Marine and Petroleum Geology xxx (2017) xxx-xxx

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Marine and Petroleum Geology

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Review article

Large salt accumulations as a consequence of hydrothermal processes associated with

‘Wilson cycles’: A review Part 1: Towards a new understanding
Martin Hovlanda⁠ ,⁠ ∗⁠ , Håkon Rueslåttenb⁠ , Hans Konrad Johnsenb⁠

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a
Tech Team Solutions, Stavanger, Norway
b
Independent Consultant, Trondheim, Norway

ARTICLE INFO ABSTRACT

The formation of large salt deposits is observed especially in areas with a geological history of high tectonic activ-

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Keywords:
Hydrothermal salt ity. Over the last decade it has become a well-established fact that heavy brines form and solid salts precipitate,
Wilson cycles due to the thermodynamic and physico-chemical properties of seawater at high temperatures and pressures en-
Physico-chemical reactions countered within hydrothermal systems. This article reviews the modern theoretical and experimental research
Thermodynamics
behind these findings, and also describes geological settings that most likely cause brine- and salt-forming hy-
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Large salt accumulations
drothermal processes to occur. This analysis has led to the identification of a set of specific conditions, properties,
Subduction
Rifting and processes (referred to as Conceptual elements) that are used to explain the often complex processes of brine
Ocean spreading behavior that leads to hydrothermal formation of solid salt.
Hidden salts The main objective of this review is to present hydrothermal conditions known to occur during Wilson cycles:
subduction, collision, and rifting, e.g., zones of repeated tectonic unrest, where brines (commonly derived from
seawater) are concentrated into heavy brines and precipitate solid salts. The internal heat of the Earth and its
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interaction with deeply-circulating seawater in hydrothermal systems and also the immense recycling of crustal
materials, including porous oceanic crust and serpentinite (hydrated) rocks via mantle processes may lead to the
formation of salt accumulations. It is also acknowledged that such brines and solid salts may often be stored
sub-surface for long time periods, extending from one Wilson cycle to another. Thus, on the basis of this analysis,
it is cautiously suggested that large amounts of salts ‘hidden’ inside subduction zones may appear on the surface
during subsequent rifting and oceanization phases.
In Part 2 of this review, the Conceptual elements, which are described and discussed herein (Part 1) are applied
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to selected cases, including the Andean Mountains, the East African Rift, the Red Sea Rift, and other locations.

tonic processes, the only conceivable process for producing solid salts
1. Introduction was solar evaporation of seawater (e.g., Alling, 1928).
As years went by, all the work done on the solar evaporation of sea-
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Over the last two centuries large volumes of salts (mostly chlorides
and sulphates) have been discovered both on and below Earth's sur-
face. (The term “salt” is here used to indicate a seawater-derived ionic
compound in its solid state). The discovery of these large volumes,
however, came much earlier than the realization of how the planet's
crust was dynamically and thermally structured. Therefore, the theories
for salt accumulations were established prior to the understanding of
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water and the formation of salts (evaporites) has formed a large and
seemingly consistent knowledge base for the explanation and explo-
ration of giant salt bodies (Hsü et al., 1973a,b; Warren, 1999, 2006;
2010, 2016). Thus, the solar evaporite theory has become so dominant
in the last century that it is more-or-less considered ‘forbidden’ to tam-
per with it.
Nevertheless, the large salt accumulations in deep marine basins

plate tectonics. Being unaware of the forces and heat involved in tec are difficult to explain with a surface seawater evaporation model
(Scribano et al., 2017, and references therein; Christeleit et al., 2015;

∗ Corresponding author.
Email address: mthovland@gmail.com (M. Hovland)

https://doi.org/10.1016/j.marpetgeo.2017.12.029
Received 30 September 2017; Received in revised form 17 December 2017; Accepted 21 December 2017
Available online xxx
0264-8172/ © 2017.
M. Hovland et al.
Lugli et al., 2015). The internal heat of the Earth and its interaction
with deeply-circulating seawater in hydrothermal systems, and the im-
mense recycling of crustal materials via mantle processes (Wilson cy-
cles with subduction, rifting, and collision; e.g., Liou et al., 2014) have,
seemingly, been neglected as a potential explanatory model for the
formation of large salt accumulations, either above or below ground
(Sozansky, 1973; Momenzadeh, 1990; Hovland et al., 2006a,b, c; 2014,
2015, 2016; Scribano et al., 2017; Hardie, 1990).
It has long been recognized that salts (evaporites) play economically
important roles in petroleum prospecting and extraction. Thus, accord-
ing to Warren (2006, 2010) and Mohriak et al. (2012), they play a ma-
jor role in i) facilitating hydrocarbon migration; ii) providing tectonic
and sealing control for hydrocarbon trap formation, and, thus, iii) play
a role in hydrocarbon reservoir distribution. However, from this current
review, it becomes evident that the roles of salt formation and accumu-
lation may deserve more attention in global tectonic (crustal) research,
as salts may produce areas of weakness in and around suture zones that
are later prone to rifting. This is evidenced by the presence of salts in
early rifts, also before the sea has invaded the rift, e.g., the East African
Rift.
1.1. Objectives and organization
The objectives of this review article are to present hydrothermal con-
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ditions known to occur during Wilson cycles, where salts may concen-
trate into heavy brines and solid salts, starting from seawater. We set
forth to identify various stages of the Wilson cycles where such condi-
tions are likely to be present. Hydrodynamics, thermodynamics and cer-
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tain properties of brines, rocks and salts, lead to predictive processes
and results. A number of ‘Conceptual elements’ are used to explain the of-
ten complex processes of brine behavior and the formation of hydrother-
mal solid salts (Table 1).
These ‘Conceptual elements’ are applied in the following chapters,
including Part 2 of the article, to explain the new model for hydrother-
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mal salt formation. In addition, a number of geological cases are dis-
cussed in order to substantiate and visualize the model (mainly found in
Part 2: ‘Application on selected cases’).
This review is divided into the current Part 1: 'Towards a new under-
standing'; and Part 2: 'Application on selected cases'. Part 1 thus, concen-
trates on the theoretical basis for the application of the ‘Conceptual ele-
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ments’ in Table 1 on the selected geological examples, mainly found in
Part 2.
Table 1
‘Conceptual elements’ applied to explain hydrothermal salt formation. The items refer to
the thermodynamics of physical and chemical reactions, including items that characterize
observable phenomena.
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Conceptual elements
‘Thermo- and fluid-dynamics’ (When seawater encounters heat at high pressures in
the Earth's crust, phase separation may occur; e.g. the formation of heavy brines,
solid salt and low-saline vapor in the supercritical and boiling domains of seawater
and derived brines).
‘Solubility and precipitation of salts’ (Salts may precipitate over large temperature
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intervals due to their wide solubility range at elevated temperatures and pressures).
‘Fresh water formation’ (Condensation of vapor in hydrothermal systems produces
fresh (‘distilled’) water that can re-dissolve solid salt along its ascending path).
‘Formation of leaky salt stocks (domes)’ (Solid salt is permeable at depths,
allowing brine to flow through. Solid salt may precipitate upon cooling during the
ascent, and thus, build the salt stock continuously higher).
‘Refining of salts’ (Marine salts have different solubilities and the more soluble salts
achieve higher concentrations than others, before precipitating. Some salts have
crystal water attached to their crystal structure (e.g. tachyhydrite). These salts may
melt in their own crystal water upon heating and leave the solid salt as flowing
brines).
‘Salt Preservation’ (Solid salts may be preserved by dry climate, dense brines, or
sheaths of anhydrite, gypsum, carbonates, or fine grained clastic or biogenic
sediments).
‘Hidden salts’ (Salts and brines may form at certain thermodynamic conditions
albeit not always observable; e.g., in subduction zones, within- or beneath oceanic-
and continental crust and within deep seated slab-remnants. This salt may become
visible at later stages in Wilson cycles).
Marine and Petroleum Geology xxx (2017) xxx-xxx
1.2. The origin of sea salts
Salt accumulations formed by hydrothermal activity, may have two
sources of origin; (a) precipitated salt from seawater; and (b) salts de-
rived directly from crust and mantle masses. Subgroup (b) may also in-
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clude previously formed and hidden salts, either in the form of solids, or
brines. Solids and brines encountered by the hydrothermal systems may
be refined relative to seawater composition.
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Serpentinite will contain both types of salts. The contribution from
the two sources is difficult to distinguish from each other, but Braitsch
(1971), who performed a thorough study of salt compositions in the gi-
ant Zechstein salt accumulations in Europe, concludes that the salt ac-
cumulations actually do not have the same composition as that of the
oceans. Thus, he found that the salt accumulations could not originate
directly from the simple evaporation of seawater.
A study aiming at determining the size of different sources of chlo-
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rine (Graedel and Keene, 1996) concluded that 99.6% of the Earth's
chlorine is to be found in the mantle, while 0.3% is found in the crust
and only a mere 0,1% resides in the oceans. However, a more modern
assessment, by Kendrick et al. (2017), suggests that the budget is much
more complicated.
According to Wallace and Anderson (2000), the “Yearly amounts of
reactive volatiles H2⁠ O and Cl that are subducted are in the range of what
is returned surfaceward by arc magmatism. If there were no surfaceward
return of subducted H2⁠ O and Cl, then the formation, alteration, and sub-
duction of oceanic crust would comprise a net drain on the water and
salt in the oceans. The geologic record and understanding of tectonism
reveal that continental crust and ocean water have existed for most of
Earth's history and subduction has not caused the oceans to dry up. Thus
water lost to altered oceanic crust is probably largely returned to the
oceans via dewatering of subducted crust and subduction-related mag-
matism.” This clearly shows that tectonic cycling of elements is active
on Earth, and indicates how important it is to understand the full im-
plications of Wilson cycles that cause seawater to interact and exchange
elements with hot, pristine mantle.
1.3. The current evaporite theory
The conventional (solar) ‘evaporite theory’ is, generally, resting on
three main pillars: a) dry climate, b) precipitation in shallow water, and
c) a relatively continuous supply of seawater that renews the content of
salt in the evaporation basin (without diluting the brine more than the
rate of evaporation). To explain the observed salt thicknesses of several
kilometers often found at great water depths, the solar evaporation the-
ory alone does not provide a sound explanation (Selley, 2005; Scribano
et al., 2017). The discussion about the possibility of accumulating such
giant deposits of ‘evaporites’ with solar evaporation alone, really made
the headlines subsequent to the DSDP (Deep Sea Drilling Project), Leg
13 drilling in the western part of the Mediterranean. How was it possi-
ble to explain the formation of thick ‘evaporite’ deposits at over 3 km
water depth?
The most cited papers from this scientific drilling were those by Ken-
neth Hsü et al. (1973a, 1977), and Ryan et al. (1973), about the history
of the Mediterranean Salinity Crisis. They also provide a rare glimpse of
the bitter controversy that arose during the interpretation and publica-
tion of the drilling results: “The significance of the DSDP discovery was,
however, shadowed by controversies. That the Mediterranean evapor-
ite is Messinian (Late Miocene) in age seemed to be just about the only
consensus after the Leg 13 drilling. Even the shipboard scientific staff
could not reach an agreement on the genesis of this unusual formation
…” “The desiccated deep-basin model (e.g., Ch. 43, of the Leg 13 cruise
report) was authored by Hsü, Cita, and Ryan because they were the only
members of the shipboard staff totally convinced on its plausibility.”
(Hsü et al., 1977).
M. Hovland et al.
For salt thicknesses of some tens of metres, the ‘evaporite’ explana-
tion may be realistic. But, according to Warren (2006): “… the scale of
lacustrine evaporite development, past and present, pales in comparison
to some ancient marine-fed saline systems. There are no modern coun-
terparts to such ancient marine-associated systems.” This is because, ac-
cording to Warren (2006, 2010), there are no places on Earth where
seawater is evaporating at a high enough rate to satisfy the climatic
and shallow-water requirements of the conventional ‘evaporite’ theory:
“Our inability to compare all aspects of evaporite deposition, past and
present, reflects a present-day lack of both longterm shallow epeiric seas
and of large drawdown basins fed by seawater seeps.” (Warren, 2006).
These disagreements and difficulties to give proper explanations to
the processes of evaporite formations show all too clearly that a revi-
sion of the traditional ‘evaporite’ theory is required. For example, the
term lacustrine evaporites, used above, easily brings ambiguities into the
discussion. This is because the evaporation of fresh water (from rivers,
etc.) gives negligible amounts of salts upon evaporation, but hydrother-
mal meteoric water may give significant amounts of salts upon evapora-
tion like we see in the East African Rift. In most cases it seems this term
is applied to evaporation of hydrothermal brines which reaches the sur-
face; for example, in Danakil (Afar), Ethiopia, where dense brines em-
anate onto the surface, dry out and become preserved in the dry and hot
climate (Talbot, 2007).
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2. Formation of hydrothermal salts
2.1. Salts forming in hydrothermal systems
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Besides plate tectonics, two of the last century's perhaps most impor-
tant discoveries within marine geology, were indeed related to salt and
hydrothermal processes: 1) The discovery of hot brines in the Atlantis
II Deep of the Red Sea (e.g., Charnock, 1964); and 2) The discovery at
the East Pacific Rise of hot vents, so-called ‘black smokers’ (Lonsdale,
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1977). Both discoveries are considered ‘game-changers’ in the quest for
understanding seawater circulation in the oceanic crust. It is now well
understood that the driving force for this circulation is heat from the un-
derlying mantle; so-called ‘forced convection’, with auto-circulation of
seawater when the temperature gradient between a hot (>1100 °C) ris-
ing pluton (igneous intrusion) and the ocean floor (at typically 2–4 °C)
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is adequately steep. Hydrothermal circulation of seawater in the Earth's
crust at temperatures above 400 °C and >3 km below sea surface, will
inevitably lead to the formation of concentrated brines and the precipi-
tation of solid salt. It is suggested that hydrothermal processes may ex-
plain both the location and the amount of salt deposits in a better way
than solar evaporation. Even so, this does not prevent solar evaporation
from being an active contributor to brine densification and precipitation
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of solid salt in many cases (Schreiber et al., 2007).
2.2. Energy considerations
Attempts to explain observed evaporites based on mantle heat act-
ing on seawater in a static setting, will not produce the accumulations
observed in nature. The concept of producing evaporites from seawa-
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ter based on the heat from stationary magma/mantle bodies is not a
straightforward evaporation process. This is demonstrated by a simple
calculation: A 1 km cube of hot mantle contains approximately the heat
necessary to evaporate a 1 km cube of seawater, which leads to a 1 km
square of salt of ∼15 m thickness; i.e., far from being comparable to the
vast amounts of salt observed in some geological settings. However, the
premises for this calculation are wrong. A more correct calculation must
take into account several other factors than the heat-transfer between
two static objects; e.g., water-rock interactions.
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Marine and Petroleum Geology xxx (2017) xxx-xxx
When seawater encounters hot mantle, the water-rock interactions
are causing dissolution and hydrolysis of minerals in the rock, resulting
in uptake of a significant amount of water in the form of OH-groups in
new formed minerals. Simultaneously, the brine becomes denser due to
its uptake of salts and other dissolved elements from the mantle rocks.
These reactions are exothermic in nature, and extra heat is produced
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during the reactions, especially if serpentinization is involved, which
is often the case. In addition, during serpentinization, hydrogen is also
produced, which represents a very strong reduction agent in chemical
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reactions involving iron-bearing minerals.
These reactions form brines that are much denser than the ini-
tial brine (seawater), without consuming large amounts of heat from
the surroundings. Also, in contrast to the static example above, the
hydrothermal processes are extremely dynamic. The initially formed
brines may indeed be subjected to heat from other parts of the system as
they move around, or by dynamic hot magma bodies (volcanism). This
is likely to happen in both rifting and subduction systems, and provides
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the necessary energy to produce accumulations of salts.
If we accept the concept that salts and brines may survive over ge-
ological time spans in the mantle/deep crust, they may also experience
energy supply from several stages of the Wilson cycle before appear-
ing as observable salt accumulations. The Earth has undergone several
periods during which supercontinents have assembled and rifted apart
again. Therefore, the supply of energy and the availability of seawater
during billions of years in the Earth's history make deep salt and brine
production unavoidable. In short, the salt accumulations we observe to-
day may be the result of processes that date much further back in time
than the latest stage in the Wilson cycle of that area.
Bearing in mind all the Wilson cycles encountered during the Earth's
history the question whether the mantle has provided the necessary
amounts of energy to produce the observed salt is not an issue. It should
also be noted that Taylor and McLennan (1985) estimated that in total
2% of the continental crust consists of salts (in sedimentary and pale-
osedimentary units). This is an enormous amount, which is undergoing
transitions during rifting, subduction, and continental collisions (e.g.,
during Wilson cycles).
2.3. Serpentinization of mantle rocks
Over the last ~40 years, there has been a revolution in our under-
standing of how the oceanic lithosphere has evolved through interac-
tion with seawater. Along slow-spreading ridges there are areas where
seismic profiling shows more than 15 km thick ‘amagmatic’ zones repre-
senting relatively cool lithosphere, where seawater has reacted with the
upper mantle to form serpentinite rocks (Pearce, 2002; Dick et al., 2003;
Mével, 2003; Snow and Edmonds, 2007; Ildefonse et al., 2007; Miranda
and Dilek, 2010 ). This zone overlies almost unaltered ultramafic mantle
rocks. On the seafloor above such areas the serpentinization processes
are recognized by the occurrences of hydrothermal venting, both hot
(∼360 °C) black smokers and low-temperature (40–90 °C) white smokers.
The black color of black smokers is due to the emittance of abundant
sulfide particles, while the ‘white smokers’ are characterized by having
high pH-values (9–10), abundant CO2⁠ and methane contents (e.g. Mével,
2003), and are precipitating carbonate and magnesium hydroxide min-
erals onto the seafloor. The water that comes up in the hot springs is
commonly found to have significantly lower salinity than seawater.
It is well known that the upper mantle consists of dry magne-
sium-rich silicate rocks (‘peridotite’), containing abundant iron-bear-
ing olivine ((Mg,Fe)2⁠ SiO4⁠ ). These minerals always coexist with orthopy-
roxene (MgFeSiO3⁠ ) ± Ca-rich clinopyroxene ± Al-Cr spinel and ± Ni-Fe
sulfides. When seawater encounters peridotite through deep cracks in
the hot oceanic crust, spontaneous water-rock reactions start. These re-
actions are referred to as serpentinization, because peridotite is trans
M. Hovland et al.
formed into serpentinite by pervasive hydrolysis reactions (Scribano et
al., 2017).
Experimental reactions show that olivine is preferentially dissolved
at temperatures around 250–300 °C, while orthopyroxene is rapidly dis-
solved at temperatures above 400 °C (Martin and Fyfe, 1970). Sev-
eral accessory minerals may also form in the serpentinization process,
such as brucite or talc ± magnetite ± FeNi sulfides ± FeNi alloys ± chlo-
rite ± tremolite, depending on the physico-chemical conditions of the
system (Früh-Green et al., 2004). In particular, the formation of NiFe al-
loys (taenite and awaruite) demand strongly reduced conditions. These
conditions are best achieved where serpentinization is at a non-equi-
librium stage; i.e. at the reaction front where olivine is present. Once
olivine is completely altered, the oxygen fugacity associated with the
rock transformation will increase markedly .
The formation of NiFe-alloys in addition to the formation of hydro-
gen, demonstrates that the serpentinization process also includes reduc-
tion processes that are balanced out by the oxidation of iron (Fe2⁠ + →Fe
3
⁠ +
) to form magnetite and also serpentinite containing some ferric iron.
A general formula, including both olivine and pyroxene with their con-
tent of magnesium and iron, is suggested by Evans (2004). This equa-
tion also illustrates the redox reactions in the serpentinization process.
The valences of iron in the minerals are indicated by (II) for ferrous and
(III) for ferric (oxidized) iron in the equation:
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1.2 Mg1⁠ .8Fe(⁠ II)0⁠ .2SiO4⁠ + 0.76 Mg0⁠ .9Fe(⁠ II)0⁠ .1SiO3⁠ + 2.088
H2⁠ O → Mg2⁠ .85Fe(⁠ II)0⁠ .11Fe(⁠ III)0⁠ .08Si1⁠ .96O5⁠ (OH)4⁠ + 0.042
Fe(⁠ II)O*Fe(⁠ III)2⁠ O3⁠ + 0.176 H2⁠
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Olivine + Pyroxene + Water → Serpentine + Magnetite + Hydrogen
(+Heat)
The reaction is strongly exothermic, causing the serpentinization
process to increase its longevity due to its own heat production.
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2.3.1. Serpentinization and salt
The average density of a fresh peridotite is approximately 3.3 g/cm3⁠ ,
while serpentine minerals have much lower density (∼2.5 g/cm3⁠ ), due to
the uptake of OH-groups in the new-formed crystal lattices. This causes
up to 40% swelling of the rock at complete alteration. Consequently,
any brine (seawater at sub-critical conditions) will increase its salinity in
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the reaction zone. However, some substitution of chloride for hydroxyl
is found in the new-formed minerals (e.g. iowaite, brucite, and serpen-
tine) in addition to other sea-salt elements incorporated in the crystal
lattices of the serpentinite minerals (Sharp and Barnes, 2004; Manuella
et al., 2016; Vogel et al., 2014).
According to Sharp and Barnes (2004) a significant amount of Mg2⁠ +
and Na+ ⁠ water-soluble chlorides are hosted in fresh serpentinite. By
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leaching of serpentinites with distilled water they extracted an amount
of salts corresponding to more than 0.5 wt% Cl. They suggest that
Cl-bearing minerals are incorporated in the serpentine both as inter-
stitial water soluble solid salts (e.g. halite and bischofite) and also
as insoluble salt components incorporated in the crystal structure of
fine-grained serpentinite (Sharp and Barnes, 2004). Because Cl consti-
tutes 55% by weight of sea salt, 0.5 wt% of Cl in the serpentinite indi-
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cates a total salt content of about 0.9 wt%.
Fluid flux rates for water that enters into serpentinization reaction
zones in the Earth's crust are calculated to be in the range of 60–600 mol
m−⁠ 2 a−⁠ 1 . This can be translated into water volumes of up to 10,000 m3 ⁠
per km− ⁠ 2 a−
⁠ 1. If it is assumed that this is mainly seawater, a corre-
sponding amount of 300 tons per km− ⁠ 2 a−
⁠ 1 of sea salt is enriched in
these reaction zones, either as heavy brines or as precipitated solid
salt (mainly magnesium and sodium chlorides), as shown by Sharp and
Barnes (2004).
According to Scribano and Viccaro (2014), the theoretical amount
of salt left or “produced” by changing one m3⁠ peridotite to serpentinite,
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Marine and Petroleum Geology xxx (2017) xxx-xxx
is 10.5 kg: “Since the serpentinization process requires pure H2⁠ O, the
involved seawater-derived serpentinization fluid will undergo total
out-salting.” However, the difficulty is to document this, in nature.
A common feature of serpentinite rocks are their patterns of perva-
sive fracturing (Malvoisin et al., 2017). The swelling of the rock exerts
strong mechanical forces on the rocks surrounding the reaction zones,
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causing fracturing on several scales. Even fractures on the micrometre
scale will immediately be filled with brine due to the high capillary
forces involved. These fine fractures provide large interaction surfaces
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between the brine and the rock and chemical reactions will cause fast
consumption of the pore water. Thus, the salinity of the brine may reach
high saturations and eventually also precipitate solid salts (Sharp and
Barnes, 2004).
The mechanisms for the migration of ‘hidden salt’ from serpentiniza-
tion zones were discussed by Scribano et al. (2017). Two mechanisms
were suggested; (a) the hydrothermal salt plume; and (b) the buoyant
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diapir. The first model depends heavily on a continued flow of hot hy-
drothermal water from the serpentinization zone that has sufficient en-
ergy to move such heavy brines and even slurries of solid salt parti-
cles in heavy brines. Dewatering of serpentinite at higher temperatures
(>400° C) may constitute sufficient energy to move such salt plumes.
The second model refers to the formation of salt stocks by hot brines
migrating in the middle of the salt body; provided that the salt stock
is situated within the ‘Holness zone’, where salt is permeable (see Ch.
2.4.7 in the current paper). This assumes subcritical conditions and flow
of hot brines that reach saturation upon cooling at the upper part of
the salt body, where solid salts are precipitating according to their spe-
cific solubility at each particular temperature and pressure interval. This
model thus, includes a refining process of the salt, where e.g. halite pre-
cipitates long before calcium and magnesium chlorides, upon cooling.
Sharp and Barnes (2004) conclude that subduction of serpentinite
may be the most important contributor to bring Cl down to mantle
depths, thereby being a main contributor to the global cycle of Cl. A
high-salinity fluid plume is suggested to evolve in the subduction zone
during serpentinite dehydration of a subducting slab that will affect and
intensify water-rock interactions and melting properties above the slab.
2.4. The hydrothermal salt model
This chapter provides some more background information pertinent
to further explain the ‘Conceptual elements’ in Table 1.
2.4.1. Model description
Based on previous work in rifted salt basins, mainly the Red Sea
(Hovland et al., 2015), a total of five relevant steps or phases have been
identified, whereby salt is naturally processed in one way or another to
eventually end up as salt accumulations. Different types of salts are in-
cluded in various structures and accumulations, including 'diapirs' (salt
stocks) and layered deposits.
These steps are:
1) Seawater encounters hot rocks at moderate depths in the fault zones.
Salt precipitation takes place due to boiling. Upon cooling of this sys-
tem, salts are dissolved and most of them are returned to the sea.
2) As fracture volume expands and hydrothermal brines move further
down towards the hot igneous body, high-pressure ‘supercritical’
phase separation occurs, resulting in salt precipitation and the for-
mation of low density (0.3 g/cc at the critical point) water vapor and
heavy brines that migrate further down and concentrate beyond sat-
uration.
M. Hovland et al.
3) The circulating fluids cool the system further, and the upwards mi-
grating low salinity vapor is condensing, and starts to dissolve pre-
viously deposited salts. The different solubilities of sea salts lead to
a refining of the salt types, whereby the most soluble ones are pre-
dominantly dissolved and displaced first. When these brines migrate
upwards due to fluid and/or tectonic pressures, they are cooled and
some salts are re-precipitated before the brine reaches the seafloor.
4) Upon reaching the seafloor, the brines are cooled further, and will
easily become supersaturated with respect to some of the salt types.
The remaing brine creates ponds of heavy brines along the seafloor
when topography and sea currents allow. Salts will then precipitate
from these heavy brines on the seafloor (ponding/mini-basin forma-
tion) and form stratified deposits. This process includes another re-
fining of the salts.
5) In the continued subsurface processes, brines will migrate through
salt deposits as they build up. This brine migration also includes
a) dissolution and re-precipitation, b) pressure build-up due to
salt-clogging and release, and c) extrusion of salts/salt slurries and
brines (e.g., the formation of salt glaciers, salt walls, salt injectites,
and ‘diapirs’).
These steps are not to be understood as completely isolated or se-
quential, as several of the steps may occur simultaneously, although one
step may at a certain time be more dominant than the other. Further-
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more, it must be noted that the accumulation of salt in specific regions,
is fully dependent on the local conditions of ‘salt preservation’, as we
discuss in Ch 2.4.12. It should therefore not come as a surprise that al-
though large quantities of salt are produced in a particular subsurface or
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near-surface area, the salt may not accumulate due to poor local preser-
vation conditions.
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Fig. 1. Phase diagram for the system H2⁠ O-NaCl showing the distribution of the three components liquid solution (L), vapor (V) and solid halite (H) in the P/T-domain. It illustrates where
the various components (phases: L, V and H) occur at different pressures and temperatures typically encountered in hydrothermal systems associated both with rifting and subduction.
(Based on Driesner and Heinrich, 2007). The blue-colored points, A, B, and C, refer to Example 1 in the text. (For interpretation of the references to color in this figure legend, the reader
is referred to the Web version of this article.)
5
Marine and Petroleum Geology xxx (2017) xxx-xxx
2.4.2. Solubility and precipitation in P/T-space
The common sea salts are polar ionic compounds. When precipitated
as solid salts the ions are mainly bound together by electrostatic forces.
When these salts are immersed in water, which has a very large dielec-
tric constant, the water molecules are weakening the electrostatic bond-
F
ing. This is causing the ions, both cations and anions, to lose contact
with the solid salt and brought into solution. For this reason, the dielec-
tric constant of water has been regarded as a proxy for the solubility of
OO
polar ionic salts, while non-polar compounds (like oil) are less soluble
in water.
However, while most of the common sea salts increase their solubil-
ity at higher temperature (with the exception of calcium sulfate, anhy-
drite), the dielectric constant of water decreases with increasing temper-
ature; e.g., from 88 units at 0 °C and down to 73 units at 100 °C (Pan et
al., 2013). Furthermore, the dielectric constant of water is reduced right
down to only 2 units, at the critical point (CP) (Hayashi and Hakuta,
PR
2010) and, thus, water is losing most of its solubility for the common
sea salts at the transition to the superctitical domain (Liebscher and
Heinrich, 2007).
Each mineral has its own thermodynamic behavior according to the
availability of water, and according to temperature, and pressure vari-
ations. This is normally described by a phase diagram for each type of
salt. But, because the sea salts interact with each other in solution, the
phase diagrams will be dependent on the total ionic composition, mak-
ing the phase diagrams even more complex than shown in Fig. 1, which
is only valid for one type of salt, NaCl (halite).
The reverse process, - precipitation of salts, is a consequence of
their solubility (Table 2). Upwards directed brine flow inside salt struc-
tures effectively maintains the salt concentration at the saturation level
as it flows and cools at the same time. This leads to precipitation of
solid salts all along the flow path; e.g., saturated NaCl brine at ∼100 °⁠ C
and ambient pressure dissolves up to 390 g of NaCl per liter of water.
M. Hovland et al. Marine and Petroleum Geology xxx (2017) xxx-xxx

Table 2 anhydrite and finely disseminated halite developed around the heating
Solubility at 20 and 100 °⁠ C for some pertinent salt minerals (CRC Handbook of Chemistry
elements. The ‘salt stock’ made its own accommodation space by push-
and Physics: Lide, 1990).
ing away the gravel (Hovland et al., 2006a). The experiment demon-
Solubility at 20 °C Solubility at 100 °C strates that anhydrite and halite precipitates even in wet environments,
Salts (g/100 g) (g/100 g) where conditions are favorable, e.g., close to strong natural heat-sources
located where seawater can freely circulate (‘wet evaporation’).
NaCl (halite) 35.7 39.1

F
Na2⁠ SO4⁠ *10H2⁠ O 11.0 92.7
(mirabilite) 2.4.4. The discovery of high-pressure phase separation
KCl (sylvite) 34.7 56.7 When seawater is heated and pressurized to near the CP a ‘two-phase

OO
KMgCl3⁠ *6H2⁠ O 64.5 decomposes mode’ occurs, i.e., most of the volume becomes a vapor (about 95 vol%)
(carnallite)
K2⁠ SO4⁠ *MgSO4⁠ *6H2⁠ O 19.2 59.8
with a density of 0.3 g/cm3⁠ , and the remaining liquid becomes a dense
(schoenite) brine as shown in the phase diagrams (Figs. 1 and 2) to be discussed in
MgSO4⁠ *7H2⁠ O (epsomite) 71 91 the next chapter.
2K2⁠ CO3⁠ *3H2⁠ O 129.4 268.3 The first to study phase separation of seawater at high pressures
MgCl2⁠ *6H2⁠ O (bischofite) 167 367
CaCl2⁠ *6H2⁠ O 279 536
and temperatures, e.g., at supercritical conditions (T = ∼407 °C,
CaSO4⁠ (anhydrite) 0.21 0.16 p = ∼300 bar), were Bischoff and Rosenbauer (1989). However, because

PR
they used pressure cells without visual access, they were unable to vi-
sually observe the phase transitions. Such experiments were later car-
Upon cooling the brine to 20 °⁠ C, solid salt will precipitate, as the solubil-
ried out by Tester et al. in the early 1990's: “When a temperature of
ity is reduced to 357 g per liter (Table 2). Thus, salt structures, like salt
around 405 °C was attained, a ‘cloud’ formed in the chamber and we
stocks (domes) or salt walls, may build up.
witnessed a sudden transition from one-phase flow to a two-phase flow,
Gypsum and anhydrite have retrograde solubilities, i.e., their solubil-
as solid salt ‘shock-crystallized’ when the solubility of NaCl dropped to
ities decrease with increasing temperature (Table 2). Furthermore, an-
near-zero over a temperature range of only a few degrees C at the crit-
hydrite has a lower solubility than gypsum, especially at higher temper-

D
ical point of brine.” (J. Tester, pers. com., 2002). The resulting NaCl
atures, and will precipitate from seawater at temperatures above 130 °C.
and Na2⁠ SO4⁠ solids inside the reaction chamber were found to consist
It is also pertinent to note that gypsum, which is essentially the same
of 10–100 μm ‘highly amorphous kernel-shaped particles’ (Tester et al.,
mineral as anhydrite, but with some additional crystal water, is rarely
1993).
observed in salt accumulations. Gypsum is the low-temperature mineral
TE
The reason why salts are practically insoluble in supercritical va-
of the two, and should be abundant in salts formed at low tempera-
por is the extreme lowering of the dielectric constant, from ∼80 to ∼2
ture, provided it does not lose its crystal water rapidly after deposition
(Braitsch, 1971). units. This causes a reduction of the ionic dissociation constant for the
Halite is actually the least soluble chloride and does not have the dissolved salts to such a degree that the salts precipitate. Other impor
ability to bind crystal water. Chlorides of magnesium, calcium and
EC

potassium, as well as more exotic salts, such as tachyhydrite, have the

ability to bind crystal water and, therefore, tend to stay in solution long
after halite saturation is reached. Thus, in hot water-deprived systems,
brines of magnesium and calcium may escape the system as very hot
liquids. Upon cooling, the water turns into crystal water and the salts
become solid. This is a viable explanation for the formation of tachyhy-
drite, a salt so hygroscopic that it does not survive as a solid when ex-
RR

posed to normal air humidity. Thus, the source for tachyhydrite would
most probably be from a mixed salt accumulation that is occasionally
exposed to more heat, which enables intergranular magnesium and cal-
cium chlorides in halite to liquefy in their crystal water (e.g., at temper-
atures above 120 °⁠ C) and escape out of the salt masses in hot liquid form.
To be preserved and solidify upon cooling, these brines must be some-
CO

how protected by equally saturated brines, a situation to be discussed

later.

2.4.3. Salt-formation by boiling – ‘wet evaporation’

A prerequisite for the formation of solid salt and observable salt
accumulations associated with hydrothermal systems is the supply of
seawater. At ocean depths of less than 2800 m (i.e., pressures below
UN

300 bars), seawater will not reach its CP. However, at sufficiently high
temperatures, seawater will boil, even when confined in sediments or
in fractures of the crust. Although it is well known that the boiling of
seawater at surface may produce large quantities of salts (e.g., Talbot,
2007), it is not readily clear what happens when seawater boils under
Fig. 2. Images showing the salt formation, from Simulation case #6 of Coumou et al.
water.
(2009). The figure shows the results from a simulation where sea water meets hot mantle,
This was, however, demonstrated by a boiling experiment in a after a period of 4000 years. Color coding reflects salinity. The grey areas indicate where
7 m × 7 m and 3 m deep pool filled with seawater, where the boiling sys- solid salts are formed and fresh vapor leaves the system. Depth is indicated in metres be-
tem included an open 200 L steel container with a 5 kW heating ele- low sea level. a) Shows the temperature distribution. b) Shows the established water flow
lines. (For interpretation of the references to color in this figure legend, the reader is re-
ment buried in gravel. The boiling was controlled by three thermome-
ferred to the Web version of this article.)
ters and continued for 11 days. An artificial ‘salt stock’ consisting of

6
M. Hovland et al.
tant properties of the supercritical vapor are its low viscosity and high
diffusivity (Tester et al., 1993; Bellissent-Funel, 2001), which facilitates
fast diffusion into porous rocks (‘stockwork’ veins/fissures) and sedi-
ments.
Butterfield (2000) shows a scanning electron microscopy (SEM) im-
age of halite-coated basalt. His interpretation of this image is that a
sub-seafloor volcanic eruption (in deep water) “… caused immediate
phase separation and halite precipitation, followed by a high-temper-
ature reaction period.” Furthermore, he concludes that: “A brine pro-
duced by condensation from seawater-derived fluid at 450 °C would
have a salinity five times greater than that of seawater. Brines produced
by exsolution of an aqueous phase from a magma at temperatures in ex-
cess of 700 °C have salinities of more than 10 times that of seawater.”
(Butterfield, 2000).
This realization, lead Lecumberri-Sanchez et al. (2015) to conclude
their world-wide study of rising upper crustal plutons with the state-
ment: “Salt precipitation appears to be a ubiquitous feature in hydrous
volcanic and geothermal environments, invoking dynamic behavior due
to rapid multiphase reactions involving liquids, vapor, and solids.”
The implications of these observations are that the interaction be-
tween seawater and hot igneous bodies at sufficiently large water depth
(>300 bar pressure) unequivocally produces concentrated brines and
local precipitation of halite and other salts in pores and fractures
(Hovland et al., 2006a, 2016, b, c; Gruen et al., 2014; Scott et al., 2017;
D
Scribano et al., 2017). It is this fundamental revelation that forms the
basis for the current hydrothermal salt theory, where the fact that sea-
water normally phase separates somewhere within every conceivable
TE
type of hydrothermal circulation cell, due to high temperatures, often
combined with high pressures, plays the central role.
2.4.5. Application of thermodynamics
Hydrothermal systems occur in highly fractured, permeable and
EC
porous rocks that typically occur above strong heat-sources, such as
hot oceanic crust, rising igneous bodies (‘magma chambers’ or plutons).
Water trapped in the fissures, fractures, and cracks will be forced by the
steep temperature gradient to convect, often vigorously. Such locations
on the deep ocean floor are also described as: ‘zones of high heat-flow’.
If brines are present in hot fractured fault zones, thermo- and
fluid-dynamics will control the brine behavior. As it most often leads to
RR
dynamic fluid flow (forced convection), interaction with side wall rocks,
and precipitation of salts, will occur, as documented by numerical mod-
elling (Hovland et al., 2006a; Driesner and Heinrich, 2007; Coumou et
al., 2009; Gruen et al., 2014; Lecumberri-Sanchez et al., 2015; Scott et
al., 2017).
Scott et al. (2017) studied the exploitation of geothermal energy on
CO
Iceland, and state: “Numerical simulation of subaerial, magma-driven,
saline hydrothermal systems reveals that fluid phase separation near
the intrusion is a first order control on the dynamics and efficiency of
heat and mass transfer. Above shallow intrusions emplaced at <2.5 km
depth, phase separation through boiling of saline liquid leads to ac-
cumulation of low-mobility hypersaline brines and halite precipitation,
thereby reducing the efficiency of heat and mass transfer. Above deeper
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intrusions (>4 km), where fluid pressure is > 30 Mpa, phase separation
occurs by condensation of hypersaline brine from a saline intermedi-
ate-density fluid. The fraction of brine remains small, and advective, va-
por-dominated mass and heat fluxes are maximized. We thus hypothe-
size that, in contrast to pure water systems, for which shallow intrusions
make better targets for supercritical resource exploitation, the optimal
targets in saline systems are located above deeper intrusions.” This is
fully in line with the hydrothermal salt theory applied here.
To understand the transition and transformation of NaCl-solutions
in high-temperature, high-pressure hydrothermal systems, it is neces
7
Marine and Petroleum Geology xxx (2017) xxx-xxx
sary to use phase diagrams (Fig. 1). With such diagrams it is possible
to state where and when (in the T/P space) salt will become saturated
and precipitate (to solid halite) and when vapor (low salinity to fresh
‘steam’) will form.
The phase diagram in Fig. 1 shows the regions in P/T-space where
the various phases occur, including the concentration of salt (% NaCl).
F
In the figure, occurrence of the liquid phase is marked with (L), the va-
por phase (V), and the solid state, e.g., halite with (H).
As simulated numerically by Coumou et al. (2009) (Fig. 2), saline
OO
water may experience a series of phase separation events during its
movement downwards through the fractured rock. Consequently, the
brine is subject to phase separation, with the partitioning of low-salin-
ity vapors and dense (high salinity) brines. Physical movement of the
brine into domains of slightly higher pressures and temperatures leads
to the next stage, resulting in increased brine density. Retaining the
brine in the fracture system depends on overcoming the lifting capacity
of the escaping vapors. Hence, pressure (hydraulic head) plays a role in
PR
regulating vapor volume and, therefore, hydrodynamic lifting capacity.
Coumou et al. (2009) state that both simulations and evidence from na-
ture suggests that brines with higher salinities than ∼12% will tend to
sink in and not be lifted out of the system, provided that phase sepa-
ration takes place deep enough, e.g. below 3,5 km in their simulations.
The salts and brines formed at such conditions may, however, be ‘mined
out’ by later influx of colder waters, or by mechanical (tectonic) forces
acting on the rocks. Such waters might be the result of condensing va-
pors from deeper phase separation processes.
To explain the phase behavior (Fig. 1), three simplified examples are
included below. Only Example 1 with lines in blue, and points A, B, and
C,- is illustrated in Fig. 1.
2.4.6. Example 1
In Fig. 1, a brine of 10% NaCl concentration encounters a pressure of
350 bars and a temperature of 450 °C (point A). Here, the brine will sep-
arate into a vapor containing traces of salt (B) and a denser brine having
40% of salt (C). In a rift system, given the right hydro-dynamical condi-
tions, this brine may now migrate downwards (due to its higher density)
and encounter even more extreme conditions leading to another stage in
the phase separation. This may eventually lead to solid salt precipitation
and accumulation. In real systems, the fluid flow is tortuous and convo-
luted, depending on local conditions within the rock fracture network.
The thermodynamically (PT)-determined alterations and phase separa-
tion stages in real systems are therefore gradual and infinitive.
If conditions take the fluids outside, or above the critical conditions
for any salinity, represented by the “critical curve” in Fig. 1, only fresh
supercritical vapor and solid salt may exist.
2.4.7. Example 2
If subsurface brines are exposed to a pressure drop due to, for ex-
ample rifting, the conditions may move below the V + L + H surface of
the phase diagram. This will lead to boiling and instantaneous solid salt
precipitation.
2.4.8. Example 3
In a subduction setting, the slab with its contained seawater is ex-
posed to gradually higher pressures while maintaining a relatively low
(inside) temperature compared to its surroundings (thermal inertia).
However, - since the fluids will experience compaction of the slab, they
may also be squeezed out and meet the conditions in the warmer hang-
ing wall above the slab. This may move brines with certain salinities
into warmer regions where they separate into vapor and even denser
brines.
Coumou et al. (2009) provide ample evidence for deep salt forma-
tion in the Earth's crust/mantle during stages of the Wilson cycles where
saline waters meets a heat source. See Fig. 2 below.
M. Hovland et al. Marine and Petroleum Geology xxx (2017) xxx-xxx

2.4.9. Fresh water formation (vapor condensation)

It should come as no surprise that when brines or seawater are in-
creasingly concentrated in salinity, some fresh water must leave the sys-
tem and may interact with adjacent salts or rocks on its way. Even if the
water leaves the hydrothermal system as vapor with little or no salt-car-

F
rying capacity, it eventually cools and condenses to pure (distilled) wa-
ter and may start dissolving (‘picking up’) salts again. Wherever de-
posited salts are exposed to this flow of fresh water, they may be re-dis-

OO
solved along the flow path of this ‘reflux’ water. This may lead to the
formation of brines that move on and even deposit salts further up in
the stratigraphy. In the hydrothermal salt model, the flow of fresh wa-
ter is not located arbitrarily in relation to the circulation cell, and very
often, it is located immediately above the centre of the hottest portions.
Numerical simulations also confirm this (e.g., Gruen et al., 2014).
Depending on the relative amount of water and salt, lean or rich

PR
brines will be the result. At the seabed, salt ‘glaciers’, as seen in the
Red Sea, may seemingly end their movement towards deeper parts of
the rift basin. This is also where this fresh water rises upwards and
emanates. During oceanic rifting and subduction, the only water in-
jected into the hydrothermal system, is seawater. This implies that any
fresh-water flows observed, must be the result of loss of salt from the
seawater. Even if the water has been involved in hydroxylation of min-
erals, it still came from seawater that lost its salt somewhere.

D
There are, however, exemptions to this ‘rule’ in shallow, meteoric
systems involving ground water and in early stage continental rifting
where water input is often meteoric. The output, however, is rarely
fresh, as it usually leaches and transports different solutes upon return-
TE
ing to the surface. Rift lakes of East Africa provide evidence for this.
The returning meteoric water has picked up salts from deeper down,
and, therefore, several saline (alkaline) lakes exist along the rift. Each
lake tells a story of what substances the water encountered in the deep
(Warren, 2006).
EC
Fig. 3. Diagram modified from Lewis and Holness (1996) showing the equilibrium halite/
water dihedral angles (θ) as a function of P and T and the corresponding distribution of
pore water. In the white area (upper right), θ is less than 60°, resulting in the formation
of continuous liquid films in the halite-water system. The light grey area (middle), defines
the P-T region in which the permeability of halite may be significant. The dark grey area
(lower), θ >60°, represents the region with (‘normal’) impermeable halite. The dashed
line indicates a geothermal P-T gradient. Drawings of halite crystals illustrating continu-
ous liquid films (upper) and disconnected liquid (lower) are also shown.
this mechanism allows refining of salt, by the fact that the various salt
types are precipitating according to their solubility at each specific tem-

perature interval.
2.4.10. Conditioned permeability of halite
Another effect of the water saturated inter-connected pore system of
When hot saturated brines migrate upwards from the deep, they will
salt is the reduction of the effective stresses in the salt body, i.e., the to-
be cooled and salts may precipitate from the solution. This crystalliza-
tal stress on the salt crystals from the overburden pressure is now partly
tion of salt will exert a pressure on the overburden and is suspected
supported by the pore liquids.
to be an important displacement mechanism for deep salt and for the
This may, in fact, well cause a dramatic change in seismic imped-
RR

formation of salt domes. Salt formations are traditionally treated as be-

ing nearly impermeable for brines and hydrocarbons. However, accord-
ing to experimental work first carried out by Lewis and Holness (1996),
halite buried at depths greater than ∼3 km and elevated temperatures
becomes permeable due to alteration of the dihedral angles of the halite
crystals.
When water is present in the salt, which is always the case in nat-
CO
ance. Thus, when the seismic waves pass from the upper ‘brittle salt’
with higher sonic velocities to a more ductile and permeable salt deeper
down with lower sonic velocities, the impedance shift will be clearly
seen on the seismic records. The so-called decollement seen on many in-
terpreted seismic images of deep-lying salt deposits (‘evaporites’) may
actually represent the ‘Holness Zone’, which causes a seismic response

ural salt deposits, the dihedral angle of the salt crystals is determinant
for the connectivity of this water (Holness and Lewis, 1997). When the
dihedral angle is less than 60° the water is spreading out on the crys-
tal surfaces as continuous liquid films and the salt becomes permeable
(Fig. 3). Vice-versa, when the dihedral angle is larger than 60° the wa-
ter film becomes disconnected and the salt is impermeable: “Our results
explain recent observations of major salt-fluid interactions at depth,
UN
to the distribution of pore water.
2.4.11. Refining of salts
The various solubilities of sea salts, which also change significantly
at higher temperatures and pressures, may result in sorting of the salt
types in the hydrothermal circulation of sea water. A water-deprived
salt accumulation in a hydrothermal system will, therefore, lose the

more soluble salts, e.g. magnesium and calcium chlorides, in contact

and suggest that deep-rooted salt diapirs may act as conduits for basi-
with any available water. Thus, refined halite may precipitate and ac-
nal formation water” (Holness and Lewis, 1997). We are referring to
cumulate, e.g. i) inside salt stocks (domes/diapirs); ii) by venting into
this PT-dependent permeable zone as the Holness Zone (Hovland et al.,
ponds of concentrated calcium and magnesium chloride brines on the
2015). In the hydrothermal model for salt formation, one of the con-
sea floor; or iii) by venting up onto the surface where it evaporates in
sequences of the Holness Zone is that any upward-migrating brine in
a hot and dry climate, as reported from Dallol (Talbot, 2007). In this
this zone will transfer the pressure in the liquid further upwards and
way salt accumulations found as salt stocks or other salt formations have
may cause hydraulic fracturing of the above lying impermeable rock
compositions significantly different from sea salt.
salt, as also pointed out by Schoenherr et al. (2007a, b), Ghanbarzadeh
Another plausible scenario is if an accumulation of different salts
et al. (2015), Warren (2016, 2017). Hot brines at depth can flow
is reheated in the subsurface, e.g. by volcanism or sill intrusions, then
through ‘solid halite’ and displace salt from the high temperature re-
the salts containing crystal water have a tendency to melt, forming hot,
gion to a cooler region where dissolved salts precipitate. Furthermore,

8
M. Hovland et al. Marine and Petroleum Geology xxx (2017) xxx-xxx

dense brines that may migrate out, driven by tectonic forces or lifted by
volcanic gases. An example of such a hydrated salt is bischofite, which
melts at temperatures above 120 °⁠ C (Schofield et al., 2014). Upon cool-
ing, these brines will again crystallize to form solid salts. Such salts will
accumulate stratigraphically above the halite and anhydrite where they
initially were deposited. It should be noted, however, that if volcanic
covery (Corselli et al., 1996; Winckler et al., 2001; Wallmann et al.,
2002).
These ponds are located on top of an oceanic subduction zone (the
Mediterranean Ridge), and the brines are venting out of these zones
(Figs. 4 and 5). It is most likely that these brines were originally part
of the salty pore water going down with the oceanic slab and therefore

F
gases like CO2⁠ or SO2⁠ are exposed to the brine, new salt types may pre- likely the result of refining processes in the subduction zone, leaving be-
cipitate; e.g. carbonates and sulfates. hind major parts of the sea salt, mainly halite, below ground.
2.4.11.1. Refining examples It is very difficult to directly observe refin-

ing processes in the subsurface, but the results of refining can be ob-
served some places on the surface, for instance in the Mediterranean
(Cita et al., 1988; Woodside et al., 2001). The Mediterranean Sea is
unique in that it overlies a zone of mantle convection and has under-
gone a long period of tectonic deformation which includes slab roll-
back and the collision of two large, slowly moving plates (Faccenna et
al., 2014). Several brine ponds are located on the seabed, which con-
tain concentrated brines of high-solubility salts (magnesium and cal-
OO
2.4.12. Preservation of salts
The previous explanation given for the formation of high-magnesium
salts is an example of solubility-based refining of salts, but also pro-
vides an example of a mechanism for the preservation of salt. Obser-
vation of seafloor hypersaline ponds (or ‘lakes’) in depressions on the
Mediterranean seafloor, and elsewhere, shows that lack of mixing en-
ergy in combination with gravitational stability, prevents mixing of the
two. Over time, supersaturation as a result of cooling may occur in the

PR
cium chlorides), e.g. the brine ponds Bannock, Urania, Nadir, and Dis brine lakes, leading to precipitation of solid salts that are protected by
already saturated brines above.

D
TE
EC
RR

Fig. 4. Image modified from Huguen et al. (2006). It clearly shows the topography of the Mediterranean Ridge accretionary wedge and its location in relation to the deep hypersaline
brine ponds: Bannock (B), Atlantis (A), Urania (U), and Discovery (D), which reach nearly 4000 m water depth. The brines are magnesium rich, and halite depleted, signifying refined
salts, due to hydrothermal processes, see text.
CO
UN

Fig. 5. Geological profile across the Mediterranean Rige, modified from Westbrook and Reston (2002). The red arrow indicates rising warm hydrothermal hypersaline brines feeding into
the anomalous seafloor brine ponds. (For interpretation of the references to color in this figure legend, the reader is referred to the Web version of this article.)

9
M. Hovland et al. Marine and Petroleum Geology xxx (2017) xxx-xxx

In more demanding environments, dry climate may protect the salts

from dissolving, even if the salts were not the result of this same climate
(but of hydrothermal activity). In the ocean, salts may also be protected
by a cover of anhydrite between seawater and other salts. This anhy-
drite might be the result of brine outflow carrying particulate anhydrite
with it, or anhydrite remaining from dissolution of anhydrite stained

F
salts on top of salt structures. Normal hemipelagic sediments may also
cover a salt structure and thereby protect it from the actions of the sea-
water. Furthermore, some salt structures are located next to leakage of

OO
hydrocarbons into the sea. The biologic community may then interact
and provide the CO2⁠ necessary to produce a protective cover of authi-
genic carbonate (Judd and Hovland, 2007).

2.4.13. Formation of leaky salt stocks (domes)

As explained in Chapter 2.4.6, saline brines will occupy the contin-
uous pore space of the permeable salts within the ‘Holness Zone’. In
this zone the salt will be more plastic than the salt above (due to less

PR
grain-to-grain contacts) and will be pressurized by the lithostatic con-
fining pressure from the surrounding rocks. This pressure will also be
transferred to the pore water, leading to higher pore pressure in the salt
body, causing also the ‘Holness zone’ to move upwards. This increased
Fig. 6. The southern Dead Sea located 400 m below sea level. SD = the Sedom diapir;
internal pressure is causing expansion of the salt body and may also LD = the Lisan diapir. The fault-lines are: JF = Jerico Fault; SF = Sedom Fault; BF = Boqeq
lead to salt extrusion/intrusion, as often observed in nature (Schoenherr fault, and AF = Arava Fault. Based on Gradmann et al. (2005). (Modified from GeoMa-
et al., 2007a; Hovland et al., 2015; Warren, 2017). Eventually, this in- pApp, e.g., www.Geomapapp.org; Ryan et al., 2009).

D
creased pore pressure may reach the solid salt above the ‘Holness zone’
with sufficient energy to cause hydraulic fracturing and allow periodic low velocity zone extending to a depth of 13–18 km under the basin,
leakage of brine, as stated previously (Table 1) and discussed in more
while the lower crust and Moho was not perturbed. These observa-
detail in Part 2.
TE
tions are supposed to be due to strain softening in the middle crust, in-
If the hydraulic fracturing happens at great depth, the fractures tend
voked to explain the isostatic compensation and the rapid subsidence of
to be vertical, while fracturing at shallow depths is likely to cause
the basin during the Pleistocene (Al-Zoubi and ten Brink, 2002). They
semi-lateral fractures, creating ‘mushroom like’ salt bodies towards the
also produced a conceptual model of the crustal deformation during the
surface (or sea floor). opening of the basin, illustrating the subsidence of the crustal blocks
Hot brines coming from the base of the salt stock (dome) will cool along listric faults and the sedimentary filling (Fig. 7).
EC

and reach over-saturation during the ascent and salts will precipitate ac- The Lisan salt diapir (in the east) and the Sedom diapir (in the west)
cording to their specific solubilities at the different temperature/pres- are the largest salt structures in the DSB (Figs. 6 and 8), up to 7 km deep,
sure conditions. However, this precipitation of salt will not necessarily
and occur as buried structures in the sediments. According to Al-Zoubi
block the flow completely; instead the entire salt body is likely to ex-
and ten Brink (2001) the formation of these structures may have been
pand, and new flow paths are formed. Some salts with higher solubil-
as short as 0.2 million years. They also report the composition of the Se-
ities, e.g. calcium chloride, may dissolve in the migrating brine, to be
dom diapir to be ∼80% halite, the remaining being anhydrite/gypsum,
transported further up; i.e. a refining of the salt body is taking place.
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marls, chalk, dolomite and shale.

The entire process works in concert with the driving pressure that feeds
2.4.14.1. The Dead Sea: accumulating salts in a non-marine
brine from below, into the salt accumulation (e.g., Holness and Lewis,
environment As pointed out by Hardie (1990) the bulk of the solutes in
1997).
the lake brines are added by the upwelling of saline springs around and
up through the lake bottom: “Thus, the Dead Sea stands as a clear-cut
2.4.14. The Dead Sea diapirs
case of a non-marine evaporite depositional site where the evaporating
The Dead Sea is a well-known site for ongoing precipitation and ac-
brines are CaCl2⁠ -rich and SO4⁠ -poor because the inflow-waters are
CO

cumulation of salts in a non-marine environment. This saline lake is sit-

CaCl2⁠ -rich and SO4⁠ -poor” (Hardie, 1990). These features are illustrated
uated in the large fault system referred to as the ‘Dead Sea – Jordan
in Fig. 8, with the sedimentary stratigraphy and the two main salt
Transform rift’; a pull-apart basin, where two overlapping faults (or a
domes, Sedom and Lisan. The structural features are also confirmed by
fault bend) creates an area of crustal extension, causing large scale sub-
Weinberger et al. (2006).
sidence of the basin, thus, providing accommodation space for the depo-
Talbot et al. (1996) made a study of the more than 600 m thick salt
sition of thick sequences of sediments and salts. The current elevation of
beds in the basin and focussed on the large, bulbous halite and carnallite
the lake surface is ∼400 m below mean sea level. A map of the southern
bodies on the bottom. These types of anomalous salt bodies had never
UN

part of the Dead Sea shows the location of the main tectonic and salt
been described before and they suggested a formation caused by the
features (Fig. 6).
slow seepage of groundwater brines through cracks, inferring conduits
Rabinowitz and Mart (1999) were able to reveal the occurrence of
through the Dead Sea lake bottom. They surmised that the band of dens-
shallow mantle masses under the southern Dead Sea using seismic to-
est bulbous salt growths (‘reefs’) occurred in the area between the Lisan
mography, and discloses that: “… the Moho under the Dead Sea is found
and Sedom diapirs (Fig. 8) and were most probably fed by “groundwa-
at a depth of (only) 22 km, and the seismic velocity in the upper lithos-
ter rising from sources deeper than 50 m, …” “… along the Boqeq fault,
pheric mantle is anomalously low”. The data actually suggest that hot
one of the en-echelon transverse fault zones that account for the rhom-
magmatic diapirs ascend along the boundary faults of the rift into the
bic shape of the southern basin”. (Talbot et al., 1996).
intermediate crust, giving a heat-flow in the basin of 40–50 mW/m2⁠ , ac-
This suggestion was further strengthened by the finding of arte-
cording to ten Brink et al. (2006).
sian pressurized groundwater brines that caused precipitation of white
The Dead Sea Basin (DSB) structures were further investigated by
halite by natural springs along the “… brown floor of the Lisan Straits.”
Al-Zoubi and ten Brink (2002), and their seismic surveys also showed a

10
M. Hovland et al.
Fig. 7. Conceptual model of the crustal deformation associated with the opening of the Dead Sea Basin (DSB), indicating a shear zone with fluid flow and earthquake epicentres at the
D
base of the upper crust. (From Al-Zoubi and ten Brink, 2002).
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Fig. 8. The southern Dead Sea Basin: Illustration of the stratigraphy and the salt domes
Lisan and Sedom. See text for further information (Based on Gradmann et al., 2005).
(Talbot et al., 1996). Here, groundwater with a constant temperature of
29 °C rises to about the level of the Jordanian salinity ponds on the east-
CO
ern flank of the straits.
The most spectacular and obvious seepage-related salt structures are
the polygonal networks of salt walls on the seafloor they document:
“Thus, patches of distinct grey halite associated with wafts (smell) of hy-
drogen sulphide probably signal venting of foetid groundwater in small
groups of reef compartments hundreds of metres apart. More spectac-
ularly, a particular screen of halite, a few decimetres thick and 1 m
UN
high, separates brines that crystallize halite for kilometres on one side
from brines that crystallize carnallite for kilometres on the other side.”
(Talbot et al., 1996). These features demonstrate that the seepage of
brines on the seafloor is derived from different compartments in the sub-
surface, where refining processes have isolated various types of salts.
2.4.14.2. Where is the source of the brines? The pattern of the venting
brines into the Dead Sea strongly indicates that the sources are of
deep-seated hydrothermal origin, where the circulation is driven by the
magmatic activity under the basin. The 3D model of the fault zone
(Fig. 7) from Al-Zoubi and ten Brink (2002) actually indicates a shear
zone
11
Marine and Petroleum Geology xxx (2017) xxx-xxx
F
OO
PR
with fluid flow at the base of the upper crust, at 13–18 km depth. It is
suggested that the hydrothermal brines are coming from this zone, as it
may explain the low temperature and high salinity of the venting brines
(29 °⁠ C), which is an effect of cooling along long migration conduits dur-
ing the ascent. The temperature in this deep shear zone is not known,
but global average vertical temperature gradients are 20–30 °⁠ C per km
(Levitte and Greitzer, 2000), indicating temperatures above 300 °⁠ C at
15 km depth.
This concept of a deep hydrothermal source is supported by the find-
ings of Eckstein and Simmonsi (1977): “Deep faults associated with the
Jordan-Dead Sea Rift system act as conduits for hot waters ascending
from deep confined aquifers …” “Most of the ascending thermal waters
are absorbed by shallow aquifers with lower hydraulic potential. Such
regions are characterized by anomalously high heat-flow; several values
exceed 2 and one value is 11 μcal/cm2⁠ s”.
However, the extensive hydrothermal system which is filling the
basin with salts must also be sourced from large accumulations of ‘hid-
den salt’ deep in the subsurface; probably below the upper crust. Such
occurrences of ‘hidden salt’ below the upper crust, interacting with an
extensive hydrothermal system must have affected the entire system sig-
nificantly, both with respect to the tectonic processes and also the seis-
mic properties; i.e. lower seismic velocities. This is actually indicated
on the model of crustal deformation associated with the opening of the
Dead Sea Basin, given by Al-Zoubi and ten Brink (2002) (Fig. 7). Here,
a shear zone at the base of the upper crust with fluid flow is indicated at
around 14 km depth, and they conclude: “The lower lithostatic pressure
(rock overburden) at mid-crust levels under the basin relative to the sur-
rounding crust and the fracturing of rock under the basin due to earth-
quakes at that depth (13–18 km) promote fluid flow from the surround-
ing crust into the middle crust below the basin. The presence of fluids
within the fractured crust helps create weak shear zones along which
the opening is concentrated.”
The large scale hydrothermal system driven by the heat of shallow
mantle masses beneath the basin and the occurrences of large scale ac-
cumulations of ‘hidden salt’ below the upper crust can also explain the
various types of salts depositing on the seafloor: halite and carnallite.
It is cautiously suggested that such accumulations of ‘hidden salts’ may
be the result of subduction in a previous Wilson cycle. Furthermore, it
M. Hovland et al.
is suggested that such salt accumulations will form zones of rock-me-
chanical weakness in the underground, thus, promoting new rifting to
preferably propagate through such zones. These items will be discussed
further in the following chapter (Chapter 3).
3. Relationships between salt formation and Wilson cycles
3.1. Introduction
Following Alfred Wegener's assertion that the Earth's continents
had fitted together, and that they later had split up and drifted apart
(Wegener, 1915, 1922), geophysicists and geologists took another 40
years to resume this model. It was the unequivocal inference from mag-
netometer transects across mid ocean-ridges with the vessel Eltanin in
1966 that turned the table and provided the ‘smoking gun’ that Wegen-
er's model was, indeed, generally correct (Pitman and Talwani, 1972).
The magnetic anomalies on both sides of the mid-ocean ridges came as
proof that the ocean bottom was young and continuously was renewed
along the ridges (Talwani and Eldholm, 1977).
During the same year (1966), John Tuso Wilson also published his
benchmark paper: “Did the Atlantic close and then reopen?” Here, he
presented the question: “How can the plate-tectonic history of the Earth
be deciphered for times earlier than the oldest in situ Ocean floor?”
(Burke, 2016). His answer was “In terms of rocks and structures char-
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acterizing stages in the life cycle of the ocean basins” (Wilson, 1968).
Soon this definition was termed “The Wilson cycle” (Dewey and Burke,
1974; Burke, 2016) and today, the concept of Wilson cycles has become
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a fundamental term in plate tectonics, despite still being debated.
Questions about the start of the Wilson cycles were addressed by
Piper (2013) who suggests a concept of Lid tectonics before Plate tec-
tonics. This suggestion is based on the fact that mobile tectonic plates
are recognized by their paleomagnetic patterns of polar wander paths,
while stagnant tectonic lids are not. These paleomagnetic patterns can
EC
be mapped, and according to Piper (2013) the change from ‘Lid tecton-
ics’ to ‘Mobile plate tectonics’ was transitional, and the Wilson cycle style
plate tectonics developed mainly in the Proterozoic eon that began at
2.5 Ga.
3.2. What are Wilson cycles?
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The stages in the Wilson cycles in their simplest form are, generally,
as follows (Wilson, 1968; Torsvik et al., 2010; Burke, 2011, 2016): Stage
A – a stable craton of continental crust exists. Due to its lower specific
gravity, it floats on top of the mantle.
Stage B – the craton experiences uplift from a rising hot-spot and
starts to rift. A system of branched rifts occurs, thereby creating a
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4–5 km relief between the edges and the bottom of the rift. Eventually,
hot, mafic or ultramafic magma flows in through its bottom.
Stage C – an early divergent margin evolves. The dense magma
starts forming oceanic crust as it cools. Its density prevents it from ris-
ing above sea level. As extension continues, the margins become more
distant from the rift. The oceanic crust cools with time and becomes
denser, sinking deeper into the mantle, thus forming the deep oceans.
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Stage D – a fully divergent margin develops. By now, the first
oceanic crust is too dense to be supported by the underlying mantle. It
starts to sink in, and thereby, starts pulling the rest of the oceanic plate
with it. As it subducts, it brings water with it that feeds volcanism at the
plate boundary.
Stage E – a volcanic margin starts building mountains, either as an
island arc (if the subduction is oceanic), or as a mountain arc if the sub-
duction is of Cordilleran type.
Stage F – eventually, the subducting plate has brought the two con-
tinents on either side of the oceanic crust into contact with each other,
and collisional mountain building starts. Continental crust from one
12
Marine and Petroleum Geology xxx (2017) xxx-xxx
plate is being pushed on top of the other. Eventually, the subducting
slab tears off and the mountains stop growing.
Stage G –brings us back to a stable craton, where erosion eventually
grinds down the mountains and the stage is prepared for a new rifting
episode.
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3.2.1. Salt-forming stages in the Wilson cycles
The stages that provide the opportunity for water or seawater to con-
tact hot mantle, are the most important stages for salt formation. The
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initial continental rifting (Stage B) is usually involving influx of mete-
oric water into deep faults within the rift system. This may easily mobi-
lize soluble substances in the mantle/deep crust and bring them to the
surface via hydrothermal processes. Water may leach out elements con-
stituting salts when interacting with pristine mantle and other rocks, or
bring out salts from previous stages of the Wilson cycle. Burke et al.
(2003) have used the presence of obducted carbonatites to show that
suture zones in the vicinity of the East African Rift represent older sub-
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duction zones that are now located at the center of rifting activities. The
implication of their work is that old salts accumulated during much ear-
lier stages, may be mobilized and re-appear on the surface, from deep,
hidden sources.
When seawater starts filling the rift during Stage C, the same
processes as above will continue and, in addition, the seawater brings
in more salts that may form heavy brines and precipitate solid salts in
the hydrothermal processes. An example of halite production from Lake
Magadi in the East African Rift clearly represents evidence of halite be-
ing accumulated despite occurring far away from current seawater.
During Stage D, the cooling oceanic crust is continually being ex-
posed to seawater down to considerable depth due to contraction and
faulting. Oceanic crust is known to have porosities in the range 20–25%
(Becker and Fisher, 2000). While still remaining hot, ‘off-axis’ hy-
drothermal processes continue at depth within the oceanic crust, thus,
making it ready for the next stage, Stage F. The oceanic crust is now
loaded with seawater, brines, and even some solid salts (Butterfield,
2000).
During Stage F, the oceanic crust and its content of components from
former seawater is subducted. It is heated and pressurized, thereby al-
lowing a new set of chemical and physical reactions to take place.
A subset of the Wilson cycles is commonly referred to as the “Su-
percontinent cycle”. During the history of Earth, several supercontinents
have assembled large landmasses, for thereafter to rift and drift apart
again. From complete assembly of landmasses to rift, it has taken on av-
erage ∼250 Ma.
These events are of great importance to the total energy input to
the formation of solid salts from dilute brines such as seawater, and
there is evidence that supercontinents are an integral part of Wilson
cycles, involving rifting, sea floor spreading, and subduction, and that
these processes have been going on for at least 2.7 Ga (Piper, 2013;
Buiter, 2016). This provides ample evidence for the existence of numer-
ous stages of Wilson cycles and vast areas of Earth that potentially have
been involved in salt formation.
3.3. Subduction and salt
3.3.1. Characteristics of the oceanic crust
The oceanic crust has an average thickness of ∼8 km and a regional
porosity of up to 25%, a porosity, which is considered mainly to be
filled with seawater (Becker and Davis, 1998). Whereas it has proved
relatively easy to find ocean floor vent sites for hydrothermal flow,
it is much more difficult to document where seawater enters into the
oceanic crust, the ‘recharge’ zones. However, one such site was found
by chance, during the drilling of DSDP Hole 395A, at Site 395 in the
Atlantic Ocean. The hole is located at an isolated sediment pond, the
M. Hovland et al. Marine and Petroleum Geology xxx (2017) xxx-xxx

‘North Pond’, measuring 8 by 15 km. The hole was drilled ∼70 km west
of the Mid Atlantic Ridge (MAR) crest, at 4440 m water depth. After
penetrating 92 m into the sediments and over 500 m into the oceanic
crust, mainly consisting of basalts, to their surprise, the researchers
found drawdown of water instead of the expected over-pressure (Becker
and Davis, 1998).
3.3.2. Hidden- and sometimes visible salts in subduction zones
A study by Scribano et al. (2017) states that serpentinites may act as
reservoirs for dense brines and salts due to the mineralogical processes
involved in serpentinization of hot peridotite in contact with seawater.
This salt may later be driven out to become visible salt deposits.

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During a re-visit to this hole, they measured that seawater was dis- Similarly, a study on the fate of salts in peridotites and serpentinites
appearing into the open hole at a rate of ∼1000 L per hour. The hole exposed to seawater was undertaken by Sharp and Barnes (2004). Some
was then fitted with a CORK (Circulation Obviation Retrofit Kit, e.g., an of their conclusions are:

OO
instrumented borehole seal) and monitored: “In the 21 years since the
(1) Serpentinite may be the major conduit for surficial chlorine transfer
initial drilling, Hole 395A has been re-entered 4 times: first during Leg
to mantle depths and an important part of the chlorine cycle. The
78B, and most recently, during Leg 174B. Each time, repeat temperature
Cl flux in serpentinites into the mantle is larger than all other previ-
logs, fluid samples, and flowmeter logs clearly demonstrated that ocean
ously identified fluxes.
bottom water was flowing down the hole at a consistent rate of about
(2) Cl is sited in both water-soluble and –insoluble components.
1000 L/hr” (Becker and Davis, 1998). Results from similar settings, i.e.,
(3) A high-salinity fluid “plume” is evolving during serpentinite dehy-
the flank of the Endeavour Ridge (ODP Leg 168), strongly supports the

notion that there are huge fluxes of low-temperature seawater flowing
through very transmissive upper basement sedimented young oceanic
crust, regardless of whether the sediment cover is continuous or patchy
and regardless of spreading rate.
Oceanic/continental subduction occurs where parts of the oceanic
lithosphere descends into the mantle beneath an overriding continental
plate. During subduction, the oceanic plate becomes dewatered as its
hydrous fluids are released and permeate the overlying mantle wedge
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dration of a subducting slab. The high-salinity fluid affects meta-
morphic reactions and melting properties above the slab and can
cause intense metasomatism.
Deeper processes within subduction zones involving granites have
been investigated by Srikantappa et al. (1992). They observe fluid in-
clusions with halite contents of up to 50–60% held in rocks having been
exposed to 500–550 °C. Based on appearance and orientation of the in-

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(Fig. 9). Similar dewatering also occurs for intra-oceanic subductions,
where oceanic lithosphere descends below another oceanic lithosphere.
Even if the subducting slabs release some of their pore water con-
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tent early in the subduction process, large masses of water and salts are
brought down to great depth and may undergo hydrothermal conver-
sion. To illustrate the potential for salt formation in just one subduction
zone, the Andean subduction can provide some hints. Faccenna et al.
(2017) have calculated the length of subducted lithosphere in the An-
dean subduction zone to be in the range of 2200 km to 7800 km, over
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clusions, the authors suggest that their content is of magmatic origin,
and not meteoric.
Studies of Eclogites from even deeper portions of subduction zones
have been performed by numerous authors, including i) Svensen et al.
(2001), and their study of the eclogites of western Norway, where they
observed salinities in eclogite inclusions of 15–25% salt content; ii)
Xiao et al. (1998) who studied eclogites in eastern China and found
high salinity inclusions in rocks having been exposed to more than
700 °C; and iii) Alexeev et al. (2017) who report from a study on dis-

a period of 25–80 Ma. This subduction zone stretches along the entire posal of highly saline brines flowing into a diamond mine in an eclog-
South America over a width of more than 15,000 km. With a suspected ite hosted kimberlite, situated within the Siberian platform. Inflow of
porosity of 5–10% (from initially 20–25%), filled with saline porewa- salt brines into the mine exceeded 75 m3⁠ per day of brines with solid
ters within the subducted, multiple kilometres thick slabs of the Pacific contents of more than 350 g/litre. These examples leave no doubt that
Ocean crust, the amount of potentially formed salt will be in the size of
millions of cubic kilometres.
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Fig. 9. Left, Zellmer et al.’s figure, showing subduction-related arc volcanism that is triggered by fluids and minerals ‘squeezed’ out of the down-going oceanic lithosphere under the sub-
duction wedge of the overlying continental plate. ‘AW’ = Accretionary wedge; ‘OC’ = Oceanic crust; ‘CC’ = Continental crust. Right, diagram from Manning (2004), which schematically
shows the path of a slab-derived fluid, with mantle H2⁠ O contents (wt%). The fluid migrates into the mantle wedge (solid orange arrows), where it is absorbed through formation of hydrous
minerals. Downward flow of solid mantle (dashed arrows) causes dehydration. After multiple hydration/dehydration steps, the fluid enters a region where it is stable with anhydrous
minerals, which allows greater travel distances. Both images illustrate important aspects of the inner ‘anatomy’ of subductions. These processes occur within the green rectangular zone
indicated on the lefhand figure (Modified from Zellmer et al., 2015; Manning, 2004). (For interpretation of the references to color in this figure legend, the reader is referred to the Web
version of this article.)

13
M. Hovland et al.
salts are transported to great depths in subduction zones, from where
they may reappear during later stages of the Wilson cycle.
It might be stated that the fraction of salt within inclusions is rela-
tively small compared to the volume of the solid rocks and hence that
they may only represent a minor source of salt. This view does not cap-
ture the full extent of the processes behind the formation of these rocks
and their inclusions. There is ample evidence that the trapped inclusions
represent just a minute part of the salts and fluids that were present dur-
ing crystallization of the rocks. The relatively low crystallizing tempera-
tures tell us that these rocks were not formed in dry melts and that much
more water was present before hardening. This is being recognized in
several studies, for example Alderton and Harmon (1991), O'Reilly et al.
(1997) and Harlov et al. (2012).
They all observe how different fluids, including brines, are trapped
during the crystallizing of the rocks, thereby proving presence of fluxes
of brines within the subducting system. When quartz is crystallizing
from solution, it produces water that tends to dilute the brines pre-
sent. It is therefore likely that many inclusions in granites and eclogites
have captured slightly diluted brines, relative to those present at the on-
set of crystallization. Regarding the question of melting versus solution
of minerals in the subduction zones, Manning (2004) states that: “Un-
der appropriate conditions, silicate solubilities may become so high that
there is complete miscibility between hydrous melts and dilute aqueous
solutions.”
D
Laumonier et al. (2017) confirm that the quantity of brines in rocks
within the deeps of subduction zones is in the order of 8–10% relative
to rock volume. They have located a vast volume of water (that origi-
nally subducted as seawater) beneath one volcano - the Uturuncu vol-
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cano on the Bolivian Altiplano. The volume of fluids beneath this sin
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Fig. 10. Conceptual drawing showing the geology of mid ocean rifting, modified from Asimow (2017). The age (millions of years) of the oceanic crust is indicated on the horizontal
axis. “The solid-state flow induced by plate spreading brings hot material upward. Upwelling mantle first crosses the hydrous solidus, where melting begins as a result of trace water in
the mantle, and subsequently the dry solidus, where melting accelerates. The thickness and composition of the crust, geophysical probes, and experiments locating the solidus constrain
estimates of mantle temperature. Sarafian et al. infer that the mantle is 60 K hotter than previously thought.” (Asimow, 2017).
14
Marine and Petroleum Geology xxx (2017) xxx-xxx
gle volcano is equivalent to 500,000 km3⁠ . The volcano is located south
of Lake Uyuni.
This is what Laumonier et al. (2017) state: “Similar high conductiv-
ity features are observed beneath the Cascades volcanic arc and Taupo
Volcanic Zone. This suggests that large amounts of water in super-hy-
drous andesitic magmas could be a common feature of active continen-
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tal arcs and may illustrate a key step in the structure and growth of the
continental crust.” The investigation by Laumonier et al. rests on the in-
terpretation of water as the cause for the high conductivity. The authors
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performed high pressure, high temperature experiments with relevant
rocks and water to establish the water content needed to produce the
observed conductivity. It may also cautiously be suggested that water at
these depths is most likely saturated with salts, e.g., it is likely that hid-
den salts or brines play a yet undetected but important role here.
During later tectonic events, e.g., rifting (like in the East African
Rift), the hidden salts may become activated and mixed with newly
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formed salts from rift-related hydrothermal processes (e.g., Lake Mag-
adi), although, however, it is not straightforward to distinguish between
the two generations of salt. Generally, however, the most soluble salt
types, e.g., magnesium chloride, disappear out of the system.
3.4. Rifting and salt
3.4.1. Introduction
In the Wilson cycle salt model, rifting represents the ‘second phase’,
following that of subduction. Rifting occurs where parts of the continen-
tal or oceanic crust is stressed to such an extent that it is pulled apart,
and causes hot mantle to be drawn upwards, so that it partially melts
(Fig. 10) (Asimow, 2017).
M. Hovland et al.
This chapter reviews how brines and solid salts may become integral
in the rifting process in both continental (non-marine) and oceanic rift-
ing.
3.4.2. Hot-spots and mantle plumes: precursors for rifting
According to Bosworth (2015) and references therein, the Red Sea
rift occurred between two hot-spots, or hot mantle plumes, the ‘Cairo
Mini-Plume’ and the ‘Afar Plume’. What do such plumes represent in
the current context?
Hot-spots arise as a consequence of physical instabilities in mantle
materials. During subduction, the first instability to appear is the com-
pression of the subducting slab, leading to the escape of some of the
saline fluids. During oceanic subduction, the fluids have a relatively
easy access to the surface - or seabed, where they escape to the water
column. This especially occurs along fault planes leading down to the
subduction zone.
As the slab decends the saline brines are causing basaltic volcanism
and the build-up of island arcs, by penetrating the hanging wall (Fig. 9).
During Cordilleran subduction, the situation is similar, but the porewa-
ter contains some extra elements due to slightly different chemistry in
the system. Some saline fluids also escape the subduction zone by flow
to the surface via hydrothermal activity and conductive faults. Brines
escaping the subduction zone in this situation have to penetrate much
thicker crust in order to emanate on the surface. Salty brines emanating
D
onto surfaces with arid climate may lead to accumulation of salt, while
those venting out on locations with wet climate will be washed back to
the sea.
Hot brines emanating on the bottom of deep oceans tend to be bet-
TE
ter protected against dissolution than brines ending up on land. This is
because brines that are venting on the sea floor will cool and precipitate
solid salts that may later be protected permanently by sediments or ma-
terial of biogenic origin such as carbonates.
During the next step of development in the Cordilleran subduction,
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the brines interact with the hanging wall to produce the physical in-
stability that leads to granitic plutons rising to the surface. The plutons
also act as a transport mechanism for saline brines. If the subduction has
been flat for extended periods of time, the original hanging wall mantle
may be pushed away, and a different form of magmatism is seen. But
the water and accompanying salts are still important components of this
inventory.
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During the last stages in the life of a subducting slab it sinks into
the so-called ‘slab graveyard’ at the lower boundaries of the outer man-
tle (Fig. 11). Here, the relatively cool remains of the slab start heat-
ing up again, and with its higher content of remaining hydroxyl-bear-
ing minerals may become buoyant and form a volcanic hot-spot that
rises to the surface. During ascent, it will interact with the surround-
CO
ing mantle and become slightly mixed with it. This does not preclude
the fact that the first parts of the hot-spot magma arriving at the
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Fig. 11. Cartoon modified from Svensen et al. (2017), showing subducted lithospheric slabs that may interact with the margins of thermochemical provinces in the deep mantle, including
‘TUZO’ (in red), located beneath much of Africa and India. This may trigger the formation of plumes, as discussed in the text. (For interpretation of the references to color in this figure
legend, the reader is referred to the Web version of this article.)
15
Marine and Petroleum Geology xxx (2017) xxx-xxx
surface must contain a higher portion of materials from the slab grave-
yard itself. This would imply a certain content of water and salts.
As a hot-spot develops into a spreading oceanic crust, the initial
surge of volatile materials may become less dominant and it releases
magma with a typical basaltic content of chlorides. The difference in
salinity between hot-spots and oceanic basalts has been documented by
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Stroncik and Haase (2004). They state: “The majority of hotspot lavas
have higher Cl/K ratios than depleted mid-ocean ridge basalts, con-
sistent with the presence of recycled crustal components in the man-
OO
tle-plume sources of hotspots.”
Kovalenko et al. (2006) studied the zonal differences within three
mantle hot-spots. They report on the source of the plumes as well as the
distribution of water, chlorine and other elements within it. They con-
clude: “The plume mantle was formed mainly by the mixing of three
sources: ultradepleted mantle, moderately enriched relatively dry man-
tle, and moderately enriched H2⁠ O-rich mantle. In addition to the three
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main components of the plume mantle, there are probably minor com-
ponents enriched in chlorine and depleted in fluorine. It is supposed that
all these components are entrained into the plume mantle through the
mantle recycling of components of the oceanic and continental crust.
The established relationships are in agreement with the zonal model of
a mantle plume, which includes a hot central part poor in H2⁠ O, Cl, and
S; an outer part enriched in volatile and nonvolatile incompatible ele-
ments; and enclosing mantle material interacting with the plume.” This
description of mantle plumes is in line with our model, where water
contained in the outer parts of the plume most likely originates from
the subducted oceanic plate and that chlorine and sulfur are remnants
of marine salts associated with pore water in the oceanic slab.
Both of these two studies on chloride contents and origin of hot-spot
magmas are basing their results on studies of inclusions trapped in vol-
canic glass as the magma crystallized. It is well known that water and
basalts exist in full miscibility at elevated pressures and temperatures,
as the water lowers the melting temperature of the mixture. However,
during ascent the magma is gradually depressurized and ultimately a
higher percentage of water escapes and may transport salts with it as
the lava solidifies. Thus, the amount of water and salts found trapped
in inclusions probably represents the later stage amount and concentra-
tions, rather than the initial stage.
Because hot spot plumes from deep in the mantle (e.g. 3000 km) in-
clude subducted oceanic crust, also sea salts are found in these lavas.
Sobolev et al. (2011) report the analysis of strontium isotopes
(8⁠ 7Sr/8⁠ 6Sr) in lava from Mauna Loa, Hawaii, which matches the com-
position of 0.3–0.5 Ga old seawater. Seawater older than 0.5 Ga is sig-
nificantly less radiogenic. Direct contact with modern seawater is not
consistent with the low values of B and Cl. Thus, they conclude that
seawater must have ‘contaminated’ the Mauna Loa source rock prior to
subduction (Sobolev et al., 2011). These results indicate that sea salts
M. Hovland et al.
used 0.5 Ga to re-appear at surface; i.e., much shorter time than earlier
expected. Based on their study, Sobolev et al. (2011) also calculated the
average circulation rate of crust through the mantle to be in the order
of 1–2 cm/year.
The differences in salinity of hot-spot volcanism, therefore, may be
explained by the origin of their magma. Hot-spots that arise as a result
of subducted materials being recycled should have higher salinity than
others. However, this salinity may not last forever as the more volatile
components must be expected to arrive early and then diminish in con-
centration over time. Initial hot-spot volcanism of recycled mantle ma-
terials should therefore be expected to produce salts with the magma.
This salt comes in addition to other salts produced by hydrothermal ac-
tivity from heat and rock-water interaction.
The composition of evaporites and various rock types were investi-
gated by Kendrick et al. (2017) and compared to seawater. Some of the
data are shown in Table 3 together with calculated ratios between the
three elements Cl, Br, and F. Interestingly, these data show very large
differences between the ratios of these elements for the various sources.
The Cl/Br ratios for evaporites are one order of magnitude higher than
for seawater, while the corresponding Cl/F ratios for evaporites are
nearly four hundred times higher than for seawater. The Cl/Br ratios
for ‘primitive mantle’ are comparable to those of seawater while the
Cl/F ratio of ‘primitive mantle’ is two orders of magnitude lower than
seawater. These elemental ratios demonstrate that evaporites have gone
D
through pervasive refining processes and interactions with the side-wall
rocks in the hydrothermal system and are no longer similar to seawater
composition.
It is important to be aware that even if concentrated brines are
TE
formed from seawater circulating in ascending mantle plumes, special
geological conditions are required for this salt to precipitate as solid
salt and to be preserved. Such relationships cannot be found every-
where. Along the MAR, for example, there is no concentration of salt,
because the seawater-rock interactions are near the seabed and the salt
is washed away. This will often be the case if the serpentinization takes
EC
place near the seabed.
3.4.3. The South Atlantic rift basins
In their analysis of the opening of the South Atlantic Ocean and the
dissection of an Aptian salt basin, Torsvik et al. (2009), argue for a con-
RR
ventional evaporite formation: “ … that the Aptian salt accumulations
belonged to a single pre-breakup (syn-rift) basin confined to continen-
tal and/or subaerial basaltic substrates.” However, water depths of up
to 500 m in this single syn-rift basin are not excluded: “It is widely ac-
cepted that the salt was deposited in a shallow-water environment, and
palaeontological evidence from the Aptian to earliest Albian dolomite
CO
and sapropel sequence of the Angolan margin, deposited just above the
Aptian salt, suggests no more than 500 m paleo-water depth (Marton et
al., 2000)”.
In order to explain evaporation in such a deep basin, Torsvik et al.
(2009) refer to work by Nunn and Harris (2007): “These authors pro-
posed a model of subsurface seepage of seawater across a barrier to ex-
plain this apparent dilemma, which also would constitute a possible ad-
UN
ditional mechanism for the syn-rift deposition of the great evaporite se-
quence.” In our opinion, however, the potential effects of hydrothermal
processes associated with high heat-flow are more plausible mechanisms
for explaining the salt accumulation in the basin.
Table 3
Contents of Cl, Br and F in seawater, evaporites and ‘primitive mantle’. Ratios between the three elements are also shown. (From Kendrick et al., 2017).
Cl (ppm)
Seawater 19,300 ± 970
Evaporites 550,000 ± 50,000
Primitive mantle 5±2
Marine and Petroleum Geology xxx (2017) xxx-xxx
3.4.4. Numerical modeling of the South Atlantic rift
In a recent numerical modeling of the ‘rift-to-drift phase’ of the
South Atlantic salt basin, Norton et al. (2016) mapped the limits of
oceanic crust and salt (Fig. 12). In accordance with the model proposed
by Torsvik et al. (2009), they suggest that salt was deposited when the
F
seafloor spreading began, that is, when the South Atlantic opened. In
addition, Norton et al. (2016), suggest that precipitated salt flowed over
and covered the spreading ridge axis, thus, sealing off the ‘extrusive
OO
components’ of the oceanic crust, resulting in the formation of intrusive
oceanic crust: “Seafloor spreading eventually broke through the thin-
ning salt, forming breakthrough volcanoes preserved today as basement
ramps at the distal limits. These ramps formed diachronously, so the dis-
tal salt limits are not isochrones, explaining the poor fit of these features
in plate reconstructions.” (Norton et al., 2016). Their results are actu-
ally much in line with recent descriptions from the Red Sea by Augustin
PR
et al. (2016), where giant salt flows seal off large tracts of the actively
rifting central axis of the Red Sea (to be discussed in Part 2).
Norton et al. (2016) actually suggest that the salt formation, in sce-
nario C, of Fig. 12, is more-or-less ‘instantaneous’: “Estimates of du-
ration of salt deposition are poorly constrained, ranging from 600 k.y.
to 5 m.y. (Davison et al., 2012). Given Aptian plate spreading rates of
50–60 km/m.y. (Heine et al., 2013), longer intervals of salt deposition
would mean that the conjugate salt basins separated before the end of
salt deposition; this is implausible. We thus prefer a short period of
salt deposition. We also assume that isostatic loading, occurring as it
does over thousands of years as opposed to hundreds of thousands of
years for salt deposition (van den Belt and De Boer, 2007), was instan-
taneous”. However, to us, this seems very improbable, especially when
we know that isostatic forces will not be powerful enough to provide the
needed subsidence.
Thus, a short period of salt deposition is likely, combined with in-
stantaneous isostatic compensation. According to van den Belt and De
Boer (2007) this scenario seems improbable, because the weight ex-
certed by the low density salt is not sufficient to isostatically push down
the heavy rocks beneath the basement floor. However, according to our
model the salt filling the basin originates from ‘hidden salt’ beneath the
basin-floor, and the removal of this salt up into the basin will give an
instantaneous subsidence of the basin floor due to mass balance condi-
tions. This process is referred to as subrosion, e.g., below-ground salt dis-
solution (Ehrhardt and Hübscher, 2015). Furthermore, the circulation of
seawater during the transportation phase added more salt to the salt al-
ready accumulated beneath the basin, as is also seen in the Red Sea, to
be described and discussed in more detail in Part 2.
Thus, it is suggested that the salt basin was filled by salt deposits
during periods of high heat-flow, e.g., during SDR-formation, and that
salt was brought into the basin by hydrothermal saturated brines from
below.
3.4.5. Indications of the same process other places
It is inferred that a similar process is currently taking place in the
northern Red Sea and Afar regions (see Part 2) and is thus, demonstrat-
ing the close relationship between hydrothermal salt production and
volcanism, as well as brine migration and refining of salts, whether they
are deposited on the surface in a dry climate or on the seafloor by pre-
cipitation in high-density brine pools. However, the most interesting as-
pect of the conclusions of Norton et al. (2016) is their transition from
Br (ppm) F (ppm) Cl/Br Cl/F
66 ± 3.3 130 ± 0.07 292 148
150 ± 100 1000 ± 300 3667 55,000
0.076 ± 0.025 17 ± 6 342 1.5
16
M. Hovland et al. Marine and Petroleum Geology xxx (2017) xxx-xxx

F
OO
PR
D
TE
EC

Fig. 12. Sketch, modified from Norton et al. (2016), represents a modern view, based on numerical geo-modeling, on how and when salt was deposited in the Central Atlantic, Campos
and Kwanza basins. ‘RA’ is the depth of the Rift Axis below sea level. The figure text of Norton et al. (2016) is as follows:”The case of seaward-dipping reflector (SDR) margins like part
of the Campos Basin is illustrated. A: Rift basin is subaerial and transitioning to oceanic crust formation. Rift axis is ∼1 km below sea level. B: Same time as in A, but now seawater has
RR

flooded the basin. Rift axis is ∼1500 m below sea level. C: Salt has filled the basin to sea level; rift axis is ∼3500 m below sea level. D: 3–4 Ma after C, with ∼100 km total motion since C.
Intrusive oceanic crust is being created under salt. E: Shortly after D, with volcanism breaking through the salt, forming the breakthrough volcanoes. F: A few million years after E, with
normal oceanic spreading”.

Stage B to Stage C (Fig. 12), where enormous salt deposits are formed tonic activity preceding salt deposition. Over the last decade it has be-
“instantaneously” (Norton et al., 2016). This is indeed parallel to what come a well established fact that heavy brines form and solid salts pre-
seems to have occurred also in the Mediterranean Sea (e.g., during or cipitate within hydrothermal systems, due to the thermodynamic and
CO

prior to the Messinian Salinity Crisis) and in the Red Sea a few million
years earlier.
But even though the bulk of the salt was deposited in the late Ter-
tiary era, salt formation continues. In the Red Sea basin, precipitation
of salt occurs in the subsurface, and slurries of solid salt and satu-
rated brines rise up and are observed venting out along the sides of
the basin, forming “namakiers” of salt that move down the slopes to-
UN
physico-chemical properties of seawater at high temperatures and pres-
sures. It is suggested that volcanism and hydrothermal activity events
associated with different stages of the Wilson cycle are the driving forces
behind salt accumulations in giant basins.
The Wilson cycle is an expression of the geodynamics of Earth,
and based on the conceptual elements highlighted in this work, it is
suggested that the formation of hydrothermal salt is associated with

wards the embryonic spreading centers of the Red Sea. This is in spite
of the fact that the basin water has salinities just above that of seawa-
ter (35,000–37,000 ppm). A completely different scenario is seen in the
Dead Sea, where the salinity in the water exceeds 300,000 ppm, and
halite and carnallite is observed to precipitate in the margins and at the
seabed (Talbot et al., 1996).
4. Concluding remarks
The formation of large marine salt deposits is mainly registered in
ancient basins, especially in areas with a geological history of high tec
deeply circulating seawater within the hydrothermal systems in the
Earth's crust and upper mantle, driven by the internal heat of the Earth.
These seawater-based processes also include serpentinization of mantle
masses and water-rock interactions by the circulating hot seawater in
the oceanic crust. The immense recycling of crustal materials, includ-
ing the subduction of the porous oceanic crust charged with brines and
probably also solid salt, brings water and salt deep down into the man-
tle.
The tectonic activity, including volcanism and associated hydrother-
mal processes bring water and salts upwards towards the surface where
huge amounts of salts may precipitate; e.g. in the high An

17
M. Hovland et al.
des Mountains. It is also acknowledged that such brines and salts may be
stored sub-surface for long periods of time, e.g. extending from one Wil-
son cycle to another. Thus, it is cautiously suggested that large amounts
of salts remain hidden inside the subduction zone including the volcanic
and sedimentary rocks above the subducted slab. During later rifting
and oceanization processes, the subducted rocks, including their con-
tents of hidden salts, may again be mobilized and deposited at the sur-
face.
Uncited references
Bird, 2003; Burke, 1975; Burke et al., 1977; Ehrhardt et al., 2005;
Engvik et al., 2011; Garfunkel et al., 2014; Gutscher et al., 2000;
Hannington et al., 2001; Pirajno, 2009; Searle and Ross, 1975; Wilson,
1966.
Acknowledgements
We would like to thank editors Massimo Zecchin and Timothy
Horsecroft for suggesting publishing this review article. Also we thank
V. Scribano and W. Mohriak for their thorough and constructive re-
views.
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