
at L.C.

TDSd mg/L

Na
mg/L

K
mg/L

ON12
ON13
ON5
ON6
ON2
ON4
ON3
ON14
ON15
OF50
OF27
OF32
OF14
OF7
OF28

B1
B1
top-B1
B1
B4
B1
B1
B4
B4
B4
B1eB4
B1eB4
B1eB4
B1eB4
B2eB4

475
508
473
471
521
533
530
553
533
470
490
475
482
488
504

O/W
W/O
O/W
O/W
O/W
O/W
O/W
W/O
W/O
W/O
W/O
W/O
W
W
W

e
142
96
104
118
117
119
130
130
121
e
148
145
e
119

8.84
9.05
9.20
8.95
8.76
8.77
9.18
8.27
8.60
9.06
8.96
8.54
7.93
8.77
8.40

1.0029
1.0033
1.0034
1.0035
1.0035
1.0036
1.0037
1.0052
1.0053
1.0036
1.0041
1.0043
1.0043
1.0043
1.0047

4.7
5.7
6.0
6.2
6.3
6.5
6.6
10.4
10.6
6.4
7.7
8.1
8.1
8.2
9.1

3033
3667
3858
3979
4026
4187
4241
6627
6798
4082
4925
5173
5184
5255
5839

855
1131
1038
1061
1056
1161
1187
2216
2285
1155
1541
1583
1659
1618
1727

48
38
84
108
110
116
133
91
165
68
102
118
113
146
194

4807e4852
5157e5179
4734e4884
4752e4824
5258e5355
5398e5444
5359e5407
5534e5691
5397e5413
4762e4784
4749e5199
4606e5039
4673e5119
4837e5204
5015e5211

NaeHCO3
NaeHCO3
NaeHCO3
NaeHCO3
NaeHCO3
NaeCl/NaeHCO3
NaeCl/NaeHCO3
NaeCl
NaeCl
NaeHCO3
NaeCl
NaeCl
NaeCl
NaeCl
NaeCl

5.99
6.04
5.91
5.92
6.02
5.96
5.98
5.53
5.68
6.13
5.97
6.14
5.74
5.83
5.79

-: not analyzed.
L.C.: Laboratory Conditions (T 25
C, P 1 bar).
cAlk: carbonate alkalinity (HCO3 CO3 as mg/l of HCO3).
tAlk: total alkalinity.
a
Calculated by static uid pressure equation P r  g  h, where r density of the uid, g acceleration of gravity, h mean depth.
b
W/O water-oil; O/W oil-water; W free water (no emulsion).
c
Calculated at deep conditions by EQ3/6.
d
Calculated by EQ3/6 at L.C.

Pauj Formation (Late Eocene) to deep areas, water is associated

with hydrocarbons. The Misoa Formation (Eocene age; from negraded quartzarenitic-lithoarenitic sandstone to arkosic, micaceous, limonite-stained sandstone) is bounded by unconformities
(Higgs, 1996), with marine sandstones, shales and limestones of the
Guasare Formation below (Paleocene), and marine strata of the La
Rosa Formation above (Miocene age; mainly composed of shale).
According to the operational classication by PDVSA, the terms C,
B-Inferior and B-Superior (where C and B coincide with two main
trasgressive cycles) are used to subdivide the lower, median and
upper sandstones in the Misoa Formation, respectively (Fig. 1C). In
the studied area, the main mineralogy is quartz86-feldspar5-0lithic9-14 (Cabrera, 2015; Perez and Boles, 2005). Where present,
feldspars showed similar proportions of albite and K-feldspar at
depth (Cabrera, 2015), whereas plagioclase are dominant in the
surroundings outcrops (Ayala et al., 2012). Authigenic minerals
developed during early burial, telodiagenesis and medium to late
burial diagenetic stages include carbonate, silica and clays phases.
These latter are composed by common kaolinite, with subordinate
discrete illite, ordered mixed-layer illite/smectite, chlorite and
expandable mixed layer illite-smectite (Manske, 1993; Perez and
Boles, 2005).

3. Methods
3.1. Historical data source and sampling strategy
The historical data (1983e2012) concerned eight major dis2
2
solved constituents, Na, K, Ca2, Mg2, Cl, HCO
3 , CO3 and SO4 ,
in the wells of offshore and onshore oilelds located in the
southeast of Lake Maracaibo (Fig. 1B). Only samples with an ionic
balance less than 10% were chosen, resulting in a dataset with 170
samples from 62 wells: 34 samples from 11 wells onshore and 136
samples from 51 wells offshore of Lake Maracaibo.
The 15 wells selected for this study (2012e2013) a) were not
affected by waterooding (i.e., use of water injection to enhance

production) and b) had a water production higher than 40%.

Sampled wells pumped water and crude from the Misoa B upper
sands (B-Superior). To guarantee sufcient amounts of water for
analyses, 25 L of uid were collected from the wellhead of every
sampling site after discharging approximately 5 L and by-passing
the oil-water separator when a crude-oil emulsion was detected
(Collins and Wright, 1982). In the next paragraph, the treatment of
the samples is discussed.
3.2. Emulsion destabilization and demulsication
The collected samples emulsions were classied according to
Kokal (2005): i) free water, with no emulsion and good separation
between oil and water; ii) oil-in-water emulsions, O/W; and iii)
water-in-oil emulsions, W/O. Physical methods were employed to
destabilize emulsions. To guarantee the integrity of the constituents dissolved in water, neither heating nor pH modication were
applied. Water samples from O/W were extracted using a modication of Method 3510C (EPA, 1996) involving ambient temperature, separatory-funnel liquideliquid extraction with CH2Cl2
(HPLC-grade, Honeywell Burdick & Jackson) as the solvent and
centrifugation of the extracted uid (30 min at 3000 rpm). The
approach used to extract water from W/O was similar, but the
addition of 0.2% TRETOLITE F46 demulsier (Petrolite Corporation,
Tretolite Division) and centrifugation (10 min at 15,000 rpm) were
necessary to destabilize the emulsions before liquideliquid
extraction. A laboratory water standard was treated in the same
manner to verify whether the analytical quality had been maintained after the treatments.
3.3. Analytical methods
pH and conductivity were analyzed at the sampling site in free
water and in the laboratory, just after extraction, on demulsied
water by a multimeter (Accumed Excel XL60, Fisher Scientic).
Sample aliquots of 20 ml dedicated to the analysis of dissolved

232

T. Boschetti et al. / Marine and Petroleum Geology 73 (2016) 228e248

Ca
mg/L

Mg
mg/L

Cl
mg/L

SO4
mg/L

cAlk
mg/L

Acetate
mg/L

Formate
mg/L

tAlkd
mg/L

SiO2
mg/L

B
mg/L

Br
mg/L

Li
mg/L

Sr
mg/L

Ba
mg/L

Rb
mg/L

Al
mg/L

Fe
mg/L

P
mg/L

d18O

d2H

7.0
8.0
5.4
9.0
9.0
1.2
3.9
33.0
73.0
24.0
40.0
58.0
25.0
63.0
69.0

1.21
1.10
1.43
4.52
4.70
4.45
5.15
89
32
2.54
5.37
8.01
7.40
7.50
7.65

210
860
178
411
414
697
697
3875
3654
223
1372
1623
2329
2165
2017

58.1
73.8
85.8
71.1
71.0
62.9
62.8
60.2
69.3
72.5
63.3
58.5
61.9
50.6
45.9

1199
1846
605
959
916
627
412
205
141
1302
1505
762
106
891
651

317
174
1243
818
857
900
1034
441
756
537
287
487
552
753
597

10
<10
40
28
30
30
31
<10
25
30
21
17
29
31
26

1921
1475
2382
2161
2155
1933
2024
683
932
2738
1952
1847
687
875
1316

e
133
141
152
150
143
150
e
e
e
e
e
158
135
163

e
22
34
30
30
29
30
25
e
e
e
e
37
46
35

<5
<5
1.5
2.1
2.1
3.1
3.2
14.6
16.0
2.5
6.3
7.8
9.2
9.1
8.6

0.48
1.06
0.44
0.51
0.52
0.51
1.04
2.38
1.93
e
e
e
e
1.54
e

e
<1
0.29
0.42
0.43
0.08
0.49
6.45
3.50
e
e
e
e
2.43
e

e
<1
0.19
0.43
0.44
0.13
0.43
2.39
1.60
e
e
e
e
3.30
e

e
<1
0.06
0.09
0.09
0.10
0.39
e
<1
e
e
e
e
e
e

e
e
0.015
0.010
0.010
0.010
0.012
e
e
e
e
e
e
e
e

0.17
e
0.09
0.09
0.08
0.02
<1
0.05
<1
e
e
e
e
e
e

e
e
0.04
e
0.05
<1
0.05
e
e
e
e
e
e
e
e

e
e
1.26
0.35
1.55
2.19
1.12
e
e
e
e
2.14
e
1.59
e

e
e
21.5
20.2
20.7
25.4
25.3
e
e
e
e
28.1
e
24.3
e

cations Na, K, Ca, Mg, Fe, B, Si, Li, Al, P, Sr, Rb and Ba were ltered
through 0.45 mm (0.1 mm for Al), acidied with 2 N HNO3 to pH < 2
and stored in a fridge at 4
C before analyses; these latter were
executed no later than 6 months after sampling, as foreseen in
Apha-Awwa-Wef (2012). Na, K, Ca, Mg, Fe, B and Si were analyzed
by ICP-OES (Prodigy, Teledyne Leeman Labs), whereas Li, Al, P, Sr, Rb
and Ba were analyzed by ICP-MS (7500 Series, Agilent Technologies). Additionally, sample aliquots for dissolved anions were
cooled and stored in the dark before analysis. Carbonate alkalinity
(cAlk CO3 HCO3) was measured on 20 ml aliquots as soon as
possible after sampling and extraction by acidimetric titration using 0.16 N H2SO4, phenolphthalein and bromocresol as dye indicators and pH monitoring by a multimeter, as in the Gran method

(Apha-Awwa-Wef, 2012; Gran, 1952). Cl, Br, SO2
4 , CH3COO
(acetate) and HCOO (formate) were analyzed on 20 ml, 0.45 mm
ltered samples (PTFE membranes) by ion chromatography (ICS
3000 model, Dionex) using an IonPac AS18 4  250 mm column
(Dionex) and KOH from an eluent generator. Total alkalinity (tAlk)
at sampling conditions was calculated by software forcing the ions
balance on total carbon (Bazin et al., 1997): i) to remediate possible
deterioration of alkalinity during extraction treatments; ii) to
compensate for the specic ions included in the alkalinity determination (organic, borate, silica anions and other bases).
Analysis of the delta hydrogen and oxygen isotope composition
of water molecules, d2H and d18O, respectively, in per mil ()
referring to V-SMOW, was performed using a CF-IRMS method on a
Gasbench II coupled with a Deltaplus XL (Thermo Finnigan) after gas
equilibration of H2OeH2 and H2OeCO2, respectively (Costinel et al.,
2009). Water samples extracted by demulsication processes were
distilled in a vacuum line before analysis (Boschetti et al., 2011). The
analytical precision (2 s) of the analyses was 0.15 for oxygen
and 2.0 for hydrogen.
3.4. Thermodynamic and kinetic calculations
To simulate the evolution of groundwater of meteoric origin,
PHREEQC Interactive, version 3.1.7.9213, along with the thermodynamic database phreeqc.dat, was used (Parkhurst and Appelo,
2015). For oileld waters, a two-step speciation and the use of
implemented thermodynamic databases were necessary for the
speciation/saturation index calculation and construction of the
activity diagrams, respectively. In the rst step, density and logfCO2
under analytical conditions (25
C and 1 bar) were calculated by the
SpecE8 tool of The Geochemist Workbench (GWB), version 7.0.6
(Bethke and Yeakel, 2008). Afterwards (second step), the dissolved
species activities and mineral saturation indexes were calculated at
the temperature of the wells and at three target pressures (200, 500

and 800 bar) by EQ3/6 software, version 8.0a, using the DebyeHckel equation for the calculation of the activity coefcients
(Wolery and Jarek, 2003). The resulting log activity ratios of dissolved species were plotted on activity diagrams. In these diagrams,
the Act2 tool of GWB and three original thermodynamic databases
were used to plot the stability elds of the minerals. The three
original databases were constructed at a temperature between 0.01
and 350
C and at the above mentioned isobaric pressures
combining different data sources (Electronic Annex 1). First, preliminary datasets were extracted from the le slop07.dat (http://
geopig.asu.edu/sites/default/les/slop07.dat) and converted in the
thermo.com.v8.r6.dat format by DBcreate software (Kong et al.,
2013). Then, the datasets were integrated with the logK data for
albite, clinochlore, microcline, and montmorillonites from the
UNITHERM thermodynamic database, version 4.4 (Shvarov, 2008),
extracted by K2GWB software (Cleverley and Bastrakov, 2005).
Additional clay minerals data for illite, montmorillonites, saponites,
and beidellites from Wolery and Jove-Colon (2007) and for vermiculites from Apollaro et al. (2013) were calculated at the targeted
T-P conditions by OrganoBioGeoTherm software (OBGT), version
1.52, a Microsoft Windows interface of SUPCRT (Johnson et al.,
1992). Additional clinochlore data were taken from Vidal et al.
(2005). This latter data are also available from the THERMODDEM
dataset: http://thermoddem.brgm.fr/(Blanc et al., 2012). The React
tool of GWB was also used to perform a kinetic reaction path
modeling by using parameters for quartz (Perez et al., 1999), chalcedony, kaolinite and albite (Manning, 2003; Palandri and Kharaka,
2004).
4. Results
Chemical results of the rst monitoring period (1980e2012) are
in the Electronic Annex 2, whereas chemical and isotopic data
obtained in the second one (2012e2013) are in Table 1. Chemical
classication of the waters was made combining major anionic and
cationic constituents on a ternary diagram (Fig. 2). Salinity was
subdivided into three groups according to the classication of
(Kharaka and Hanor, 2014): fresh < 1 g/l, 10 g/l > brackish > 1 g/l,
35 g/l > saline > 10 g/l, and brine > 35 g/l. The samples collected
during the rst monitoring campaign revealed two main chemical
water groups, NaeHCO3 and NaeCl, in which the salinity ranged
from 1.3 to 12.9 g/l for NaeHCO3 (mean 5.2 2.1 g/l,
median 4.9 g/l; 71 analyses) and 1.4e21.4 g/l for NaeCl
(mean 7.8 3.6 g/l, median 6.6 g/l; 96 analyses). Therefore,
both water groups are brackish to saline. A third, minor NaeSO4
group had a salinity of 12.0e17.1 g/l. Samples with this composition
were revealed in two wells (OF49, two analyses; OF25, one

T. Boschetti et al. / Marine and Petroleum Geology 73 (2016) 228e248

233

Fig. 2. CaeMgeNa and SO4eClecAlk (carbonate alkalinity as HCO3) ternary classication diagrams (Equivalent/L basis). Maracaibo Basin oileld waters from this study (colored
symbols, triangle-inscribed square: Na-tAlk; open symbol: PDVSA data in Electronic Annex 2) and literature are distinguished. The terms oileld (black), regional background (dark
gray) and inltration (light gray) represent a water classication proposed by Rachinsky and Kerimov (2015) in which the amount of fresh meteoric water input increase from the
former to the latter. Lake Maracaibo (Montero, 2006; Seelkopf and Luis Boscan, 1960), groundwaters from southwestward (Montero, 2006) and eastward (Quibor aquifer; Mella,

ndez and Sa

nchez, 2004; Moreno et al., 2007) and Caribbean seawater (Boschetti et al., 2015a) are also shown for comparison.
1982) of the lake, local thermal waters (Herna

Fig. 3. LangeliereLudwig (A) and Hounslow brine differentiation square (B) diagrams (Equivalent/L basis), respectively modied from Boschetti (2011). Symbols and data as in
Fig. 2. In both diagrams, green and pink areas represent CaeCl brines of sedimentary origin and NaeCl waters derived from halite and gypsum-anhydrite dissolution (Boschetti,
2011; Hounslow, 1995). In B, blue area represents interaction with Na-sulfates from evaporites (Boschetti et al., 2013). (For interpretation of the references to color in this gure
caption, the reader is referred to the web version of this article.)

T. Boschetti et al. / Marine and Petroleum Geology 73 (2016) 228e248

analysis), both located in fault-intersection zones at the WNW and

N boundaries of the study area. In the 15 samples collected during
the second monitoring campaign, no samples with NaeSO4
composition were revealed. The salinity of the waters was coherent
with
the
previous
monitoring
campaign:
NaeHCO3
(mean 5.9 0.6 g/l, median 6.1 g/l; 6 samples) and NaeCl
(mean 8.4 1.4 g/l, median 8.1 g/l; 9 samples). The slight increase in the median values may be due to the reduced number of
collected samples. Temperatures at the production depths were
between 96 and 142
C (120 15
C) in the onshore and 119e148
C
(133 15
C) in the offshore wells (PDVSA Occidente, personal
communication; Table 1). In three wells (ON12, OF7, OF27), temperature data are lacking; therefore, we use geothermometric
equations to estimate the temperature before the thermodynamic
calculations (see paragraph 4.3).
The laboratory pH was slightly more alkaline for NaeHCO3
(mean median 9.0) in comparison with NaeCl waters
(mean 8.8; median 8.5). However, CO2 degassing at the wellhead during sampling and then during laboratory treatment
increased the pH; therefore, it was recalculated for deep T-P conditions (see paragraph 5.1 for details).
The concentration of dissolved organic species showed a predominance of acetate (mean 650 mg/l, median 597 mg/l) over
formate (mean 27 mg/l, median 29 mg/l) with peaks up to
1243 mg/l (acetate) and 40.3 mg/l (formate) in the well at lower
temperature (ON5, 96
C), as expected for waters from the sedimentary basin (Kharaka and Hanor, 2014). The mean contributions
to total alkalinity (tAlk) of these two monocarboxylic anions (mAlk)
are approximately 48 23% (acetate, with a peak up to 80% in OF14)
and 3 1% (formate), respectively, compared to approximately
49 24% for carbonate alkalinity (cAlk). Generally, the slight predominance of mAlk over cAlk did not inuence the chemical classication made in Fig. 2, in which only cAlk was used to permit
comparison with the data from the literature. The ON4 and ON3
samples are an exception in that they are classiable as NaeCl if
only cAlk is considered (cAlk < Cl in meq/l) and as NaeHCO3 if tAlk
is considered (tAlk > Cl in meq/l). Most likely, the pH variation at
different P-T conditions can inuence the activity of the organic
species; therefore, these parameters are further discussed in the
speciation paragraph 5.1.
4.1. Ternary classication diagrams
Other than the scope of classication, the ternary diagrams
revealed some useful characteristics when historical data from the
investigated area and surroundings were plotted along with samples from this study (Fig. 2). In particular, anion diagrams showed
that three NaeCl waters (OF14, ON14, ON15) fall near the more
evolved CaeCl oileld brines (Bockmeulen et al., 1983; Porras et al.,
2007; Rachinsky and Kerimov, 2015). A strict correlation with this
evolved water facies should be made with caution because the
authors published the maximum and minimum values of the water
chemical parameters for every formation complex, but neither the
median nor the mean value of the sample database were given. The
calculation of the Ca/(SO4HCO3) parameter, on an equivalent basis
(Rosenthal, 1997), may be useful in conrming this hypothetical
relation. Onshore (ON14, ON15) and offshore (OF14) samples
showed values of 0.36, 0.97 and 0.41, respectively, which are lower
than the characteristic Ca/(SO4HCO3) > 1 that is typical of CaeCl
oileld brines (Rosenthal, 1997) but quite higher than the values
obtained for NaeHCO3 (mean 0.039; median 0.027) and NaeCl
(mean 0.077; median 0.041) during the rst monitoring
campaign.
The anions distribution in oileld waters (Fig. 2) is quite similar
to that of the shallow groundwaters analyzed in the south/

235

southwestward area of the lake (Montero, 2006; Montero et al.,

2008). Differently, the NaeSO4 composition was probably due to

ndez
the mixing of oileld waters with local thermal waters (Herna

nchez, 2004; Moreno et al., 2007) or to shallow cold
and Sa
groundwater (Mella, 1982) that have interacted with evaporites.
According to Sulin's classication, the sodium sulfate facies is an
usual representative of uncovered formations and/or the involvement of continental water of meteoric origin (Chilingar et al., 2003;
Collins, 1975). However, our ternary classication clashes with
Sulin's; in other words, our NaeSO4 waters would not be classied
as NaeSO4 using Sulin's classication (Collins, 1975). In Sulin's
classication, NaeSO4 waters should have the ratio (rNa-rCl)/
rSO4 < 1, where r is equivalents per million (Collins, 1975). However, our NaeSO4 samples had a lower value of Sulin's ratio (from
1.53 to 1.61) in comparison with NaeCl and NaeHCO3 waters,
which were 2. Moreover, NaeSO4 waters are characterized by a
SO4/HCO3 1.4 (mg/l basis). This agrees with studies conducted in
other basins worldwide, where SO4/HCO3 < 3 ratios were revealed
in water associated with hydrocarbons (Van Voast, 2003; Vel'kov,
1960). In the anion ternary diagram (Fig. 2), the mixing line from
the NaeSO4 samples intercepts three NaeCl samples from two
wells (OF47 and ON9) and the Eocene-Oligocene oileld endmember of Rachinsky and Kerimov (2015) in the Na/cAlk side.
Therefore, for these samples, the connection between shallow
groundwater and deep oileld waters is conrmed.
As expected, most of the oileld waters were indistinguishable
on the cation ternary diagram because they clustered on the Na K
corner, whereas more shallow groundwaters scattered towards
seawater, the Lake Maracaibo eld and the Ca corner, the latter of
which is according to the CaeHCO3 composition of a fresh
groundwater source (Fig. 2B). Starting from this source, sodium
enrichment due to NaeCa cation exchange is a common effect in
the shallow groundwater of coastal areas (Boschetti et al., 2015a),
whereas different and more complex watererock interaction processes must be invoked to explain the chemical differentiation of
the oileld waters.
4.2. Square diagrams
To obtain more information on the origin and evolution processes of the oileld waters, LangeliereLudwig and brine differentiation plots are shown in Fig. 3. In the former, NaeHCO3 and
NaeCl waters were better distinguished from local groundwater,
except for more diluted samples likely due to mixing. NaeCl waters
fell in the typical overpressured eld of the LangeliereLudwig diagram (Boschetti, 2011), whereas OF14 and ON14-ON15 samples
were more shifted towards the CaeCl eld (Fig. 3A). In particular, a
better distinction between pre-Cretaceous and Cretaceous CaeCl
brine is possible using this diagram. These characteristics were also
conrmed in the brine differentiation plot (Fig. 3B), in which the
involvement of the Cretaceous CaeCl in the ON14-ON15 samples is
more clear. Furthermore, in this latter plot, NaeSO4 waters and
mixed samples (OF47 and ON9) were better distinguished because
they fell in the eld devoted to interaction with Na-sulfates from
evaporites (Boschetti et al., 2013).
The Na decit versus Ca excess plot of Davisson and Criss (1996)
may help further clarify the evolution of oileld waters by
comparing Na, Ca and Cl concentrations with that of mean seawater
(Fig. 4):


Caexcess 2 Cameas  Ca=ClSW Clmeas 40:08

(1)


Nadeficit Na=ClSW Clmeas  Nameas 22:99

(2)

236

T. Boschetti et al. / Marine and Petroleum Geology 73 (2016) 228e248

where meas sample concentration and SW seawater, both in

mg/l. Surprisingly, only the oileld water from Tia Juana Field
(Fig. 4B; Chacn, 2011) fell on the basinal uid line (BFL), which is
representative of CaeCl brines that produce albitization/zeolitization processes during diagenesis (Boschetti et al., 2011; Davisson
and Criss, 1996). However, Cretaceous and pre-Cretaceous CaeCl
waters along with ON14, ON15 and OF14 samples from this study,
plotted near the line parallel to the BFL passing through seawater or
near the BFL passing through the point of halite precipitation after
seawater evaporation (Fig. 4). Most of the NaeCl waters clustered in
the negative sector of the eld, i.e., showed a Na excess-Ca decit
compared with seawater (origin of the plot). In particular, a trend
from the abscissa to the Eocene, Oligocene and Miocene formation
main values (Rachinsky and Kerimov, 2015) was evident (Fig. 4).
Similar to NaeCl waters, NaeHCO3 waters showed an Na excess,
but these latter waters were characterized by a Ca excess up to
approximately 5, different from most NaeCl waters with a Ca
decit to approximately 5. The opposite shifts from the calcium

axes were likely a consequence of the fact that, whereas NaeCl

waters are more related to oileld reservoirs, NaeHCO3 waters in
part inherit the shallow groundwater composition in spite of the
deep burial. In fact, groundwater showed a more pronounced Ca
excess, in particular when samples interacting with evaporites such
as thermal waters were considered (Fig. 4). The three anomalous
NaeSO4 samples showed the highest Na excess and plotted near
the BFL (till to 190; Fig. 4). However, three NaeCl waters from the
OF47 and ON9 wells were shifted towards that value starting from a
Na excess of approximately 90 (Fig. 4). These samples could be
(mis)interpreted as CaeCl-evolved brine but, according to the
NaeSO4 genesis (Chilingar et al., 2003; Collins, 1975) and in line
with mixing trends deduced from Fig. 2, we suspect that an
involvement of shallow groundwater in the deep circuit could have
produced this Na excess. In other sedimentary basins, similar high
Na excesses were revealed both in overpressured and hydropressured wells and were interpreted as being due to albite hydrolysis (Boschetti et al., 2011; Du et al., 2010; Xie et al., 2003). To

Fig. 4. Na-dect vs. Ca-excess diagram for oilled waters from the Maracaibo Basin (symbols as in Fig. 2; data from this study and the literature). The basinal uid line (BFL)
characterizes CaeCl formation uids in sedimentary basins and it is similar to a 1Cae2Na exchange line during albitization (Davisson and Criss, 1996). Black dashed-dotted lines are
parallel to BFL. Colored dotted lines represent the interaction between sandstone minerals and groundwater modeled at different temperature (50, 75, 125, 150
C) and pressure
(200, 500, 800 bar). See text for details. (For interpretation of the references to color in this gure caption, the reader is referred to the web version of this article.)

T. Boschetti et al. / Marine and Petroleum Geology 73 (2016) 228e248

237

conrm this hypothesis, we modeled the interaction between a

NaeSO4 shallow groundwater as uid and three primary minerals
of the sandstone as solid reactant at different temperatures (from
25
C to 150
C) and pressures (200, 500 and 800 bar) using
PHREEQC code (Parkhurst and Appelo, 2015). The saturation indexes of the minerals and CO2 fugacity of the uid were xed at
SIquartz 0.2, SIK-feldspar 0.6, SIalbite 0.2 (as the mean values
detected in the oileld waters of Lake Maracaibo, see paragraph 5.1)
and logfCO2 1.5, respectively. The CO2 fugacity value is similar to
that typically measured in shallow groundwaters from cultivated
areas (Appelo and Postma, 2007) or to that calculated from the

ndez and Sa

nchez, 2004).
analyses of Trujillo thermal waters (Herna
Minerals composing the lithic fraction of the sandstone were the
solids allowed to precipitate: calcite, chalcedony, chlorite, kaolinite
and illite. The interaction process showed decreasing Na-decit and
Ca-excess values (or, in other words, increasing Na excess and Ca
decit), the former being higher at higher pressures, and a switch
from a NaeSO4 to a NaeHCO3 composition due to high logPCO2. The
200 bar process path intercepted the BFL exactly at the Tia Juana
Field sample, which had a NaeHCO3 composition (Fig. 4). After
intercepting the abscissa of the plot at the 50
C step, the Ca decit
decreased to zero, and the Na increase trended backwards towards
the seawater value, while the interacting waters again switched
their composition from NaeHCO3 to NaeSO4 (Fig. 4).
4.3. Geothermometry and Br, B geochemistry
Chemical geothermometers are useful in determining the deep
temperature of waters, especially when bottom-hole measures of
temperature are lacking or to gain information on the thermal
history of the reservoir. In the investigated MB formation waters,
the relatively high concentration of silica and lithium (Table 1)
prompted the use of the theoretical equilibrium equations of silica
phases and/or the use of the empirical equations related to the Na/
Li and Mg/Li ratios (Kharaka and Hanor, 2014; Kharaka and Mariner,
1989).
Generally, wells with higher measured temperatures showed
better concordance with the geothermometric results (Fig. 5). In
particular, the low standard deviation obtained from the quartz
(160 5
C) and chalcedony (134 4
C) equations of Verma (2001)

rsson et al. (1983), respectively, which gave the best reand Arno
sults in low-enthalpy systems (Awaleh et al., 2015), testies that the
silica phases are not sensible to the subsurface temperature variations (Fig. 5). This is probably due to the persistence of silica supersaturation at low temperatures, as occurs in the Gulf Coast and
Gulf of Mexico sedimentary basins (Land, 1997; Land and
Macpherson, 1992). Such an effect occurs when high amounts of
dissolved silica (e.g., from biogenic opal or feldspar dissolution,
kaolinite illitization, quartz pressure dissolution) are preserved
from precipitation due to clay or authigenic chlorite coatings on
quartz seeds or to the nucleation of microcrystalline quartz
(Worden and Morad, 2000). It is important to evaluate this effect
because silica supersaturation balances quartz pressure dissolution,
thus preserving porosity to greater depths than expected (Jahren
and Ramm, 2000). Thermodynamic speciation is useful to depurate the eventual physico-chemical effects from equilibrium
equations (Kharaka and Hanor, 2014) that are, in this case, not due
to salinity but to the pH increase after sampling. Therefore, other
evaluations of silica phase equilibria are postponed in the speciation paragraph 5.1. The Mg/Li equation produced underestimated
values probably due to precipitation of Mg-carbonates or exchange
with clays (Fig. 5). According to Land and Macpherson (1992), Na/Li
agreed better with the measured values; therefore, it was more
successful in the subsurface temperature estimation at different
depths. For the two samples ON12 and OF7 which the deep

Fig. 5. Calculated (this work) vs. measured temperatures at the producing depth in the
oileld water samples from Maracaibo Basin. In the geothermometric equations used
for calculation (see references in the key), concentration values in mg/l of SiO2, Na, Li
and Mg were used.

measured temperature was missing, Na/Li geothermometer gave

121
C and 145
C, respectively.
Boron has great potential to be used as a geothermometer in
sedimentary basins. However, applicability of a boron geothermometer is precluded when seawater-derived formation waters are diluted by meteoric waters (Boschetti et al., 2015b).
Combining the d11B-T
C and 1/B-T
C equations inferred by
Boschetti et al. (2015b), it is possible to relate the boron concentration to temperature in formation waters:

h
T
C

i
5:1364  ln1=Bmg=1 5:7280:180
0:1640:012

(3)

The effectiveness of the equation can be tested further. For

example, a boron concentration of 75 mg/l (approximately 15 times
that of present-day seawater) at 100
C is calculable from equation
(3), which corresponds to the boron extracted from marine porewater at the same temperature (Hpers and Kopf, 2012). B/Cl
weight ratios are also useful to determine water origin and mixing
processes. In Fig. 6A, formation waters from the MB were out of a
seawater-derived brine area, but grouped between the elds of
overpressured waters and typical terrestrial NaeHCO3 waters. A
mean boron content of 32 7 mg/l in the MB oileld waters

238

T. Boschetti et al. / Marine and Petroleum Geology 73 (2016) 228e248

Fig. 6. Chloride vs. boron (A) and bromide (B) plots (in mg/l, logarithmic scale). Symbol as in Fig. 2. Dotted lines represent binary mixings. If no specied in the keys, elds as in
Boschetti (2011) and Boschetti et al. (2011), respectively.

(approximately 100 times that of Lake Maracaibo, Fig. 6A) testies a

boron release from clay and/or kerogen during diagenesis. However, most of the NaeHCO3 samples depicted a characteristic path
showing a chloride decrease at a constant boron concentration
(Fig. 6A), similar to the freshening effect related to clay dewatering
(Hpers and Kopf, 2012). Presumably, the boron geothermometer

gave better results in oileld waters falling on the boundary of the

overpressured eld (Fig. 6A; Boschetti et al., 2015a, b). For example,
sample OF7 fell near the dilution lines departing from diagenetic
boron at 150
C (Fig. 6A). Therefore, the temperature of 145
C
estimated for OF7 with the Na/Li geothermometer would be
plausible.

T. Boschetti et al. / Marine and Petroleum Geology 73 (2016) 228e248

239

Fig. 7. A: logf(H2)gas versus temperature showing the values of H2 calculated for each oileld waters of Maracaibo Basin (symbols as in Fig. 2). Pressure effect is not relevant at the
scale of the diagram. Gray eld: formation waters sampled worldwide in which H2 was calculated from acetic and propanoic acids (Shock, 1994). Colored lines: logf(H2)gas values
consistent with ratios of hydrocarbons (Shock, 1994). B: Quartz and chalcedony saturation indexes of the Maracaibo Basin oileld waters. Small, medium and big symbols are related
to results obtained after speciation at the pressures of 200, 500 and 800 bar, respectively. (For interpretation of the references to color in this gure caption, the reader is referred to
the web version of this article.)

Bromide concentrations and Cl/Br weight ratios are widely used

tracers in sedimentary basins because bromide is similarly conservative as is chloride and a signicant difference in Cl/Br ratios
between most oileld waters (Cl/Br < 286 in CaeCl brines) and
halite-solution brines (Cl/Br > 286) can be established (Boschetti
et al., 2011; Eggenkamp, 2014; Rosenthal, 1997). The MB waters
match the oileld waters group, with no relevant difference in
bromide content with respect to local groundwater (Fig. 6B).
5. Discussion
5.1. Speciation of organic constituents, saturation indexes and
kinetic constraints to minerals precipitation
The activity of the species dissolved in the water samples
collected during the second sampling campaign was calculated at

deep P-T conditions by EQ3/6 software. The measured-calculated

temperature at the sampling depth and at three pressure values
(hydrostatic: 500 bar, high pressure: 800 bar, low pressure:
200 bar) were used. LogPCO2 1.0 and logPCH4 2.0 were also
imposed at deep conditions according to the composition of the
extracted gases (Gonz

alez and Garca, 2012). This pH estimation
approach was preferred over the carbonate equilibrium (Hutcheon,
2000; Smith and Ehrenberg, 1989). The results (Electronic Annex 3)
showed a mean pH value of 5.91 0.17, while the fugacity of dissolved molecular oxygen and hydrogen was logfO2 53.0 and
logfH2 2.7 (median values), respectively. The obtained logfH2
values agree with those calculated in other sedimentary basins
sampled worldwide, in which logfH2 was estimated from
the equilibrium between petroleum compounds or between acetic
and propanoic acids (Fig. 7A; Shock, 1994). Therefore, the activities
of propanoic acid and propanoate could be estimated in the

240

T. Boschetti et al. / Marine and Petroleum Geology 73 (2016) 228e248

Fig. 8. Results of the kinetic reaction path modeling (begins at t 0 years, T 150
C, P 500 bar, ends at t 4  103 years, T 80
C, P 500 bar). Solid reactant: albite_low; liquid
reactant: sample OF14 (logfCO2 1). Red lines represent solid phases with known kinetic parameters (see references in methods paragraph 3.4), whereas minerals in gray were free
to precipitate and chosen by GWB-React tool to equilibrate the uid during modeling. (For interpretation of the references to color in this gure caption, the reader is referred to the
web version of this article.)

samples from the MB (Electronic Annex 3). At hydrostatic pressure,

the results of organic acid and relative anion speciation revealed
the following log-activity trend: acetic acid > formic
acid >> propanoic acid, with logaacetic_acid 6.44 0.03,
logaformic_acid 7.10 0.18, logapropanoic_acid 9.47 0.06, and
formate > acetate >> propanoate, with logaformate 5.2 0.2,
logaacetate 5.5 0.2 and logapropanoate 8.6 0.2. A slight
increase and decrease characterized the speciation of organic anions at low pressure and high pressure, respectively. The activity of
acetate and formate under depth conditions showed a reverse
trend compared to the measured concentrations under laboratory
conditions. In oileld waters, formate and formic acid are usually
found at much lower concentrations than are acetate and other
organic acids such as propanoate (Kharaka and Hanor, 2014).
However, these general observations usually involve mg/l concentrations under laboratory conditions, whereas the activity of the
species under depth condition is often neglected. The obtained

mean values of loga(formate/formic acid) 1.9 0.2 and loga(acetate/acetic

1.0 0.2 at hydrostatic pressure and mean temperature
(125
C) and pH (5.91) are in accord with the published activity
ratios plots from other basins (Shock, 1994). The highest logaformic
acid and logaformate were obtained in the sample with the highest
temperature (OF32 148
C). Therefore, these results concerning
organic acids and anions could be easily explained as a speciation
effect, but are also in accord with the experiments of McCollom
and Seewald (2003), who found that thermodynamic equilibrium
with CO2 and H2 exerts a predominant inuence on the abundance
of formic acid and formate at high temperatures (>100
C). Acetate
and formate were also found in local Maracaibo rainwater (Morales
et al., 1994, 1998). Apart from an anthropogenic source of organic
acids used to stimulate oil production (Burgos et al., 2005), their
presence in the atmosphere could be related to hydrocarbon
extraction. However, a link to anaerobic fermentation by lake algae
is more probable due to the presence of pyruvate in rainwater
acid)

(a)

2.5
8.5

3.0

3.5

4.0

2.5

3.0

2.5

3.0

Vermiculite-Mg-Mg

8.0

Montmor-Mg

+ 2

8.5

Saponite-Mg

ON14

Montmor-Mg
Microcline

ON15

Microcline

Microcline

K-feldspar

K-feldspar

K-feldspar

7.5

4.0

125C - 800 bar

100C - 800 bar

Saponite-Mg
OF32

Vermiculite-Mg-Mg

3.5

150C - 800 bar

100C - 500 bar

Saponite-Mg

Montmor-Mg

2+

4.0

125C - 500 bar

125C - 200 bar

100C - 200 bar

log[(Mg )/(H ) ]

3.5

150C - 500 bar

150C - 200 bar

8.0

log[(K )/(H )]

7.5

OF7

Vermiculite-Mg-Mg
Vermiculite-Mg

OF14

Vermiculite-Mg

7.0

ON13

Vermiculite-Mg

7.0
Kaolinite

Kaolinite
Kaolinite

6.5

6.5

6.0

6.0
Albite_K2GWB

Albite_K2GWB

Albite_K2GWB

5.5

5.5

Vermiculite-Na-Al
Vermiculite-Na-Al

5.0

5.0

log[(Na )/(H )]

Vermiculite-Na-Al

OF32

ON15

ON13

4.5

Microcline

Beidellite-Na
OF14

ON14

OF7

Microcline

4.0

K-Feldspar
Kaolinite

K-Feldspar

Microcline

Maximum
Microcline

K-Feldspar

Kaolinite

Maximum
Microcline

Kaolinite

4.0

Maximum
Microcline

3.5

3.5
150C - 500 bar

150C - 200 bar

3.0
2.5

4.5

150C - 800 bar

125C - 200 bar

125C - 500 bar

125C - 800 bar

100C - 200 bar

100C - 500 bar

100C - 800 bar

3.0

3.5

4.0

2.5

3.0

3.5

4.0

2.5

3.0

3.5

3.0
4.0

log[(K+)/(H+)]
Fig. 9. Activity plots for the system K2OeAl2O3eSiO2eH2OeMgO/Na2O at 100e125e150
C and 200e500e800 bar. Chalcedony saturation was imposed at 100
C and 125
C, whereas quartz at 150
C. Muscovite (a minor mineral in
comparison to silica and feldspar phases; Perez and Boles, 2005) and clinochlore elds were disabled in (A) and activated in (B).

log([K ]/[H ])
2.5
8.5

3.5

3.0

4.0

2.5

3.0

Saponite-Mg

125C - 200 bar

2.5

125C - 500 bar

Clinochlore

OF32

Clinochlore

8.0

ON15

Montmor-Mg

8.5

Saponite-Mg

125C - 800 bar

Microcline

Montmor-Mg

Microcline

Montmor-Mg

Microcline

4.0

100C - 800 bar

ON14

Clinochlore

3.5

3.0
150C - 800 bar

Saponite-Mg

+ 2
2+

4.0

100C - 500 bar

100C - 200 bar

8.0

3.5

150C - 500 bar

150C - 200 bar

K-feldspar

K-feldspar

K-feldspar

7.5

7.5

Vermiculite-Mg

OF7

OF14

Vermiculite-Mg
Vermiculite-Mg

FRA8

7.0

Muscovite

7.0

Muscovite

Muscovite

Kaolinite

Kaolinite

Kaolinite

6.5

6.5

6.0

6.0
Albite_K2GWB

Albite_K2GWB

Albite_K2GWB

5.5

5.5

Vermiculite-Na-Al

Vermiculite-Na-Al

5.0
OF32

Microcline
FRA8

Microcline

ON15

4.5

K-Feldspar

4.5

K-Feldspar

Kaolinite

Muscovite

Muscovite

ON14

K-Feldspar

4.0

OF7

Kaolinite

OF14

Microcline

Kaolinite

log([Na+]/[H+])

Vermiculite-Na-Al

5.0

Muscovite

4.0

3.5

3.5
150C - 200 bar

150C - 200 bar

3.0
2.5

150C - 200 bar

125C - 200 bar

125C - 200 bar

125C - 200 bar

100C - 200 bar

100C - 200 bar

100C - 200 bar

3.0

3.5

4.0

2.5

3.0

log([K+]/[H+])
Fig. 9. (Continued).

3.5

4.0

2.5

3.0

3.5

3.0
4.0

T. Boschetti et al. / Marine and Petroleum Geology 73 (2016) 228e248

log([Mg ]/[H ] )

242

(B)

T. Boschetti et al. / Marine and Petroleum Geology 73 (2016) 228e248

243

Fig. 10. d2H(H2O) vs. d18O(H2O) values diagrams. In both: colored symbols (as in Fig. 2) circumscribed in the green area are the oileld waters from Maracaibo Basin (this study).
Dashed area and open diamond: groundwater southwestward of the Lake Maracaibo and Orinoco River, respectively (Montero, 2006); GMWL: Global Meteoric Water Line with
deuterium excess d 10 (Rozanski et al., 1993); red line represents the best t between oileld waters and local groundwater. Data from this study are compared with: A e
formation waters in sedimentary basins from North America (gray elds and tting lines from Sharp, 2007, updated with JujoeTecominoac
an elds from Gulf of Mexico, Birkle et al.,
2009); B e mean and sigma values of shallow aquifers from Merida ranges (MR), Maracaibo (MA) and Quibor (QU) (IAEA, 2009); waters from Lake Valencia (LV) and Lagoon
Taguaiguay (LT) (Jegat et al., 1995); Venezuela Basin porewaters (Friedman and Hardcastle, 1973; Lawrence, 1973); Caribbean Seawater (SW; Boschetti et al. 2015); generic diagenetic
water elds from kaolinite/smectite (scaly eld; Boschetti et al., 2011) and chlorite (bricked eld; Longstaffe, 2000) water-mineral equilibrium. Arrows depict possible fractionation
effects (in italic; S slope). Maracaibo Lake eld (LM) was deduced projecting the d2H(H2O) data (Friedman and Norton, 1956) between the lines corresponding to meteoricseawater mixing and evaporation effect (see Fig. 11). (For interpretation of the references to color in this gure caption, the reader is referred to the web version of this article.)

244

T. Boschetti et al. / Marine and Petroleum Geology 73 (2016) 228e248

Fig. 11. Chloride concentration (mg/l and logarithmic scale) vs. d2H(H2O) diagram. Symbols and elds as in Fig. 10 except data from Friedman and Norton (1956). Chloride concentration in porewaters of Venezuela Basin were from Hammond (1973). Curves represent binary mixing. Dashed line represents the tting of the MB formation waters of this
study, which extend towards the diagenetic eld.

(Chapelle, 2001).
Concerning water-mineral saturation indexes of the sampled
waters, the calculation results at hydrostatic pressure revealed
(Electronic Annex 3): calcite (0.44 0.53) and albite
(0.23 0.21) undersaturation; equilibrium with chalcedony
(0.01 0.12); quartz (0.22 0.13), kaolinite (1.02 0.71) and Kfeldspar (0.55 0.30) oversaturation. This means that calcite and
albite dissolve whereas kaolinite could precipitate, altering the
reservoir porosity and permeability. Actual precipitation of silicabearing phases necessitate a more accurate inspection from a kinetic point of view, in particular to verify the possibility of quartz
and K-feldspar overgrowth in sandstone. Apparently, saturation
indexes of quartz and chalcedony increased more at lower temperature than at lower pressure (Fig. 7B; Electronic Annex 3).
Therefore, to test this effect, a kinetic reaction path was calculated
lowering the temperature from 145
C to 80
C during an arbitrarily
chosen time window of 4  103 years. The most analytically complete and hot sample OF14 was chosen as chemical composition of
the initial uid, with logfCO2 1 and P 500 bar xed during
modeling. Only albite_low was chosen as solid reactant, whereas
the precipitation of quartz and K-feldspar was monitored due to
their oversaturation in oileld waters. However, though these as
well as all solid phases of the thermodynamic database were left
free to precipitate, only six minerals formed during the modeling
(Fig. 8). Notwithstanding the oversaturation increase, the quartz
amount was lower than 4e5 order of magnitude in comparison
with chalcedony and kaolinite. Moreover, the lack of K-feldspar in
the produced phases should exclude the hypothesis of its overgrowth. In facts, this phenomenon is typical of early diagenesis,
whereas K-feldspar dissolution commonly gone to completion at
T > 100
C (Bjrlykke et al., 1995). In the study area, water of

meteoric origin promoted the leaching of feldspar, rock fragments,

and clays from the Misoa Formation and produced a highly porous
and permeable diagenetic quartzarenite during Oligocene uplift
(Ghosh et al., 1990). Differently, most of dissolving calcite was
precipitated during hydrofracturing and sealed microfractures after
hydrocarbon migration (approximately 36e28 MY from present;
Perez and Boles, 2005).
5.2. Activity diagrams
In this paragraph, the results of the water sample speciation are
inspected in the activity diagrams that describe the
MgOeNa2OeK2OeAl2O3eSiO2eH2O system (Fig. 9). This type of
diagram is a powerful graphical tool to depict the stability of both
primary minerals and clays with respect to the composition of the
coexisting solution (Apollaro et al., 2013; Cortecci et al., 2005).
Temperature and pressure were varied according to those used for
speciation.
In the diagrams with magnesium, at T 100
C, the K-feldsparmontmorillonite and the microcline-montmorillonite stability lines
include most of the sampled waters (Fig. 9A). Kaolinite is the
favored mineral at hydrostatic pressure (500 bar) or overpressure
(800 bar) but is not favored at lower pressure (200 bar). Differently,
the saponite and vermiculite stability elds increase with temperature (Fig. 9A).
Montmorillonite disappeared in the plot with sodium, where
the vermiculite-Na-Al eld includes all of the samples at 150
C,
according to the kinetic modeling. In addition, beidellite-Na appears in the low-pressure diagram (200 bar).
In the fresh sediments of Lake Maracaibo, most of the kaolinite
with minor illite, chlorite and mixed layer illite-chlorite may be

T. Boschetti et al. / Marine and Petroleum Geology 73 (2016) 228e248

allogenetic because it is transported by rivers to the lake from the

surroundings ranges (Hyne et al., 1979; Weingarten et al., 1990).
Differently, kaolinite and chlorite are the main clay minerals of the
Misoa Formation of the MB; kaolinite predominates in the central
lake elds (Gonzales and Gustavo, 1991), and chlorite increases
until it predominates southeastward (Marcano, 2011). According
to this latter evidence, illite did not appear in the diagram;
therefore, it is metastable in contact with water samples, whereas
chlorite as clinochlore is found in activity plots with Mg (Fig. 9B).
Vermiculite formation is favored at higher temperatures (Fig. 9A
and B).
Generally, authigenic chlorite and illite are produced during
deep burial diagenesis at the expense of montmorillonites,
whereas vermiculite or mixed layers of vermiculite/chlorite
(corrensite) are found in intermediate stages (Larsen and
Chilingarian, 1983). However, chlorite and illite can be weathered back to vermiculite and montmorillonite, respectively
(Chilingar et al., 2003; Larsen and Chilingarian, 1983); therefore,
the mixed layers could also be the intermediate stages for
weathering processes (Essington, 2015). The evaluation of clay
dehydration and the consequent release of water during diagenesis are important not only because they may determine the pore
pressure (Chilingar et al., 2003) but also because they may
contribute solvent to the formation waters (Boschetti et al., 2011).
It would be difcult to evaluate the kinetics of the involved reactions, especially considering the relatively low temperatures
involved and the presence of organic matter. However, the
calculated logK of illite weathering to produce kaolinite, smectites
(saponite or montmorillonite) or vermiculites at the temperature
and pressure of the MB and using the activity of the dissolved
constituents in the sampled waters conrmed that the reactions
are shifted towards the right side (products favored) and water is
consumed (hydration; Electronic Annex 4):

245

and 2.14 < d18O < 1.59 in two samples distributed onshore
of Lake Maracaibo (Table 1). Explanations for the stable isotope
systematics of basinal uids are peculiar for each basin, complicated by many processes occurring during the origin and evolution
of formation waters (Clark and Fritz, 1997): 18O exchange with
rocks, 2H exchange with hydrocarbons, H2S and hydrated minerals,
clay dewatering, anhydrite hydration-dehydration, and hyperltration. Some features, such as the involvement of meteoric water
and evaporated marine components, are common to brines from all
basins (Sharp, 2007). In fact, the formation waters from North
America showed both 18O and 2H enrichments from the global
meteoric water line (GMWL, Fig. 10A). The enrichment of the water
isotope composition of the oileld waters from the MB analyzed in
this study compared to the shallow groundwater of meteoric origin
(d18O 4.98 0.6, d2H 33.4 3.9, N 16; Montero, 2006)
is similar to those of the formation waters from North America
(Fig. 10A). However, it is difcult to distinguish the main cause of
this enrichment because the water samples from tropical areas may
be affected by primary (during rain events) and secondary (from
open surface water bodies) evaporation effects, which could produce enrichment similar to meteoric-seawater mixing (Boschetti
et al., 2015a). Concerning rainwater, the isotope dataset performed by IAEA in Venezuela is old (1961e1998) and not complete
because most of the samples, from the 4 stations distributed in the
Venezuela Andes, were collected discontinuously during the hydrologic year (IAEA/WMO, 2015). Despite this lacking data, most of
the rainwater samples from IAEA are distributed between two
meteoric water lines, one with a deuterium excess of 10 (i.e., close
to the GMWL) and one with a deuterium excess of 15 (Fig. 10B).
The groundwater (SW of Lake Maracaibo; Montero, 2006) depicts a
small 18Oe2H enrichment probably due to underground evaporation. However, it intercepts GMWL similarly to the mean data of
Maracaibo, Merida range and Quibor aquifers (IAEA, 2009), testi-

K0:6 Mg0:25 Al1:8 Al0:5 Si3:5 O10 OH2 1:653H2 O 0:6CO2 g 0:6K 0:07899Mg3:165 Al0:33 Si3:67 O10 OH2
saponiteMg

illite

1:137Al2 Si2 O5 OH4 0:9362SiO2 0:6HCO

3
kaolinite

Additionally, in reactions in which chlorite produces vermiculites, the logKs are shifted towards the right side, but, in these cases,
water molecules are generated (dehydration; Electronic Annex 4):

Mg5 Al2 Si3 O10 OH8 4SiO2 16:5Al2 Si2 O5 OH4

clinochlore

chalcedony

kaolinite

24:5H2 O 12:5Mg0:4 Al2:8 Si3:2 O10 OH2

(5)

vermiculiteMg

Only reactions involving clinochlore thermodynamics from

Vidal et al. (2005) (Thermoddem dataset) and producing
vermiculite-Na-Mg had logK values favoring the reactants. For all of
the clinochlore thermodynamics considered in this work, the logK
increased at lower pressures in the reactions, producing
vermiculite-Mg, whereas it decreased in the reaction with
vermiculite-Na-Mg (Electronic Annex 4).
5.3. Water isotope composition
The seven oileld waters analyzed for isotopic composition
showed 25.4 < d2H < 20.2 and 2.19 < d18O < 0.35 in
ve samples distributed offshore and 28.1 < d2H < 24.3

(4)

quartz

fying that isotope composition of shallow groundwater does not

underwent fractionations depending by provenance (Fig. 10B). The
primary evaporation effect on meteoric waters is represented by a
line with slope S 5, calculated by a best t between the shallow
groundwater eld of Montero (2006) and a very enriched rainwater
sample (not shown in Fig. 10B, 1964-11-15 rain event, Maracay
station: d18O 5.6; d2H 19.3; IAEA/WMO, 2015).
Considering that the slope of the best t line describing evaporation
is a function of relative humidity (Clark and Fritz, 1997), the obtained value S 5 is in accord with the mean relative humidity at
Maracaibo, which is approximately h 0.75. In the same Fig. 10B,
secondary evaporation effects are shown by two elds representing
the isotopic compositions of Lake Valencia and Taguaiguay Lagoon
(Jegat et al., 1995), respectively. These open water bodies are
approximately 350 km ENE away from the study area, but at similar
latitude. Both the lake and lagoon elds fall on the S 5 line
(Fig. 10B); therefore, both primary and secondary evaporation effects produce similar fractionation. Conversely, the oileld waters
analyzed in this study did not fall on the evaporation line, but between this line and the mixing line between the elds of local
groundwater and diagenetic water elds for chlorite or kaolinite/

246

T. Boschetti et al. / Marine and Petroleum Geology 73 (2016) 228e248

smectite. These elds represent the water contribution from clay

dehydration processes occurring during diagenesis at 150
C
(Boschetti et al., 2011; Longstaffe, 2000). Surprisingly, the porewater extracted from the present-day to Eocene sediments of the
Venezuela Basin in the Caribbean Sea (Friedman and Hardcastle,
1973; Lawrence, 1973) showed a hydrogen isotope composition
that was different both from the oileld waters of the MB and from
generic diagenetic waters (Fig. 10B). This is probably due to the
waxing and waning of the last glaciation ice sheets and/or to the
inux of fresh water (Birkle et al., 2002; Savin, 1980). In fact, the
eld that encloses the porewater from the Venezuela Basin extends
from V-SMOW and intercepts the meteoric water lines, conrming
a seawater dilution by Late Pleistocene meteoric waters (19
than recent one for d2H, Ferronsky, 2015). Differently, freshwater
ood derived from deicing had a composition from 12 to 17
in d18O and 88 to 129 in d2H (Birkle et al., 2009; Ferronsky,
2015; Polissar et al., 2006). However, no shift towards these isotopic
range of values is visible neither for Venezuela Basin porewaters
nor for formation waters of this study (Fig. 10B).
Another process that could inuence the formation waters is
hyperltration, also known as ultraltration or membrane ltration. However, the experiments conducted to study the isotopic
fractionation related to this process produced contrasting results
(Longstaffe, 2000). In spite of this, researchers often explain water
isotope results by simply looking at the slope of their d18O-d2H
data; if the slope is equal or similar to 3.1, obtained from the laboratory experiments of Coplen and Hanshaw (1973), hyperltration
is conrmed, and the other processes are ignored. In MB oileld
waters, we could heedlessly jump to the same conclusion. In fact,
when tting the oileld waters alone, the slope is 3.26, and it is 2.94
when shallow groundwaters are included; therefore, the central
value of 3.10 exactly meets the expectations of ultraltration. As a
consequence of this, hyperltration should not be rejected a priori,
but rather it should be compared with other potential fractionations and water sources. For example, in Lake Maracaibo, porewater entrapped in the sediment may have inherited the isotopic
composition of the lake, and this could be another potential water
source for the oileld waters. This hypothesis is conrmed in Fig. 11.
In this gure, it is evident that the oileld waters are very similar to
the deep Lake Maracaibo waters, which has been extensively
studied by Friedman and Norton (1956). Hyperltration, if present,
was quite minimal because chloride should increase with d2H
following the Rayleigh equation (Phillips and Bentley, 1987), but, in
this case, the Cl concentration decreased opposite to d2H (Fig. 11). In
particular, offshore NaeCl samples are more shifted towards
seawater-meteoric mixing, whereas onshore NaeHCO3 samples are
more shifted towards evaporitic fractionation. However, the d2HeCl
best t of the MB samples extrapolated towards low Cl values
shows that the contribution of diagenetic waters cannot be ruled
out (Fig. 11). An extended isotope monitoring of onshore waters
could better clarify the contributions of different water sources.
Finally, the difference between the d18O of Lake Maracaibo, not
available and not analyzed by Friedman and Norton (1956), and the
oileld waters would give more information on the O-shift due to
diagenesis: at this stage of research, a enrichment of 2 might be
imputable to this effect (Fig. 10B). Moreover, isotope analysis of
local diagenetic chlorite minerals and calculation of equilibrated
water could dene the eld of the local diagenetic water in the
2
He18O diagram (Longstaffe, 2000).
6. Conclusions
Formation waters from southeast of the Maracaibo Basin (MB)
showed two main geochemical facies: NaeHCO3 and NaeCl. While
both inherited the hydrogen isotope composition of the lake, the

former facies was located mainly in the onshore area and the latter
in the offshore elds. Two onshore eld waters (ON14, ON15) were
an exception that presented a NaeCl composition and a supposed
connection with more evolved CaeCl Cretaceous brines. This information was furnished mainly by square plots which, being a
powerful tools to discriminate water from the different sources
rocks, could be helpful to the hydrocarbon exploration. The NaeSO4
chemical facies is rare and only revealed in the faulted area in the
northwestern boundary of the study area. In particular, thermodynamic modeling demonstrated that thermal shallow groundwater of meteoric origin (or cold water interacting with evaporites)
showed a NaeSO4/NaeHCO3 alternating composition when interacting with albite at increasing temperatures. It is not excluded that
a similar composition was generated during waterooding of the
eld. The theory of Rachinsky and Kerimov (2015) was partially
conrmed: the presence (Na)-sulfate waters in the overlying
complexes could be explained as a result of the vertical hydraulic
communication between the lower and upper stages of the sedimentary section. Thermodynamic speciation revealed that formate
activity is higher than that of acetate under deep conditions,
especially at higher temperatures and pressures, i.e., the reverse of
the concentrations measured under laboratory conditions. Calculation of saturation indexes also revealed that oversaturation of
silica phases is higher at low temperatures and pressures, but kinetic model showed that precipitated amounts of chalcedony,
kaolinite and clays prevail when compared with quartz (this latter
practically irrelevant). Calcite and albite dissolution (undersaturation) and recrystallization of diagenetic chlorite-illite into
smectites and vermiculites were also detected. Clay dehydration
characterized these reactions, with a possible enrichment of the
d18O values particularly for NaeHCO3 waters. Differently from
sedimentary basin of North America, other water contributions
(deicing, evaporated seawater) or fractionation effects (hyperltration) were minor or not revealed. However it should be noted
that pure CaeCl brines, in which these would occur, were not
revealed in the studied area. Therefore as a future prospective,
isotope analysis of this water facies and of the diagenetic minerals
involved would better clarify the origin and the sequence of
diagenetic reactions that characterize the evolution of formation
waters.
Acknowledgments
We wish to thank PDVSA-Intevep for providing the water
samples dataset and authorizing its publication. We are grateful
also to Dr. Peter Birkle and one anonymous reviewer for their
insightful suggestions and comments that greatly improved the
manuscript.
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.marpetgeo.2016.02.020.
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