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Journal of Geochemical Exploration 108 (2011) 126130

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Journal of Geochemical Exploration

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / j g e o ex p

Application of brine differentiation and LangelierLudwig plots to fresh-to-brine

waters from sedimentary basins: Diagnostic potentials and limits
Tiziano Boschetti
Department of Earth Sciences, University of Parma, 157a Parco Area delle Scienze, 43100 Parma, Italy

a r t i c l e

i n f o

Article history:
Received 6 August 2010
Accepted 6 December 2010
Available online 13 December 2010
Keywords:
Sedimentary basins
Brine waters
Salinization processes
Major dissolved constituents

a b s t r a c t
Classical chemical classication plots that use major anions and cations can discern between different water
facies but they do not offer sufcient discriminatory power for salt waters from sedimentary basins, whose
origin is therefore frequently misunderstood.
The Brine Differentiation Plot (BDP) was proposed by Hounslow (1995) in order to investigate the brine
genesis, principally evaporite dissolution, alkali lakes and oileld brines. However, its diagnostic potential has
been undervalued so far.
In this paper, the potential of BDP was tested and compared with the classical LangelierLudwig plot using
concentration of major dissolved constituents of fresh to brine waters from different sedimentary basins
(Northern Apennine Foredeep, Italy; Provence Basin, Western Mediterranean; Caucasus; Trinidad). Mixing
processes between different water types as evaluated by these diagrams would seem to be constrained by the
boronchloride plot.
2010 Elsevier B.V. All rights reserved.

1. Introduction
Chemical classication of subsurface waters from sedimentary
basins aids in interpreting the complex processes involved in
producing their dissolved solids, to better understand their origin
and evolution, and the origin of water that is more likely to be
associated with hydrocarbon accumulation (Collins, 1975). From a
general point of view, hydrocarbon accumulations are primarily
related to Ca-chloride and secondarily to Na-bicarbonate waters
(Sulin, 1946). The relative arrangement of the major constituents on a
square plot was rst proposed by Tolstikhine at the end of 1930, and
was applied to distinguish between hydrocarbon-bearing Ca-chloride
and Na-bicarbonate waters (Chilingar, 1957; Chilingar et al., 2003). A
similar plot but with inversion of the axis was proposed by Langelier
and Ludwig (1942), and is nowadays universally employed in water
classication (hereafter LLP). However, classication plots that use
major dissolved constituents are unsuccessful to distinguish between
salinization mechanisms like seawater evaporation and salt dissolution because waters of different origin fall in the same Na-chloride
eld; therefore other elements like Br and I coupled with Cl in binary
diagrams should be used (e.g. Richter and Kreitler, 1993). Recently, a
Brine Differentiation Plot (hereafter BDP) was proposed as a tool to
discriminate between different brine origins (Hounslow, 1995). The plot
uses molar Ca/(Ca + SO4) and Na/(Na + Cl) on the vertical and
horizontal axes, respectively. On this diagram, eld characteristic of

E-mail address: work@tizianoboschetti.com.

0375-6742/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.gexplo.2010.12.002

oileld brines, evaporite solutions and seawater is separate and distinct.

Despite its clarity, it is still practically neglected by geochemists.

2. Distinction between seawater-derived Ca-chloride brines and

Na-chloride waters from evaporite dissolution
Ca-chloride waters were rst dened as waters with qNa/qClb 1 and
q(Cl-Na)/qMg b 1, where q is the equivalent % (Sulin, 1946); most
recently, the denition of this water class was revised as rNa/rClb 0.86
0.05 (seawater ratio) and rCa/r(SO4 + HCO3) N 1, where r is the mEq/L
concentrations (Rosenthal, 1997). In the brine waters from Northern
Apennine Foredeep (NAF) sodium and chloride are the most abundant
ions. Therefore these waters should be classied as Na-chloride.
However, they are also denable as Ca-chloride waters using the
above ratios (Boschetti et al., 2011). Chemical and isotope composition
revealed that Ca-chloride brines derive from a Miocene seawater
evaporated up to a stage between gypsum and halite saturation, then
diluted by Miocene or present-day waters of meteoric origin and
modied by waterrock interaction (Boschetti et al., 2011). Contrary,
Picotti et al. (2007) concluded for a meteoric origin of these waters
followed by interaction with rocks. In Fig. 1B, major chemistry of
Ca-chloride brines from NAF is plotted on LLP along with waters of
meteoric origin dissolving evaporite minerals (Poiano springs, ~6 g/L;
Forti et al., 1988 and our unpublished data). All of them are displaced in
the Na-chloride area and no genetical distinction is possible because
waters from evaporite could be interpreted as diluted Ca-chloride
waters.

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T. Boschetti / Journal of Geochemical Exploration 108 (2011) 126130

127

Fig. 1. LangelierLudwig plot, where (Na + K) = (rNa+K/rcations)50 and (HCO3) = rHCO3/ranions)50, where r is the mEq/L concentration of the constituents. The (Ca + Mg) and
(SO4 + Cl) are complementary values. (A) Reading key; dashed lines represent binary mixings. (B) Waters from Northern Apennine Foredeep (NAF); brine, saline and brackish
waters from mud volcanoes: Boschetti et al. (2011); Martinelli and Ferrari (1991). Bold cross: brackish groundwater enriched in Na and depleted in Ca due to overpressure (SALV,
Boschetti et al., 2011); black crosses (Lesignano waters, Boschetti et al., 2011) and grey crosses (Porretta waters; Bencini and Duchi, 1980; Ciancabilla et al., 2007): Ca-chloride and
overpressured waters mixed with Na-bicarbonate waters, respectively. Fresh Na-bicarbonate waters (sp, f10 and f14 are brackish samples mixed with hydrocarbon-bearing waters):
Duchi et al. (2005); Venturelli et al. (2003); our unpublished data. Water of meteoric origin dissolving evaporates: Forti et al., 1988; our unpublished data. Double arrow in the alkalibicarbonate eld represents mixing with or evolution from Ca-bicarbonate fresh waters. (C) Saline to brine interstitial waters from Provence Basin (site 372, Western
Mediterranean; McDuff et al., 1978); mud volcanoes from Caucasus (Lavrushin et al., 2003) and Trinidad (Dia et al., 1999).

In Fig. 2 waters are shown on BDP. In this type of diagram, seawater

has Na/(Na + Cl) = 0.46 and Ca/(Ca + SO4) = 0.26, whereas Na-chloride
waters from evaporite dissolution arrange exactly in the center of the
plot because dissolution of gypsum-anhydrite and halite is the main
source of dissolved constituents. In the same diagram, Ca-chloride brine
waters have 0.38 b Na/(Na + Cl) 0.46 and 0.9 b Ca/(Ca + SO4) 1, thus
falling in the oil-eld brine space (Fig. 2B). However, in spite of the
original BDP representation in which the oil-eld waters are connected
with the area of evaporite dissolution and their great distance from
seawater point, no contribution from evaporite dissolution is manifest
in Ca-chloride brines from NAF. In fact, they derive from evaporated
seawater up to gypsum precipitation followed by variations in the
cationic concentration due to deep burial diagenetic processes
(Boschetti et al., 2011; Davisson and Criss, 1996). In particular,
plagioclase albitization

CaAl2 Si2 O8 + 4 SiO2 aq + 2 Na aq = 2NaAlSi3 O8 + Ca

anorthite

2+

aq

albite

and/or zeolitization

seawater and evaporated seawater solutions up to gypsum precipitation have an almost constant Na/(Na + Cl) ratio of about 0.46, that is
similar to the maximum ratio revealed in the NAF Ca-chloride brines
(Fig. 2B).
In order to conrm the potentiality of the BDP to describe the
seawater origin and the diagenetic processes, interstitial waters from
Provence Basin have been added to the plot (grey triangles in Fig. 2C;
site 372, Western Mediterranean; McDuff et al., 1978). Similar to NAF
waters, they were misinterpreted as evaporite-dissolving waters
(McDuff et al., 1978), but most recently their evaporated-seawater
origin has been conrmed by chemical and boron isotope investigations (Vengosh et al., 1994, 2000). In fact these waters, classiable as
Ca-chloride brines [1 b rCa/r(SO4 + HCO3) b 16], are displaced in the
reversed triangle eld of the BDP, and have Na/(Na + Cl) b 0.46 and
0.55 b Ca/(Ca + SO4) b 0.95, that is they evolve from seawater towards
typical oil-eld brines because of sulfate loss (reduction) and Ca
increase (albitization and/or zeolitization) related to an early burial
diagenesis (eogenesis).
3. Na-bicarbonate waters and terrestrial mud volcanoes

0:995 CaAl2 Si2 O8 + 1:02SiO2 aq + 2:647H2 O + 0:676Na aq =

anorthite

= Na0:676 Ca0:657 Al1:99 Si3:01 O10  2:647H2 O + 0:338Ca2+ aq

mesolite

involve a 2:1 exchange of Na for Ca, whereas sulfate drop is ascribed to

sulfate reduction. Therefore, seawater-derived brines may be well
represented by a reversed triangle having Ca-chloride waters as base
and seawater as vertex (Fig. 2A). In fact, its worthy of note that

Fresh Ca-bicarbonate is the dominant facies of the shallow

groundwaters and its origin, i.e. shallow meteoric water interacting
with calcite-bearing sediments, is well known and common also in
other places of the world, therefore it is not discussed further.
Na-bicarbonate waters are less common than Ca-bicarbonate but they
are considered as a favourable, shallow indicator for the presence of
hydrocarbons (e.g. Chilingar et al., 2003; Collins, 1975). In the NAF
and elsewhere, these waters have fresh to brackish salinity, are

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T. Boschetti / Journal of Geochemical Exploration 108 (2011) 126130

Fig. 2. Brine Differentiation Plot (BDP), where Ca/(Ca + SO4) and Na/(Na+ Cl) are molar ratios of the constituents. (A) Reading key (inset redrawn from Hounslow, 1995); G and H are
gypsum and halite precipitation points after seawater evaporation (Pierre, 1982). (B) Waters from Northern Apennine Foredeep (NAF; samples references as in Fig. 1). (C) Saline to brine
interstitial waters from Provence Basin, mud volcanoes from Caucasus and Trinidad (samples references as in Fig. 1 plus other data from Azerbaijan from Mazzini et al., 2009).

sulde-bearing and represent evolved Ca-bicarbonate waters of

meteoric origin interacting with albite, clay and silica phases resulting
in the acquisition of Na and loss of Ca by calcite deposition (Toran and
Saunders, 1999; Venturelli et al., 2003). These waters are characterized by a rNa/rCl 0.86 and they are easily identied in the specic
upper right side sector of the LLP (Fig. 1A and B). In this diagram
should be also noted that most of Na-chloride brackish water
associated to CH4-rich mud volcanoes cluster in a distinctive ternary
shape area, revealing intermediate characteristics between Cachloride and Na-bicarbonate waters but with higher rNa + K/rcations
ratios. In fact, uids from mud volcanoes consist of formation waters
diluted by clay dewatering, caused by overpressure that produces
deep uids with Na excess (rNa/rCl N 0.86) combined with a Ca
decrease, and shallow groundwaters (Boschetti et al., 2011). A Ca for
Na exchange between water and clay could be supposed as the easier
explanation for this shift. However, the origin of the Na-excess/Ca-

decit in Na-bicarbonate waters from sedimentary basins is most

probably due to an interaction with Na-silicate like albite and calcite
precipitation (Cheng et al., 2006; Du et al., 2010). In NAF, a brackish
groundwater shows a water isotope composition quite similar to mud
volcanoes and an extreme Na-excess thus representing a typical endmember for overpressured waters (SALV in Fig. 1B; Boschetti et al.,
2011). In the LLP, a mixing triangle between this point, a Ca-chloride
brine with the highest rNa + K/rcations value and a pure Nabicarbonate end-member identied in the left corner of the diagram
contain terrestrial mud volcano waters from different countries
(Fig. 1C). Most probably, in the mud volcano waters the Na-bearing
silicate hydrolysis is enhanced by hydrocarbon oxidationbiodegradation, a process characterized by heavy 13C(CO2) up to + 20 and
occurring at shallow depth (b2000 m) and low temperature (b70 C)
(Capozzi and Picotti, 2002; Feyzullayev and Movsumova, 2010;
Pallasser, 2000).

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T. Boschetti / Journal of Geochemical Exploration 108 (2011) 126130

In the BDP, mud volcanoes and Na-bicarbonate waters plot on the

right side, the former with 0.50 b Na/(Na + Cl) b 0.55, the latter with
0.9 b Na/(Na + Cl) b 1.0, both spanning most of the Ca/(Ca + SO4)
range due to calcite precipitation and sulfate reduction (Fig. 2). The
shifts shown in the LLP by some Na-bicarbonate samples towards
alkaline-chloride eld and vice versa (Fig. 1B) are magnied in the
BDP (Fig. 2B), but in this latter plot it is impossible to distinguish the
end-member. However, the linking between Na-bicarbonate and deep
alkali-chloride waters supposed in the LLP may be conrmed using
chloride versus bromine or iodine, as often observed in deep waters
(e.g. Richter and Kreitler, 1993). In NAF, the maximum content of
bromine and iodine was revealed in brines and overpressured
brackish waters like mud volcanoes, that is in uids that underwent
active decomposition of marine organic matter owing to burial
diagenesis and compressional tectonics, respectively (Boschetti et al.,
2011). Same conclusions could be derived using boron content.
4. Mixing trend elucidation by boronchlorine diagram
In Fig. 3, mixing between Na-bicarbonate waters and Ca-chloride
brines or mud-volcanoes is conrmed by boronchloride binary plot.
In the same diagram it is possible to discern the end-member of mixed
Na-chloride brackish groundwater (see also Figs. 1 and 2). Boron
adsorbed to clay minerals is preferably released to the uid in a deep

129

environment, where either tectonic stress (vertical and/or lateral

compaction) or temperature increases, with a maximum enrichment
in uid phase where fault roots are deepest and deformations are
strongest (Kopf and Deyhle, 2002). The B released during the
smectiteillite transformation is accompanied by salinity reduction
due to dehydration, thus explaining the water isotope composition of
the mud volcanoes (Boschetti et al., 2011; Fitts and Brown, 1999;
Moore and Vrolijk, 1992). For T N 120 C the partition coefcient
sedimentwater for boron is 0, that is the element is full partitioned in
uid (You et al., 1996). This is in accord with the temperature up to
150 C reached by the deep source inferred for mud volcanoes
(Capozzi and Picotti, 2002) and some brine waters (Boschetti et al.,
2011) in which highest boron contents were revealed (up to 138 and
400 mg/L, respectively). At lower temperature, clay uptake could be
important as shown in particular by deep-sea interstitial waters
(Fig. 3C; Vengosh et al., 2000). Waters with low chloride and high
boron content could be related to geothermal degassing and/or phase
separation followed by uid condensation at shallow depth (e.g.
Arnrsson and Andrsdttir, 1995; Truesdell et al., 1989) as shown in
some Caucasian mud volcanoes (Fig. 3C; Lavrushin et al., 2003).
However, an investigation using boron isotopes could be useful to
better determine the effect of increasing burial temperatures at depth,
the different uid sources (clay dewatering and formation water) and
smectite-to-illite transformation.

Fig. 3. Boron versus chlorine, mg/L contents. Symbols as in Figs. 1 and 2. Condensate eld depicts shallow condensation of geothermal uids (e.g. Arnrsson and Andrsdttir, 1995;
Truesdell et al., 1989). Dashed lines represent binary mixings. (A) Reading key. (B) Waters from NAF (see Fig. 1 captions for sample references); the evaporite-dissolving waters from
NAF were not shown because of their quite low B contents (mean 0.05 mg/L). (C) Saline to brine interstitial waters from Provence Basin, mud volcanoes from Caucasus and Trinidad
(sample references as in Fig. 2 plus other data from Azerbaijan from Planke et al., 2003).

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T. Boschetti / Journal of Geochemical Exploration 108 (2011) 126130

5. Conclusions
Seawater evaporation and evaporite mineral dissolution are the
main salinization processes associated with the origin of brine and
saline waters from sedimentary basins. The Brine Differentiation Plot
proposed by Hounslow (1995) may help in the differentiation of these
processes. In that diagram, evaporite dissolving waters are clustered
towards the center of the plot, Ca/(Ca + SO4) = Na/(Na + Cl) 0.5,
whereas seawater-derived Ca-chloride brines have Ca/(Ca + SO4) 1
and Na/(Na + Cl) 0.46. Saline to brine waters from different
sedimentary basins (Northern Apennine Foredeep, Italy; Provence
Basin, Western Mediterranean) cluster between these latter values
and the seawater. This is the result of the diagenetic reaction as
albitization, zeolitization and sulfate reduction that modify the
original seawater signature.
The classic LangelierLudwig diagram allows a clear subdivision and
classication of the three hydrocarbon-bearing water types commonly
found in sedimentary basins (Ca-chloride brines, overpressured/mud
volcanoes and Na-bicarbonate waters) and may help to discern the
possible mixing between them. In particular, terrestrial mud volcanoes
from different countries (Northern Apennine Foredeep, Caucasus,
Trinidad) describe a mixing triangle between these water types.
Mixing trend and relative end-members could be supported by
chlorideboron plots that represent an effective alternative to the
halogenhalogen binary plots.
Obviously, investigations on waters from sedimentary basin
cannot prescind by use of stable isotope and minor and trace element
analysis (e.g. boron and halogens). However, a conscientious use of
these (LLP and BDP) and other diagrams (e.g. Basin Fluid Line plot;
Davisson and Criss, 1996) that use major constituents could clarify
origin and processes behind the chemical composition of waters from
sedimentary basins and rationalize the analysis and use of other
minor-trace elements and isotope ratios.
Acknowledgments
The manuscript beneted from the constructive comments of two
anonymous reviewers and Editor-in-Chief, Prof. B. de Vivo. Special
thanks to Prof. G. Cortecci for his review of an earlier version of this
manuscript.
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