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Secular variation in seawater chemistry and the origin of calcium chloride

basinal brines

Article  in  Geology · October 2003

DOI: 10.1130/G19728R.1

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Secular variation in seawater chemistry and the origin of
calcium chloride basinal brines
Tim K. Lowenstein Department of Geological Sciences and Environmental Studies, State University of New York, Binghamton,
New York 13902, USA
Lawrence A. Hardie Department of Earth and Planetary Sciences, Johns Hopkins University, Baltimore, Maryland 21218, USA
Michael N. Timofeeff  Department of Geological Sciences and Environmental Studies, State University of New York,

Robert V. Demicco  Binghamton, New York 13902, USA

ABSTRACT geologic time, necessitating significant rock-

CaCl2 basinal brines, which are present in most Phanerozoic sedimentary basins, in- water interaction to make the radical change
herited their chemistries and salinities from evaporated paleoseawaters when the world from an MgSO4-rich seawater bittern to a
oceans were Ca rich and SO4 poor (CaCl2 seas). CaCl2 seas coincided with periods of CaCl2 basinal brine. These ideas, including
rapid seafloor spreading, high influxes of mid-ocean-ridge brines rich in CaCl2, and ele- the assumption about constancy of seawater
vated sea levels, conditions that favored accumulation of marine CaCl2 brines in marginal chemistry, influenced later workers (Nesbitt,
and interior continental basins. Typical basinal brines in Silurian–Devonian formations 1985; Spencer, 1987; Stueber and Walter,
of the interior Illinois basin, United States, show the same compositional trends as those 1991; Hanor, 1994). Cl-Br systematics were
of progressively evaporated CaCl2-rich Silurian seawater. Chemical deviations can be ac- used to argue that basinal brines now found in
counted for quantitatively by brine-rock reactions during burial (dolomitization, dolomite Devonian formations of the western Canada
and K-feldspar cement). This explanation for the origin of CaCl2 basinal brines contrasts basin (Spencer, 1987) and Silurian–Devonian
with others that assume constancy of seawater chemistry and involve more complex brine- formations of the Illinois basin (Walter et al.,
rock interactions. 1990) were originally derived from residual
evaporated seawater that was subsequently al-
Keywords: basinal brines, paleoseawater chemistry, Illinois basin brines. tered by rock-water interactions such as do-
lomitization, clay-mineral reactions, and albi-
INTRODUCTION CaCl2 basinal brines has significance for un- tization of feldspars. Others suggested that the
The deeper parts of most sedimentary ba- derstanding the origin and distribution in time assemblage calcite 1 kaolinite 1 illite (K-
sins (e.g., the U.S. Gulf Coast, European and space of hydrocarbon resources, dolomi- mica) 1 Na-clay buffered the Na1/H1, Ca21/
North Sea basin, western Canada basin) are tized reservoir rocks, and sedimentary metal- H1, Mg21/H1, and SiO2(aq) values in basinal
saturated with large volumes of brine and in lic ore deposits. Here we report that CaCl2 ba- brines and that these values were independent
places, hydrocarbons. Basinal brines (also sinal brines stored in Phanerozoic sedimentary of the cation composition of the initial brine
called oil-field brines or formation waters) basins inherited their chemistries and salinities (Nesbitt, 1985). A similar argument was pre-
have salinities that typically range from from evaporated paleoseawaters formed dur- sented by using a computer simulation to
10,000 to .300,000 mg/L (Hanor, 1994). The ing geologic periods when the oceans were show that the assemblage quartz 1 muscovite
CaCl2 seas, enriched in Ca21 and depleted in 1 albite 1 K-feldspar 1 calcite 1 dolomite
majority of these brines are of the Na-Ca-Cl
SO242. at 100 8C, 1 bar pressure, and pCO2 5 1023
type, chemically distinct from seawater and
atm buffered the composition of CaCl2 brines,
other common surface and near-surface waters
PREVAILING VIEWS ON THE ORIGIN producing cation concentrations in the order
(Na-Cl-SO4, Ca-HCO3, or Na-CO3 types;
OF CaCl2 BASINAL BRINES of abundance Na1 . Ca21 . Mg21 . K1
Drever, 1997) in their high Ca21 concentra-
Carpenter (1978) proposed that basinal (Hanor, 1994). However, there are significant
tions, which exceed the combined concentra-
brines originated from marine evaporite bit- mass-balance problems with applying this ap-
tions of SO242, HCO23 , and CO232 ions, specif-
terns with the same Na-Mg-K-SO4-Cl chem- proach toward the generation of basinal CaCl2
ically mCa21 . S (mSO2421 ½mHCO23 1 mCO232). brines. It was pointed out, for example, that if
istry as that produced by evaporation of mod-
Evaporative concentration of modern seawa- ern seawater. During burial, these brines were the major ion chemistry of Jurassic seawater
ter, for example, leads to brines depleted in expelled into the surrounding sediments and was close to that of today’s seawater, then
Ca21 as required by the principle of chemical sedimentary rocks, with which they chemical- there is not enough replacement dolomite and
divides for any evaporating water with mCa21 ly interacted at the ambient temperature and diagenetic anhydrite of Jurassic age in the Me-
, mSO242at gypsum (CaSO4·2H2O) saturation pressure to produce CaCl2 basinal brines. The sozoic sedimentary rocks of the U.S. Gulf
(Hardie and Eugster, 1970). Basinal brines are following reactions were invoked by Carpen- Coast to match the vast amount of Jurassic
chemically similar to CaCl2 brines forming ter (1978) to transform MgSO4-rich seawater seawater that must have evaporated to form
under hydrothermal conditions at modern bitterns into CaCl2 basinal brines: (1) dolo- the Louann Salt, a ‘‘saline giant’’ evaporite
mid-ocean ridges, where seawater is being mitization of limestones (Mg ↔ Ca ex- (Land et al., 1995).
converted into low-salinity Na-Ca-Cl brines, change), (2) loss of SO242 by precipitation of
depleted in Mg21 and SO242, by interaction gypsum or anhydrite or by reduction to H2S, SECULAR VARIATIONS IN
with basalt at elevated temperatures (Von (3) loss of dissolved carbonate species as cal- SEAWATER CHEMISTRY
Damm, 1995). However, the origin of CaCl2 cite, (4) loss of K1 by conversion of clay min- Secular variations in the major ion chem-
basinal brines remains problematical because erals to K-feldspar, and, in some cases, (5) al- istry (Mg21, Ca21, Na1, K1, SO242, and Cl2)
there are no simple pathways by which mod- bitization of detrital plagioclase (Ca ↔ Na of Phanerozoic seawater have been docu-
ern seawater and other surface waters trapped exchange). Key to Carpenter’s (1978) argu- mented from fluid inclusions in marine halites
in sedimentary deposits can be converted to ment was the assumption that the chemistry (Lowenstein et al., 2001; Horita et al., 2002),
CaCl2 brines during burial. The genesis of of seawater has remained unchanged over the magnesium content of fossil echinoderms

q 2003 Geological Society of America. For permission to copy, contact Copyright Permissions, GSA, or editing@geosociety.org.
Geology; October 2003; v. 31; no. 10; p. 857–860; 3 figures; Data Repository item 2003130. 857
 marine basin with restricted circulation and an
arid climate would produce instant CaCl2
brines with elevated concentrations of Na1,
Ca21, Mg21, K1, and Cl2 that are typical of
basinal brines. This new scenario greatly sim-
plifies the mineral-brine interactions required
to transform a CaCl2 seawater brine into a ba-
sinal brine.

ILLUSTRATION FROM THE ILLINOIS

BASIN
Formation waters from the Illinois basin,
United States, provide a specific example of
how basinal brines may be derived from evap-
orated CaCl2 paleoseawaters. The Illinois ba-
sin contains Paleozoic carbonate and silici-
clastic rocks as thick as 4 km that have
produced oil and gas for a century (Swann and
Willman, 1961; Leighton et al., 1991; Stueber
and Walter, 1991). Formation waters from
Figure 1. Secular variation in Ca21 and SO22 4 concentrations of seawater during Phanerozoic these Paleozoic rocks have salinities greater
time, estimated from fluid inclusions in marine halites (Table DR1 [see footnote 1 in text]).
21
Ca and SO4 concentrations (in millimolal, mmol/kg H2O) and principle of chemical di-
22 than seawater (but below halite saturation) and
vides for any evaporating water at stage of gypsum (CaSO4·2H2O) precipitation are used chemically, they are typical CaCl2 oil-field
to differentiate CaCl2 seas (mCa21 > mSO422) from MgSO4 seas (mCa21 < mSO422). Also plotted are brines with higher Ca21 and lower K1, Mg21,
temporal distributions of primary Phanerozoic nonskeletal carbonate minerals (Sandberg, and SO242 than evaporated modern seawater
1983) and KCl and MgSO4 evaporites (Hardie, 1996).
(Fig. 2) (Stueber and Walter, 1991). Figure 3
shows ion-ion compositional plots of 51
(Dickson, 2002), and the strontium concentra- nian and Jurassic through Cretaceous) (Fig. 1; brines from the Illinois basin previously sam-
tion in biological calcites (Steuber and Veizer, Table DR11), evaporative concentration in a pled from Silurian–Devonian carbonates
2002). Here it is proposed that these known (limestones and dolomites, 47 samples) and
changes in the major ion chemistry of sea- 1GSA Data Repository item 2003130, Table sandstones (4 samples) at depths of ,2000 m
water can explain the distinctive chemical sig- DR1, Ca21 and SO242 in ancient seawater (0–544 and temperatures ,100 8C (Graf et al., 1966;
nature of CaCl2 basinal brines and apparent Ma) used in Figure 1, and Table DR2, mineral mass- Stueber and Walter, 1991). Also plotted in
mass-balance discrepancies such as described balance calculations, is available online at Figure 3 are the major ion evaporation paths
www.geosociety.org/pubs/ft2003.htm, or on request
by Land et al. (1995). During those times from editing@geosociety.org or Documents Secre- of modern seawater and Silurian seawater, the
when seawater had a CaCl2-rich composition tary, GSA, P.O. Box 9140, Boulder, CO 80301- latter calculated from chemical analyses of
(CaCl2 seas of the Cambrian through Devo- 9140, USA. brine inclusions in Silurian marine halites
(Brennan and Lowenstein, 2002). Silurian sea-
water had lower concentrations of Na1,
SO242, and Mg21 and much higher concentra-
tions of Ca21 (29–36 mmol) compared to
modern seawater (10.6 mmol) (Table DR1;
see footnote 1) (Brennan and Lowenstein,
2002).
Comparison between Illinois basin brines
and brines predicted on evaporation of Silurian
seawater reveals important chemical similari-
ties. Illinois basin brines overlap the Silurian
seawater path on the Na1 vs. Cl2 plot (Fig.
3A), both brines having Na1 concentrations be-
low those of evaporated modern seawater.
Evaporation of modern seawater produces
brines with elevated SO242 concentrations (Fig.
3B), whereas Illinois basin brines are highly
depleted in SO242, close to, but still below, the
SO242 concentrations produced during simulat-
ed evaporation of Silurian seawater. During
simulated evaporation of Silurian seawater
(with mCa21 . mSO242), precipitation of gypsum
Figure 2. Chemical compositions of typical Illinois basin brine (sample 257 in effectively removes most SO242 from the brine,
Stueber and Walter, 1991), Silurian seawater (Brennan and Lowenstein, 2002),
and modern seawater (in molal percent). Silurian and modern seawater are allowing the concentration of Ca21 to rise dur-
shown evaporated 3.6 and 3.9 times, respectively, to same Cl2 molality (2183 ing further evaporation. Illinois basin brines
mmol) as Illinois basin brine 257. show scatter on the Ca21 vs. Cl2 plot (Fig. 3C),

858 GEOLOGY, October 2003

Figure 3. Concentrations of (A) Na1, (B) SO224 , (C) Ca
21
, (D) Mg21, and (F) K1 vs. Cl2 and (E) Mg21 vs. Ca21 in Silurian–Devonian Illinois
basin brines (Graf et al., 1966; Stueber and Walter, 1991). Dotted curves and solid curves track compositional paths for evaporation of
modern seawater and Silurian seawater, respectively (Brennan and Lowenstein, 2002), calculated by Harvie-Møller-Weare computer program
of Harvie et al. (1984). Computer program calculates concentrations (in molalities) of all major ions at each evaporation step along with
number of moles of salts precipitated during each evaporation step. Evaporation paths are functions of major-ion chemistry of parent
water, extent of evaporation, and type and amount of salt precipitated. Drops in SO224 (Silurian seawater, ~1500 mmol Cl2) and Ca21 (modern
seawater, ~2000 mmol Cl2) reflect precipitation of gypsum and loss of Ca21 and SO22 4 from evaporating brines. Similarly, drop in Na1 at
~6000 mmol Cl2 reflects precipitation of halite and loss of Na1 and Cl2 from brines.

but in all cases, Ca21 concentrations are well step, a Ca21 imbalance remains in the basinal
above those predicted from evaporation of brine (Fig. 3C). To correct this imbalance, an
modern seawater and reflect the Ca enrichment additional process—direct precipitation of do-
found in simulated evaporation of Silurian sea- lomite cement that removes Ca21 and Mg21
water (Brennan and Lowenstein, 2002). These from the brines in equal molar proportions—is
brines are depleted in Mg21, below the concen- required. Mass-balance calculations (Table DR;
trations predicted by simulated evaporation of see footnote 1) show that through this combi-
Silurian seawater (Fig. 3D). This loss of Mg21 nation of dolomitization of limestone and pre-
can be accounted for by dolomitization of lime- cipitation of lesser amounts of dolomite ce-
stones via the reaction 2CaCO3(s) 1 Mg2(aq)
1
↔ ment, the Mg21 and Ca21 concentrations in
(CaMg)(CO3)2(s) 1 Ca2(aq)1
. However, after this evaporated Silurian seawater can be trans-
formed into their measured amounts in the Il-
linois basin brines. The dolomitized limestones
and dolomite cements in the Paleozoic carbon-
ates of the Illinois basin (Leighton et al., 1991;
Stueber and Walter, 1991) support the results
of these calculations. The nearly constant Ca/
Mg ratio of the Illinois basin brines (Fig. 3E),
regardless of individual ion concentrations,
suggests that dolomitization of the host lime-
stones buffered the Ca/Mg ratio of the basinal
brines. The Ca/Mg ratio of brines in equilibri-

GEOLOGY, October 2003 859

um with limestone and dolomite has been
shown experimentally to depend strongly on
temperature (Rosenberg and Holland, 1964).
The Ca/Mg ratios of the Illinois basin brines
give temperatures for dolomitization of lime-
stone of 75 to 100 8C. The K1 concentrations
of Illinois basin brines (Fig. 3F) are below
those predicted by evaporation of Silurian sea-
water and modern seawater. Potassium feldspar
cements in the Illinois basin host strata (Pitman
et al., 1997; Chen et al., 2001) as well as dia-
genetic illites (Grathoff et al., 2001) offer a
simple explanation for these lower potassium
concentrations in the basinal brines (Table
DR2; see footnote 1).
DISCUSSION AND CONCLUSIONS
We conclude that Illinois basin formation
waters originated as evaporated CaCl2-rich
seawater. The chemical trends produced dur-
ing progressive evaporative concentration of
this CaCl2-rich seawater can explain most of
the major ion chemical characteristics of the
Illinois basin brines. The higher Ca21 and
lower Mg21 and K1 concentrations compared
to those predicted from evaporation of Silu-
rian seawater can be accounted for quantita-
tively (Table DR2; see footnote 1) by partial
dolomitization of limestones and direct pre-
cipitation of dolomite and potassium feldspar
cements at elevated temperatures during burial
(;75–100 8C).
It is now known that CaCl2 seas existed
during periods of geologic time, such as the
Silurian, when seafloor spreading rates were
high, fluxes of CaCl2-rich mid-ocean-ridge
hydrothermal brines into the global ocean
were high, and Earth was subjected to hot-
house climates and elevated sea levels—all
due to high global volcanicity (Hardie, 1996).
During such times, this combination of cir-
cumstances favored the accumulation of
CaCl2 marine evaporites and brines in mar-
ginal and interior basins of continents. Also of
interest is the chemical composition of basinal
brines formed during times when the oceans
were MgSO4 seas (Fig. 1) and how such wa-
ters and associated diagenetic brine-sediment
interactions differ from those described here
from the Illinois basin. Basinal brines from the
U.S. Gulf Coast, for example, vary in their
major ion chemistry by age; those from Ju-
rassic and Cretaceous rocks (CaCl2 seas) are
relatively enriched in Ca21, with low Na/Cl
and high Ca/Cl ratios compared to most brines
from Cenozoic rocks (MgSO4 seas) (Land and
Macpherson, 1992). These differences in ba-
sinal brine chemistries may be related to sec-
ular changes in seawater composition and the
chemical evolution of seawater-derived brines.
We propose that many, if not most, of the
CaCl2 brines stored today in Phanerozoic sed-
imentary basins overlying continental base-
860
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ment inherited their Ca-rich, SO4-poor chem- prediction of mineral solubilities in natural
istry and elevated salinities directly from waters: The Na-K-Mg-Ca-H-Cl-SO4-OH-
HCO3-CO3-CO2-H2O system to high ionic
evaporated paleoseawaters formed during ex- strengths at 258C: Geochimica et Cosmochim-
tended periods in Earth history when the ica Acta, v. 48, p. 723–751.
world oceans were CaCl2 seas (Fig. 1). This Horita, J., Zimmermann, H., and Holland, H.D.,
explanation for the origin of CaCl2 basinal 2002, Chemical evolution of seawater during
the Phanerozoic: Implications from the record
brines is simpler than currently favored ap- of marine evaporites: Geochimica et Cosmo-
proaches, all of which are based on the pre- chimica Acta, v. 66, p. 3733–3756.
mise that the major ion chemistry of seawater Land, L.S., and Macpherson, G.L., 1992, Origin of
has not changed over the Phanerozoic. The saline formation waters, Cenozoic section,
connections in space and time among ancient Gulf of Mexico sedimentary basin: American
Association of Petroleum Geologists Bulletin,
seawater chemistry, CaCl2 basinal brines, do- v. 76, p. 1344–1362.
lomitization of limestones, hydrocarbon re- Land, L.S., Eustice, R.A., Mack, L.E., and Horita,
sources, and sedimentary metallic (lead-zinc) J., 1995, Reactivity of evaporites during buri-
ore deposits remain to be explored. al: An example from the Jurassic of Alabama:
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p. 3765–3778.
ACKNOWLEDGMENTS
Leighton, M.W., Kolata, D.R., Oltz, D.F., and Eidel,
This research was supported by National Science
J.J., eds., 1991, Interior cratonic basins: Amer-
Foundation grant EAR-9725740. Acknowledgment
ican Association of Petroleum Geologists
is made to the donors of the American Chemical
Memoir 51, 819 p.
Society Petroleum Research Fund for partial support
Lowenstein, T.K., Timofeeff, M.N., Brennan, S.T.,
of this research. We thank David Vanko and Jay
Hardie, L.A., and Demicco, R.V., 2001, Os-
Gregg for their helpful reviews.
cillations in Phanerozoic seawater chemistry:
Evidence from fluid inclusions: Science,
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