Salty Matters

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Calcium Chloride (CaCl2), Article 2 of 2: CaCl2 minerals in evaporites

John Warren - Wednesday, May 31, 2017

 

Introduction

Found in association with some highly-saline calcium chloride brines are four naturally occurring CaCl2 minerals with evaporite associations, namely; 1) tachyhydrite CaMg2Cl6.12H2O), 2) antarcticite (CaCl2.6H2O), 3) sinjarite (CaCl2.2H2O) and 4) chlorocalcite (KCaCl3). For any CaCl2 salt to precipitate in a saline setting requires a Ca-enriched mother brine completely depleted in sulphate (Table 1). Otherwise, gypsum precipitates and in so doing removes all calcium from the concentrating brine, well before the bittern stage.

 

Of the four, tachyhydrite is perhaps the most common solid phase, sinjarite or chlorocalcite the least. Bischofite is sometimes a co-precipitate with tachyhydrite and indicative of a mother brine with an elevated MgCl2 content (Figure 1). Even so, tachyhydrite is still a rare bittern mineral phase across the Phanerozoic of Earth, although as we shall see later, the situation may be a little different on the martian surface. Along with carnallite and bischofite, tachyhydrite typifies highly saline marine bittern assemblages in only a few ancient potash-rich evaporite systems. These same systems are also MgSO4 poor, and tend to define times in Earth history of MgSO4-depleted seas. Occurrences include: Silurian potash in Michigan Basin; Carboniferous potash in the Canadian Maritimes and the Paradox Basin; Permian Zechstein-2 Stassfurt potash seams in Stassfurt, Germany; Triassic Saharan potash of North Africa; Cretaceous potash evaporites in Brazil, Gabon and Thailand and Oligocene potash in the Rhine Graben. Tachyhydrite-bearing successions are much less common within a broader MgSO4-poor group of potash deposits (see Warren 2016, chapters 2 and 11; Warren, 2017).


To form antarcticite (CaCl2).6H2O) at the bittern stage, a CaCl2 brine must be depleted in Mg, otherwise tachyhydrite forms, along with carnallite and bischofite. Carnallite, bischofite and tachyhydrite are not part of the bittern suite precipitated from today’s MgSO4-rich oceans, where sulphate and magnesium levels are too high relative to calcium. At times in the past, these three salts were more common precipitates in the bittern stages of ancient CaCl2 or MgSO4-depleted oceans. These tended to be at times when rates of seafloor spreading, and hence volumes of through-circulated seawater, were greater than today (Lowenstein et al., 2014). It seems that most the highly saline calcium chloride brines form in sedimentary basins with a thick evaporite near the base of the sediment fill (see article August 11, 2015). But, not all are basins with highly saline CaCl2 brines are co-associated with bedded tachyhydrite occurrences in the buried and dissolving evaporite units.

Antarcticite

Antarcticite (CaCl2.6H2O) is extremely hygroscopic, colourless with perfect basal cleavage and good to perfect prismatic cleavage, is brittle with a hardness between 2 and 3, and has a specific gravity of 1.715 ± 0.010 (14 °C), and a density of 1.700 g/cm3 (Dunning and Cooper, 1969). The lowest temperature for antarcticite to precipitate is -50 °C and it’s melting point is 30 °C.

There are only two known modern hypersaline saline deposits where the pure calcium chloride mineral antarcticite (CaCl2.6H2O) is present as thin crystal beds and efflorescences; they are, Bristol Dry Lake (BWh) in California and Don Juan Pond (EF) in the Wright Valley, near Lake Vanda in Antarctica (Dunning and Cooper, 1969; Horita, 2009). Both saline lakes possess similar CaCl2-enriched, MgCl2-depleted chemistries and are fed in part by hydrothermal waters. In Bristol Dry Lake the concentration process is driven by solar evaporation, while cryogenesis is the primary driver in Don Juan Pond. Only in Bristol Dry Lake is a CaCl2 brine is commercially extracted from Quaternary sediments. There is also a minor occurrence as isolated small crystals in the Kunteyi Lake of the Tibetan Plateau (Kezao and Bowler, 1986; Zheng and Liu, 2009)


Don Juan Pond, Antarctica

Don Juan Pond is a perennial free-standing water body, approximately 300 m long and 100 m wide, surrounded by glacial moraine deposits in the Wright Valley, Antarctica (Figure 2). It defines the outcrop portion of a liquid water drainage sump that retains a 10-cm-deep CaCl2 brine at the surface (Torri and Ossaka, 1965; Marion, 1997; Burt et al., 2003) (Figure 2). This pool contains some of the saltiest free-standing perennial waters on the earth’s surface, with concentrations ranging up to 40% (by mass; Dickson et al., 2013). Mean annual precipitation the Don Juan Pond region is 5 to 10 cm and air temperatures range from –55°C to +10°C (Marion, 1997). The pond does not freeze because it is a eutectic brine of H2O, CaCl2, and NaCl, with a freezing point of -52°C and a density of approximately 1.4 (Marion, 1997; Burt et al., 2002). Crystals of antarcticite were first found sticking out of the brine at the bottom of the pond, with halite and gypsum fringes at the edges of the pond (Torri and Ossaka, 1965).

Precipitation of antarcticite in this cryogenic environment is the result of the arid climate, ongoing cold temperatures and a CaCl2 brine chemistry (Torri and Ossaka, 1965). The CaCl2 brine is in part derived from springs fed by a deep, confined, basaltic aquifer, with a groundwater similar in composition to the surface brine (Harris et al., 1979; Marion, 1997; Burt et al., 2002). The origin of the CaCl2 is still contentious, but is most likely be related to mineral weathering and periodic deliquescence of calcium chloride held in the sediments(Dickson et al., 2013).


Brine in the Don Juan Pond is predominantly from CaCl2 solutions (Figure 3; Marion, 1997). Only Na of the remaining cations contributes significantly to the overall charge balance. Both Mg and K are present at very low concentrations, and SO4 is usually not detectable. In contrast to low ionic variability in seawater composition, levels of the dominant ions (Ca, Na, and Cl) in the Pond are highly variable (Figure 3). The concentration of the brine varies seasonal, controlled mainly by a complex hydrologic system including groundwater discharge, melting of nearby permafrost, rare precipitation, and evaporation or sublimation (Harris et al., 1979; Dickson et al., 2013). Despite the changes in the absolute concentration of Ca and Cl across an annual cycle, the Ca/Cl molal ratio remained relatively constant over the 23-year sampling period; it varies between 0.432 and 0.506 with an average of 0.462 ± 0.018 (Figure 2; Marion, 1997).

Bristol Dry Lake, California

Bristol Dry Lake is a 155 km2 continental playa located within a closed Basin and Range valley in the Mojave Desert of southern California (Figure 4a). It is the second known location of natural antarcticite and is thought to precipitate from lake brines via a lowering of brine temperatures (Dunning and Cooper, 1969). No antarcticite was identified in the nearby Cadiz or Danby dry lakes. Lake brines first concentrate by solar evaporation beyond halite precipitation Mountains surrounding Bristol Dry Lake are composed mostly of pre-Cambrian and Mesozoic granite, some Palaeozoic carbonates, and Tertiary and Pleistocene volcanic rocks including Quaternary olivine basalts that erupted from nearby Amboy Crater. Alluvial fans are present between the mountains and the lowest parts of the valley (Dunning and Cooper, 1969; Handford, 1982).


Bristol Dry Lake playa contains more than 300 m of interbedded halite and salt-bearing sands, silts and clay. Halite and gypsum are currently deposited from ephemeral bodies of water under evaporative conditions, with a gypsum pavement surrounding more saline halite-saturated sumps in the central lake depression (Figure 4a; Dunning and Cooper, 1969; Handford, 1982; Rosen and Warren, 1990). The primary evaporite minerals at Bristol Dry Lake are gypsum, anhydrite, and halite with rare antarcticite, celestite (SrSO4), calcite, and possibly chlorocalcite (KCaCl3). Bristol Dry Lake is mined for its chloride minerals and has been since the 1900s, and so is covered with pits and trenches (Figure 4b).

Antarcticite was identified in one of these previously excavated trenches approximately 9 kilometres south of Amboy, near the road from Amboy to Twenty-nine Palms. Dunning and Cooper (1969) examined this and other trenches during the winters of 1961, 1962, and 1968. Only one trench had antarcticite. The trench was 3 m deep, 20 m long, and contained a 10 to 25 cm deep pool of CaCl2 brine extending along the length of the trench. At the base of the pit was a massive halite deposit, with acicular groups of antarcticite protruding outward from the halite and within the brine. Antarcticite is not present on the playa surface as no surface brines are present. The only CaCl2 brines exposed to solar radiation are subsurface brines that have seeped into, and are now exposed within, the excavated trenches.


Dunning and Cooper (1969) suggested that CaCl2 brines at Bristol Dry Lake originated from chlorine of volcanic origin interacting with calcium carbonate in surrounding alluvial deposits (Figure 5). Lowenstein et al. (2009) argue that the nearby active magma chamber drives the formation of Ca-Cl brines at elevated temperatures, as well as the thermally-driven transportation of these brines to the surface. Other evidence for the magma chamber is the Amboy crater and its associated recent lava flows, which occur directly North of Bristol Lake. Evaporative concentration of this calcium chloride brine, driven by an arid climate and typical surface temperatures below 30°C, encourage antarcticite precipitation (Dunning and Cooper, 1969).

Sinjarite (CaCl2.2H2O)

Sinjarite is a modern ephemeral precipitate in surficial alluvial fan sediments near Sinjar in Iraq (Figure 6). No natural occurrences of either antarcticite or sinjarite have been documented in ancient salts, except as a volumetrically insignificant mineral phase in brine inclusions in both sediments and igneous rocks (Polozov et al., 2016), even in sedimentary basins containing highly saline CaCl2-rich pore fluids.


Sinjarite is an extremely rare pink-tetragonal-hygroscopic mineral that is highly soluble with 117 g dissolving in 100 g of water at 20 °C (Table 1; Aljubouri and Aldabbagh, 1980). The lowest temperature for sinjarite to precipitate is 42.3 °C, while its melting point is 175.5 °C (Wardlaw, 1972). Theoretical composition of sinjarite is 27.26% Ca, 48.24% Cl, and 24.50% H2O but the actual chemistry for sinjarite present at its type locality in Iraq is 25.84% Ca, 46.64% Cl, 26.55% H2O, and 0.85% Na with 226 ppm K and trace amounts of Mg, Sr, and Fe (Aljubouri and Aldabbagh, 1980). Properties include; good cleavage, average density of 1.81 g/cm3, a very deliquescent habit, hardness of 1.5, vitreous to resinous lustre, white streak, and occurs naturally in massive to granular forms.

Little research has been performed on sinjarite and knowledge of the environment of formation comes from the only place it was discovered. Sinjarite occurs in detritus in a wadi cutting through the Sinjar anticline near the town of Sinjar, Iraq (west of Mosul). Sinjarite precipitates via slow evaporation of groundwater saturated with Ca and Cl ions. CaCl2 in the groundwater solution must be 3.5 times greater than NaCl for sinjarite to precipitate instead of halite. The extremely deliquescent nature of sinjarite means that the mineral is ephemeral and quickly dissolves in wet seasons or changes to the hexahydrite antarcticite when the temperature is less than 30°C (Aljubouri and Aldabbagh, 1980).


CaCl2 salts and liquid water flows on current-day Mars

On the current Martian surface it has been recently proposed that aqueous solutions form seasonally, via the deliquescence of hygroscopic salts in contact with atmospheric water vapor. Regions of these hygroscopic salts are thought to be indicated by occurrences of surface features known as recurring slope linae - RSL (Figure 7a, b; Chevrier and Rivera-Valentin, 2012). Older studies largely focused on perchlorate species as the most likely set of hydroscopic salts driving the periodic formation of RSLs, but another Mars-relevant set of salts, with similar low eutectic temperatures, relevant to ambient conditions with a significant deliquescence potential, are the calcium chloride hydrates, antarcticite and sinjarite. Gough et al. (2016) propose hydrated calcium chloride salts are linked to RSL formation on Mars. They also note deliquescence of CaCl2, not perchlorate, is also known to be responsible for the only terrestrial RSL analog known thus far: these are the seasonal water tracks in the McMurdo Dry Valleys, especially in the vicinity of the Don Juan Pond, as documented by Dickson et al., 2013 (Figure 8).

Soluble regolith salts like perchlorate and calcium chloride salts with low eutectic temperatures are likely to deliquesce at low relative humidity (RH) values at a wide range of temperatures (Gough et al., 2016). Deliquescence is the process by which a solid crystalline phase absorbs water vapor to form a saturated aqueous (liquid) solution. This phase transition from solid salt to liquid brine occurs at a deliquescence relative humidity (DRH), the value of which is specific for each hydration state of each salt and often varies with temperature. A salt is expected to be aqueous whenever the temperature is above the eutectic temperature of the salt and the relative humidity is above the DRH, although at much higher RH values ice may form. The low temperature deliquescence of perchlorates has been extensively studied (Gough et al., 2011, 2014; Nuding et al., 2014; Zorzano et al., 2009). Many perchlorate species have deliquescence relative humidity (DRH) values below 40% RH, and so should deliquesce and be stable or metastable liquids under Martian surface conditions (Chevrier et al., 2009), although slow reaction kinetics may limit their formation (Fischer et al., 2014). Not as much attention has been paid to other soluble, deliquescent salts, especially the calcium chloride salts, that may be present in the martian regolith.

Chlorine has been detected by rovers and landers in every Martian soil sample analyzed to date and is found at similar concentrations (≈0.2 to 1%) in all locations (Glavin et al., 2013). The form of the chlorine (i.e. chloride vs. perchlorate) is unknown at some sites, although measurements of the regolith at the Phoenix landing site confirmed chloride, perchlorate (Hecht et al., 2009) and probably chlorate (Hanley et al., 2012). The identity of the associated cation(s) is also generally unknown, although calcium, sodium, magnesium and potassium are the most likely candidates (Hecht et al., 2009). Regionally and globally widespread chloride deposits have also been detected by orbiting spectrometers (Figure 7c; Osterloo et al., 2010; Keller et al., 2006).

The global distribution of chloride deposits across the Martian surface is similar to that of recurring slope lineae (RSL), prompting hypotheses of a relationship between the two (Figure 7c; McEwen et al., 2011; Stillman et al., 2017). Chevrier and Rivera-Valentin (2012) suggest that CaCl2 is one of the best candidates for the formation of RSL, the narrow, dark features that appear and grow seasonally on Mars and appear to be caused by flowing liquid.


Two hydrated chloride salts, MgCl2 and CaCl2, may be the most appropriate salts because the seasonality of observed RSL formation best matches the seasonality of the melting of ice associated with these salts (Chevrier and Rivera-Valentin, 2012). Specifically, these chloride salts have eutectic temperatures less than or equal to the threshold temperature of 250 K that seems to mark the start of RSL activity (McEwen et al., 2011), but the eutectic temperatures of these salts are not so low that brines on Mars would be permanently liquid. Additionally, calculations show that CaCl2 in particular will cause seasonal melting of water ice throughout the top 20 cm of the martian regolith, therefore providing greater potential fluid flow than other salts (Chevrier and Rivera-Valentin, 2012). More recently, hydrated chloride salts (although not specifically calcium chloride) were observed to be present in RSL but not in surrounding regions (Ojha et al., 2015). It is not generally believed that deliquescence could be fully responsible for RSL formation because the small amount of water vapor in the martian atmosphere would limit the condensed phase water that could form. It is certainly possible, however, that salt deliquescence may be involved in the formation of RSL or in their appearance or behavior (McEwen et al., 2011; Ojha et al., 2015; Dickson et al., 2013; Stillman et al., 2017).

In summary, determining whether liquid water exists on the Martian surface is central to understanding the hydrologic cycle and potential for extant life on Mars (Ohja etal., 2015; Stillman et al., 2017). Recurring slope lineae, narrow streaks of low reflectance compared to the surrounding terrain, appear and grow incrementally in the downslope direction during warm seasons when temperatures reach about 250–300 K (-23°C to +26°C), a pattern consistent with the transient flow of a volatile material. Brine flows (or seeps) associated with seasonal deliquesence of hydrated salts (possibly hydrated calcium chloride salts or perchlorates) are proposed to explain the formation of recurring slope linea. As yet, no direct evidence for either liquid water or actual hydrated salt mineralogies has been found.


Tachyhydrite

Tachyhydrite (CaMg2Cl6.12H2O) (occasionally spelled tachydrite or tachhydrite) is a yellow, transparent to translucent, trigonal-rhombohedral mineral with very high solubility. Pure tachyhydrite is composed of 7.74% Ca, 9.39% Mg, 41.10% Cl, 37.09% O, and 4.67% H (Wardlaw, 1972). Its chemical formula is most accurately expressed as [Mg(H2O)6]2[CaCl6] because the structure consists of Mg(H2O)6 octahedra and CaCl6 octahedra loosely linked together by hydrogen bonds. Physical properties include; good cleavage, vitreous to greasy lustre, white streak, massive habit, bitter taste, deliquescent habit (dissolves or liquefies upon exposure to air), a density of 1.66 g/cm3, a hardness of 2, and it is hygroscopic (Braitsch, 1971).

Tachyhydrite is extremely soluble with 160 g dissolving in 100 g of water at 20 °C, and its solubility increases with increasing temperature (D’Ans, 1961; Wardlaw, 1972). Its hygroscopic and extremely deliquescent nature means at earth surface temperatures a crystal becomes liquid by absorbing moisture in the air. On exposure, tachyhydrite quickly alters to a residue of bischofite (MgCl2.6H2O) and a CaCl2.nH2O phase (Wardlaw, 1972). This is why tachyhydrite is typically documented in natural occurences where a crystal is still encased in halite. Tachyhydrite has a wide thermal stability field from 21.95°C to at least 167°C (Braitsch, 1971; Clark et al., 1980). The lowest temperature for tachyhydrite precipitation is 21.95°C at a concentration of 92.7 mol CaCl2/1000 mol H2O (450 g CaCl2/liter (D’Ans, 1961; Braitsch, 1971; Wardlaw, 1972). Its lowest temperature of formation increases by 0.0162ºC for every atmosphere of pressure (D’Ans, 1961).

Modern tachyhydrite occurrences

Natural tachyhydrite is documented only in a few modern hypersaline settings and it never forms a bed with primary precipitation textures (Figure 9). It is found in greater quantities in some ancient potash deposits. Tachyhydrite occurs seasonally as a minor interstitial cements and efflorescences, along with antarcticite (the hexahydrate form of calcium chloride), in the modern ephemeral halite crusts, atop sabkhas, of the Gavkhoni Playa (BWk), southeast of Isfahan, Iran (Pakzad and Ajalloeian, 2004), in mine wates in the Salar de Pedenales in the andean Altiplano, and perhaps as minor salt effloresecnes in the uppermost parts of the Abu Dhabi sabkha (Wood et al., 2005).

Much of the elevated ionic content of various Iranian playas in the Great Kavir is due to salt dissolution of the crests of nearby at- or near-surface diapirs and namakiers, where the mother salt sourced in halokinetic Miocene marine salts (Warren, 2008). These outcropping diapirs have carried carnallite and sylvite remnants into the namakiers that now reside at the surface (Rahimpour-Bonab and Kalantarzadeh, 2005). Tachyhydrite is also found as white feathery efflorescences within waste piles at an abandoned borate working along the southwestern margin of Salar de Pedernales, Chile (a BWk Koeppen climate location very near the ET climate boundary; Ericksen et al., 1989).

It seems that tachyhydrite’s high solubility means it has little or no preservation potential as a solid salt in any modern at-surface depositional setting; in the Peruvian case, it is a winter precipitate that disappears with the end of winter. In Abu Dhabi it, along with other highly soluble salts in the salty surface efflorescences, can disappear in morning dew (Warren, pers. obs.). In both the Iranian and the Peruvian settings the climate is cool and elevated. It seems the arid desert environments where bedded subaqueous-textured tachyhydrite accumulated in the drawndown Aptian seepage basins of the opening Atlantic were very different to its occasional rare occurrence in the evaporite settings of today.

Cretaceous of Brazil & W. Africa

Lower Cretaceous (Aptian) evaporite deposits in Sergipe, Brazil, and Gabon and Congo in western Africa contain significant amounts of tachyhydrite in halite-carnallite beds, along with other SO4-poor bitterns (Figure 10; Wardlaw, 1972; Borchert, 1977; de Ruiter, 1979; Hardie, 1990; Garrett, 1995; Zhang et al., 2017). These evaporite basins formed during the early Cretaceous rifting of Africa and South America. In each basin, potash-rich halite-dominant evaporites are transitional between older continental pre-rift and rift siliciclastics and younger post-rift marine shales and carbonates (Wardlaw, 1972, Borchert, 1977; de Ruiter, 1979; Szatmari et al., 1979; Hardie, 1990; Garrett, 1996).


The basic salt cycle of the Gabon and Congo basins includes from bottom to top: (1) thin black shale, (2) halite, (3) combination of halite and carnallite (carnallitite, and (4) bischofite and/or tachyhydrite (Figure 10;de Ruiter, 1979; Zhang et al., 2017). Although variations exist, a similar sequence is present in Sergipe, Brazil comprising the Ibura Member of the Muribeca Formation. The Ibura Member includes from bottom to top: (1) halite, (2) carnallite, (3) tachyhydrite, (4) sylvite (KCl) and halite, and (5) anhydrite (CaSO4) (Wardlaw, 1972; Borchert, 1977; Garrett, 1996). Tachyhydrite is located within the central and deepest portions of the Sergipe basins (Wardlaw, 1972; Borchert, 1977; Szatmari et al., 1979).

The origin of the evaporite sequences in Sergipe, Gabon and Congo is controversial with some authors suggesting a marine origin (Wardlaw, 1972; de Ruiter, 1979; Szatmari et al., 1979) or diagenetic origin (Borchert, 1977). More recent literature discussing Sergipe, Gabon, Congo, and other similar tachyhydrite deposits cite a non-marine/hydrothermal origin based on geochemical and textural studies (Lowenstein et al., 1989; Hardie, 1990; Garrett, 1996; El Tabakh et al., 1999). Yet other recent authors indicate a marine source based on its dominance in beds with a CaCl2 oceanic timing (Warren, 2016; Zhang et al., 2017).

The brine that tachyhydrite precipitated from must have been high in Ca because in waters with more SO4 than Ca present, the Ca is used-up by gypsum or anhydrite. Only if the Ca level is greater than SO4 in the early stages of precipitation will Ca stay in the brine allowing for potential precipitation of tachyhydrite (Wardlaw, 1972; Hardie 1990). The CaCl2-rich brine that produced the tachyhydrite and other potash salts is thought to have formed either by the interaction of hot meteoric groundwater with rift-related sediment and bedrock, or an influx of seawater at a time of a MgSO4-depleted ocean. Based on figure 1, Hardie (1990) suggests heated seawater could also have interacted with sediment and/or bedrock to produce a CaCl2 brine. This hot CaCl2 brine was perhaps driven to the surface by thermal circulation (Hardie, 1990). Alternatively, without arguing that the proportions of major ions in seawater change over time, the fact that modern marine water cannot precipitate tachyhydrite precludes it being the dominant mother brine in the Sergipe, Congo, and Gabon Basin evaporite basins,  (Lowenstein et al., 2014; Warren  2016).

Textures recovered in core, and visible in mine walls in Brazil, indicate Sergipe tachyhydrite was a primary bedded precipitate in those circum-Atlantic Cretaceous evaporite basins with stratiform tachyhydrite units in potash beds (Figure 10; Wardlaw, 1972). The Cretaceous world ocean at the time this tachyhydrite precipitated was a MgSO4-free marine bittern. Figure 9 shows tachyhydrite does not occur as a bittern phases in many other potash sequences deposited in basinwide settings at other times of CaCl2 oceans (e.g. the Devonian of Canada, the Silurian of the Michigan Basin). This has led to the argument that stratabound tachyhydrite in potash beds indicates an additional hydrothermal/basinal source for the mother brine. If so, the presence of tachyhydrite is not solely indicative of a MgSO4-depleted marine feed to the basin (Hardie 1990).

Cretaceous occurrences in Thailand

Another significant tachyhydrite occurrence is within slightly older mid Cretaceous (Cenomanian) evaporites of the Maha Sarakham Formation on the Khorat Plateau of northeastern Thailand (Figure 11). The majority of the Maha Sarakham Formation consists of alternating anhydrite and halite, separated by mudstone and siltstone “redbeds”. A 10- to 75-m-thick salt unit overlies a lower halite unit and underlies mudstone red beds of the lower clastic unit. Carnallite is most abundant in this salt unit, but sylvite and halite are also locally abundant. Tachyhydrite is present with halite and carnallite, but not with sylvite and is perhaps concentrated more in former basin centre or sump positions (El Tabakh et al., 1999; Warren 2016). Hite and Japakasetr (1979) estimated that tachyhydrite comprises less than 30% of the total carnallitite deposit, but tachyhydrite can form pure layers up to 16 m thick. Tachyhydrite crystals are euhedral and average 1 mm in size (El Tabakh et al., 1999). Sylvite and halite are also associated with accessory amounts of hilgardite [Ca2BCl(OH)2] and boracite (Mg3ClB7O13).


The origin of the Maha Sarakham Formation evaporites is still contentious; Hite and Japakasetr (1979) advocate a purely marine origin (highly restricted and concentrated sea), Hardie (1990) advocating an exclusively non-marine origin (hydrothermal CaCl2 brines), and El Tabakh et al. (1999) advocate an alternating marine and non-marine origin. They envisage an inland basin that was periodically inundated by the rising sea and at the time of tachyhydrite deposition received an additional influx of hydrothermal CaCl2 brines. Hardie (1990) states that formation of Maha Sarakham evaporites may have been similar to that of tachyhydrite formation in the Cretaceous basins of Brazil and western Africa, although he offers no evidence for the origin of the hydrothermal CaCl2 brines. El Tabakh et al. (1999) suggested that hydrothermal CaCl2 waters entered the restricted marine basin and created the right conditions for tachyhydrite precipitation and they cite contemporaneous granitic intrusions as possible evidence of thermal activity during the time of tachyhydrite formation.

Hydrothermal oceanic CaCl2 brine

Today, large volumes of relatively dilute, oceanic CaCl2 brines form via hydrothermal circulation and thermally-driven alteration of mid-ocean ridge (MOR) lithosphere (see part 1). These CaCl2 waters occur in and near active fracture zones, wherever seawater interacts with labile basalt (oceanic crust) at elevated temperatures and converts the circulating fluid from a Na-Mg-Cl water into a low-salinity Na-Ca-Cl brine, depleted in Mg and SO4. Similar hydrothermally-driven alteration of continental basalts via deeply circulated seawater interactions forms modern CaCl2-rich brine seeps, for example, within the thermally active continental Danakil rift valley (Hardie, 1990).

Tachyhydrite is a 'Swift Water" mineral

There may be an additional factor at work in terms of our recognition of tachyhydrite’s basin-by-basin distribution across the Phanerozoic. That factor is tachyhydrite’s high solubility in most subsurface waters and drilling muds. Even the name, tachyhydrite, was chosen from the Greek tachy hydros for “swift water” to indicate its rapid deliquescence on exposure to atmospheric conditions. This property means that any ground-up remains (rock chips) of tachyhydrite in a return mudstream in a conventional drilling operation typically do not make it to the surface. So, as most oil companies prefer not to core evaporites when drilling for hydrocarbons trapped beneath salt, there may be more tachyhydrite occurrences in deeply buried basin evaporites than the few currently documented.

Ancient tachyhydrite has only been found encased in halite in recovered cores and mine walls, never in drill cuttings, and its presence or absence can be easily misinterpreted in wireline logs, especially when drilling through thick salt masses in the search for oil and gas (companies tend to run a more limited log suite in thick salt units).

 

Tachyhydrite’s lack of shear strength and extremely high solubility makes mining any associated potash beds difficult; it presence leads to head beam and floor stability problems in conventional underground mines in Brazil and West Africa. Holle, a West African potash mine in the 1970s, was never economical and was lost to flooding after a few years of conventional mining and the Brazilian mine has ongoing floor and wall stability problems ties to tachyhydrite-induced heave. Today, solution mining is proposed as a more efficient means to exploit areas of Cretaceous potash associated with tachyhydrite beds, as in Aptian halite-potash associations on both sides of the Atlantic. High levels of tropical humidity mean at-surface potash evaporation pans are not viable in either area, so brine concentration and processing will probably require a more expensive option involving motorised dryers.

 

Not only is tachyhydrite highly soluble, but it is also highly reactive whenever in comes into contact with subsurface bitterns. Based on its occurrence in the Permian Stassfurt series in Germany, D’Ans (1961) suggested that much of the widespread polyhalite found in the CaCl2 brine-rich parts of the Zechstein Basin was a reaction product indicating former tachyhydrite. He noted that, at temperatures higher than room, there is a reaction between gypsum/anhydrite, sylvite and tachyhydrite-bischofite, or their dissolution-related brines, which removes tachyhydrite to form diagenetic polyhalite and calcium chloride brines;

CaMg2Cl6.12H2O+4KCl+8CaSO4--> 2CaSO4Mg(SO4)4(H2O)2 + 5CaCl2 + 4H2O

This was the mechanism suggested by Manheim (1974) to explain the lack of tachyhydrite, and the formation CaCl2-rich brines that characterise hydrothermal pore waters circulating in sediments associated with buried Miocene evaporites along the deep axial trough of the Red Sea.

Terrestrial CaCl2 minerals across time

The high solubility of CaCl2 minerals means that, with the exception of some parts of the Aptian Atlantic Potash association, even in past times of likely CaCl2-rich oceans, calcium chloride minerals are relatively rare as primary-textured occurrences in solid salt beds. On the other hand, as we saw in part 1, CaCl2 brines are commonplace in basinal or formation waters in many Phanerozoic sedimentary basins entraining thick sequences of dissolving ancient salt. For example, since 1914, CaCl2 brines have been extracted from Silurian strata adjacent to Salina Salt of the Michigan Basin USA, yet there are no significant volumes of tachyhydrite documented in the Michigan Basin(Garrett, 2004).

Historically, before micro-inclusion studies of chevron halite showed that the ionic proportions of seawater likely varied across the Phanerozoic, the various CaCl2 basinal brines occurrences in Silurian and Cretaceous strata were explained as an indicator of widespread dolomitisation and other diagenetic reactions, which preferentially extracted magnesium from pore waters. Since then, some authors have argued that CaCl2 enrichments in many ancient basinal brines, including brines in the Detroit group are partial leftovers of primary seawater chemistries (Lowenstein and Timofeeff, 2008). That is, Ca-enriched (MgSO4-depleted) pore brines are indicators of ancient CaCl2 oceans, with the pore brines being remnants from time the enclosing evaporitic and marine sediments were deposited (relict or connate brines).

Others, such as Houston et al. (2011), conclude this is not necessarily so, they agree that there are two end-members typifying highly saline subsurface brines. But they conclude that end-member chemistries relate to either substantial subsurface halite dissolution, or to preservation of early reflux-related seawater. Houston et al. (2011) go on to argue that CaCl2-enriched formation water chemistries from many basins worldwide, including the Michigan Basin, do not support an interpretation of variation in ionic proportions in seawater across the Phanerozoic. They find that CaCl2-rich brines formed either by dissolving bittern salts in the subsurface, or simply lost water in the subsurface after significant rock-fluid interaction had taken place. Water loss might be achieved by interaction with a gas phase at the elevated temperatures of deep burial or, alternatively, water may have been lost to clays. Both these mechanisms would have the effect of dehydrating (concentrating) the brine.

However, whatever the mechanism, it does seem that there is a Quaternary continental/pre-Quaternary marine dichotomy in the nature and distribution of CaCl2 brines and the associated antarcticite/tachyhydrite minerals, much as there is for the world’s potash deposits (MgSO4-enriched versus MgSO4-depleted). On Earth, there are no documented examples of pre-Quaternary bedded antarcticite. The situation may be different on Mars.

Today terrestrial antarcticite either precipitates in the hot-arid Bristol Dry Lake or the icecap-polar setting of Don Juan Pond, neither is associated with brine sourced in seawater or derived by the recycling of older (“connate”) marine evaporite successions. Rather the occurrenceof the calcium chloride minerals is in part a reponse to low temperatures and regolith cycling. Other present-day examples of regions with somewhat enriched levels of CaCl2 surface waters, lack both tachyhydrite and antarcticite precipitates, and contain higher levels of Mg that are tied to deeply circulated marine/hydrothermal waters and variable interactions with MgSO4-enriched marine salts (e.g., Lake Asal and the Dallol Salt Pan). CaCl2 brines of the Dead Sea and the Red Sea show even more elevated levels of MgCl2 as they are derived, at least in part by the fractionated dissolution of bedded and halokinetic Miocene marine evaporites. The Mg-rich clay palygorskite is co-associated with these CaCl2 brines in the subsurface of the Red Sea and the Dallol.

In contrast, tachyhydrite in some ancient marine-fed basinwide evaporite associations is found as somewhat rare, but at times bedded, units in the bittern-rich portions of the halite succession, as in the Cretaceous basinwide evaporites of Brazil, the Congo and Thailand, and as a cementing phase in the Permian Stassfurt 2 in the Zechstein (where it is commercially extracted in association with MgCl2 brines).

All the ancient tachyhydrite examples mentioned above, are associated with the presence of widespread potash salts within adjacent salt beds. However, there are many other even larger and richer ancient potash deposits, such as the intracratonic Alberta basin (Devonian) and the Kama basins (Permian) where no tachyhydrite is documented. It seems that the terrestrial precipitation of bedded tachyhydrite is not just favoured by times of CaCl2 oceans, it also requires additional input from saline hydrothermal/basinal waters. Such settings are most likely in the transition phases in an actively-opening hydrothermally-influenced continental rift as passes into the marine seepage realm at a time when the adjacent ocean was a MgSO4-depleted system.

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Calcium Chloride (CaCl2), Article 1 of 2: Usage and brine chemistry

John Warren - Sunday, April 30, 2017

 

Introduction

Calcium chloride minerals in the natural state are rare and only found in a few specific evaporite associations. On the other hand, calcium chloride-rich brines are commonplace in the burial diagenetic realm, especially in deep high-salinity basinal brines and in a number of hypersaline lake waters, especially in rift settings. In the subsurface, these brines also play a significant role in the formation of a number of metal ores. Occurrences of both the brine and the minerals have significance in modelling rock-fluid interactions and seawater chemistry across geological time.

At earth-surface temperatures, calcium chloride can exist in the solid state as the anhydrous form (CaCl2) as well as in four levels of hydration – CaCl2.H2O; CaCl2.2H2O; CaCl2.4H2O; CaCl2.6H2O (Table 1). Of this group, CaCl2 occurs naturally as two rare minerals; antarcticite and sinjarite. All of the early studies on calcium chloride and its hydrates were done with laboratory-prepared samples of brines and hydrates, since CaCl2 was not produced on a commercial scale until after the ammonia–soda process for the manufacture of soda ash (Solvay Process) was in operation. Before its industrial uses were discovered, calcium chloride was considered a waste product of brine production. Today, its primary industrial use is predicated on the very high enthalpy change of solution, indicated by considerable temperature rise accompanying dissolution of the anhydrous salt in water (Table 1 – Heat of solution in water). This property is the basis for its largest scale application, namely road de-icing.

 

In the natural state, most CaCl2 occurs in solution in basinal waters in sedimentary basins and modified pore waters in specific hydrothermal associations. Calcium chloride, in a mineral state in the natural world, occurs as the rare evaporite minerals; sinjarite (CaCl2.2H2O) and antarcticite(CaCl2.6H2O). The related potassic and magnesian calcium chloride minerals, chlorocalcite (KCaCl3) and tachyhydrite (calcium magnesium chloride, CaMg2Cl6•12H2O) are also rare in the sedimentary realm, and have particular evaporite associations and implications (see Part 2).

Outside of an industrial byproduct of the Solvay Process, most CaCl2 is derived from the processing of hypersaline basinal brines. The only current commercially, exploited natural CaCl2 surficial brine source is in Bristol Dry Lake, California (Figure 1). In the USA, for example, basinal brines are the primary commercial source of calcium chloride. Some of these brines in Michigan, Ohio, West Virginia, Utah, and California contain >4% calcium, with the Michigan Basin as the dominant producer. In the USA, a former commercially important source of calcium chloride was as a by-product of the Solvay Process used to produce soda ash. Because of environmental concerns and high energy costs, the Solvay Process has been discontinued as a source of CaCl2 in the USA.

This article will focus on the utility and geological significance of CaCl2 brines, while the next will focus on the geochemical significance of various calcium chloride minerals in particular evaporitic settings.


Usage

Calcium chloride depresses the freezing point of water, and its principal use is to prevent ice formation, especially on winter roads. Calcium chloride released to the environment is relatively harmless to plants and soil in diluted form. As a de-icing agent, it is more efficient at lower temperatures than sodium chloride. Solutions of calcium chloride can prevent freezing at a temperature as low as -52 °C (Figure 2). Hence, more than 50% of world CaCl2 usage is for road de-icing during winter. The second largest application of calcium chloride brine exploits its hygroscopic properties and the tackiness of its hydrates. In summer, it is used for roadbed stabilisation in unsealed roads and as a dust palliative. When sprayed onto the road surface, a concentrated CaCl2 solution maintains a cushioning layer on the surface of dirt roads and so suppresses formation of road dust. Without brine treatment dust particles blow away, eventually larger aggregate in the road also begins to shift around, and the road surface breaks down. Using calcium chloride reduces the need for grading by as much as 50% and the need for fill-in materials as much as 80%.


Calcium chloride’s low-temperature properties also make it ideal for filling agricultural implement tyres as a liquid ballast, aiding traction in cold climates. It is also used as an accelerator in the ready-mix concrete industry, although there is concern about its usage because of possible long-term chloride-induced corrosion of steel in highways and buildings. Calcium chloride is also widely used to increase mud fluid densities in oil- and gas-well drilling. It is also used in salt/chemical-based dehumidifiers in domestic and other environments to absorb dampness/moisture from the air.

Calcium chloride is used in the food industry to increase firmness of fruits and vegetables, such as tomatoes, cucumbers, and jalapenos, and prevent spoilage during processing. Food-grade calcium chloride is used in cheese-making to aid in rennet coagulation and to replace calcium lost in pasteurisation. It also is used in the brewing industry both to control the mineral salt characteristics of the water and as a basic component of certain beers.


Calcium Chloride brines production

Generally, CaCl2 brines are found in permeable strata either below, adjacent to, or above evaporite deposits, gradually becoming more dilute as brines approach the surface, and modified somewhat in proportion to distance from a potash or salt layer (Figure 1; Table 2). Other natural calcium chloride brines are derived from hydrothermally-modified marine waters. Dilute calcium chloride brines are also occasionally found in coastal aquifers, and some oil or gas formation waters that have been formed from seawater, possibly by a dolomitization reaction supplemented by the leaching of certain types of rocks (Garrett, 2004).

Basinal brines are chemically similar to CaCl2 brines forming hydrothermally at modern mid-ocean ridges, where seawater is being converted by interaction with basalt at elevated temperatures into low-salinity Na-Ca-Cl brines, depleted in Mg and SO4. These CaCl2 waters occur in and near active fracture zones, wherever seawater interacts with labile basalt (oceanic crust) at elevated temperatures and converts the circulating fluid from a Na-Mg-Cl water into a low-salinity Na-Ca-Cl brine, depleted in Mg and SO4. Similar hydrothermally-driven alteration of continental basalts via deeply circulated seawater interactions forms modern CaCl2-rich brine seeps, for example, within the thermally active continental Danakil rift valley (Hardie, 1990; Warren, 2016).

 

Calcium chloride is produced in commercial amounts using a variety of procedures: 1) refining of natural brines, typically with heating to increase concentration, 2) reaction of calcium hydroxide with ammonium chloride in Solvay soda ash production, and 3) reaction of hydrochloric acid with calcium carbonate. The first two processes account for over 90% of the world’s total calcium chloride production. Historically, natural brines sources are the dominant CaCl2 source. There is currently an excess of capacity in the calcium chloride industry, a situation which is only expected to become more acute as synthetic and byproduct capacity increases.

As we shall see in the next article, calcium chloride crystals are relatively rare as primary-textured occurrences in solid salt beds. On the other hand, CaCl2 brines are commonplace in basinal or formation waters in many Phanerozoic sedimentary basins entraining thick sequences of dissolving ancient salt. For example, since 1914, CaCl2 brines have been extracted from Silurian strata adjacent to Salina Salt of the Michigan Basin USA (Figure 1; Ludington; Oxy Chemicals, Formerly Dow Chemicals)). These brines are recovered from Detroit Group sediments that overlie the Silurian Salina evaporites. Based on fluid inclusions in primary halite chevrons in the Salina Salt, the Silurian was a time characterised by a CaCl2-enriched MgSO4-depleted ocean (but no tachyhydrite is known from Silurian strata, here or elsewhere). Industrial production of CaCl2

CaCl2 brines in the Michigan Basin (commercial)

This Silurian halite/potash basin has many aquifers with calcium chloride brines, both above and below the Silurian Salina Group’s halite and potash levels (Figures 3, 4; Garrett, 2004). Major aquifers are the overlying Devonian carbonate and sandstone beds, with many lesser aquifers. In the first porous bed above the potash (Sylvania Sandstone Formation) there is an extensive area of rich calcium chloride brine sitting directly above the potash deposit and extending to the south-southeast. Brine concentrations at nearly the same concentration as potash end liquor in fractures in the intrasalt carbonates. The less voluminous sandstone of the Filer Formation to the northwest contains a similar, but slightly more dilute CaCl2 brine. Several thinner and less abundant aquifers also occur under the potash beds with equally strong, or stronger calcium chloride brines (Figure 3).


The porous 0-90 m thick Sylvania Sandstone lies at the base of the Detroit River Group and is the main source of CaCl brine production. It is in direct erosional contact with the salt succession (Figure 4). The remainder of the Group consists of 0-350 m of variably porous carbonates (Garrett, 1995, 2004). Both sandstones and carbonates contain CaCl2-rich brines and extend across some 40% of the Michigan Basin at depths of from 300-1,400m. Brine concentration and the relative amount of CaCl2 increases with depth. Typically, the brines are only considered to be of economic importance below about 880 m depth. In carbonate hosts, the CaCl2 content varies from 3-23% and KCl from 0.2-2.9%, usually increasing in concert with concentration, as the NaCl content decreases. CaCl2 content in the Sylvania Sandstone varies from 14-22%, KCl from 0.6-2.1%, and both are more uniformly concentrated compared to the carbonate-hosted brines (Garrett, 2004).


Each aquifer entrains roughly the same ratio of ions, but pore waters become progressively more dilute as beds approach the surface about the basin margin. It seems likely that in this basin, a potash liquor originally seeped through and under the potash deposit (and reacted with calcite) was much later forced from its original sediments into the overlying porous strata into the overlying porous strata as they were compressed by deep burial, possibly aided by load-induced pumping induced by the waxing and waning of thick glacial ice that formed over this basin (McIntosh et al., 2011). Variable ionic content, as seen in Table 2, results from their considerably different migration history and variable dilution by meteoric or other groundwater (as is strongly indicated by the brine’s deuterium and 18O analyses), precipitation (such as gypsum), and their different contact with rocks that they could partially leach or react with. However, in the Michigan Basin these reactions were limited, since the porous carbonate strata (average, 20%) contains fairly pure carbonates, and the sandstone strata fairly pure silica (quartz arenites) cemented by dolomite or quartz (Martini, 1997).

There is a general synclinal structure to the strata under the Michigan Basin, and examples of the specific stratigraphy to the southeast of the centre of the basin at Midland are shown in Figure 4. The Detroit River Group consists of 0–350 m of variable porosity carbonates, and at its base there is 0–90 m of porous sandstone called the Sylvania Formation. Each of these formations cover about 40% or more of the Michigan Basin, and contain strong calcium chloride brines at depths of 300–1400 m. Their brines have been commercially recovered in the past, and were generally only considered to be economic below about 880 m. The brines’ total dissolved solids (TDS) and the amount of CaCl2 increases fairly consistently with depth from 3 to 23% CaCl2, and the NaCl and MgCl2 concentrations vary inversely with the CaCl2 . In the Sylvania Formation, the CaCl2 usually ranges from 14 to 22% (Figure 3). Additional information on the brine in other aquifers and the various reactions and changes that have occurred with them are discussed in Martini a(1997), Wilson and Hewett, (1992) and Wilson and Long (1992).

The Michigan Basin brines’ very low pH (4.5 to 5.3) helps to explain an ability to leach and react with other rocks, as is indicated by their high contents of strontium, barium and metals, much of the Sr and Ba probably came from the reaction with calcite. Geothermal water also probably mixed with some of the formations, as indicated by the variable presence of iodine, boron, lithium, caesium, rubidium and other rare metals. With most of the brines, the calcium concentration is somewhat higher than its magnesium equivalent in seawater end-liquor from a potash deposit, and the potassium a little lower. Wilson and Long (1992) speculated that this occurred by the conversion of the clays kaolinite and smectite to illite: Small amounts of glauberite (CaSO4.Na2SO4) and polyhalite (2CaSO4.K2SO4.MgSO4; have also been found in the basin. Finally, some of the calcium chloride aquifers have a slightly elevated ratio of 87Sr/86Sr (range from 0.7080 to 0.7105; seawater is 0.70919), further indicating that there was some rock leaching during burial(Martini, 1997).

What does a CaCl2 basinal brine indicate?

Pore fluids in the deeper parts of many sedimentary basins, especially if they contain a significant unit of evaporite, tend to be CaCl2 brines, entraining large volumes of hypersaline brine and in places, hydrocarbons (e.g., Michigan Basin, the U.S. Gulf Coast, European North Sea Basin, Western Canada Basin and Volga Basin).

Worldwide, one of the principal geochemical characteristics of saline waters in sedimentary basins is the progressive shift in their major ion composition from Na–Cl to Na–Ca–Cl to Ca–Na–Cl dominated waters with increasing chlorinity or salinity (Hanor and McIntosh, 2006). Such basinal brines (also called oil-field brines or formation waters) with significant calcium chloride contents have salinities that typically range up to 300,000 mg/l (Hanor, 1994; Lowenstein et al., 2003). The majority of these basinal brines are chemically distinct in their high Ca concentrations, separating their hydrogeochemistries from modern seawater and other common surface and near-surface waters which tend to be Na-Cl-SO4, Ca-HCO3, or Na-CO3 types (Drever, 1997).

Calcium levels in a CaCl2 basinal brine typically exceed the combined concentrations of SO4, HCO3, CO3 ions, (specifically, mCa > ∑(mSO4 + 1/2mHCO3 + mCO3); Lowenstein et al., 2004). And yet, the evaporative concentration of modern seawater leads to brines depleted in Ca, as required by the principle of chemical divides (CaCO3 and CaSO4 divides) for any evaporating water (Hardie and Eugster, 1970). Explanations for the origin of CaCl2 basinal brines remain problematic.

There is no simple pathway by which modern seawater, and most other surface and near-surface waters trapped in sedimentary deposits, can be converted to CaCl2 basinal brines during burial, without invoking significant rock-fluid interaction. Historically, before micro-inclusion studies of chevron halite showed that the ionic proportions of seawater likely varied across the Phanerozoic, the various CaCl2 basinal brines occurrences, for example in in Silurian and Cretaceous age strata were explained as an indicator of widespread dolomitisation and other diagenetic reactions, which preferentially extracted magnesium from pore waters (Garrett, 2004).

Since the mid-1990s, others have argued that CaCl2 enrichments in many ancient basinal brines with thick evaporites in the stratigraphy, including brines in the Detroit Group, are partial leftovers from times of CaCl2-enriched seawater chemistries (Table 3; Lowenstein and Timofeeff, 2008; Lowenstein et al., 2014). That is, Ca-enriched (MgSO4-depleted) pore brines adjacent to thick evaporites are indicators of ancient CaCl2 oceans, with the pore brines being remnants from the time the enclosing evaporitic and marine sediments were deposited (relict or connate brines).


Other authors, such as Houston et al. (2011), conclude this is not necessarily so; they agree that there are two end-members typifying highly saline subsurface brines (MgSO4 depleted or enriched). But, they conclude that end member chemistries relate to either substantial subsurface halite dissolution, or to preservation of early reflux-related seawater. Houston et al. (2011) go on to argue that CaCl2-enriched formation water chemistries from many basins worldwide, including the Michigan Basin, do not support an interpretation of variation in ionic proportions in seawater across the Phanerozoic. They find that CaCl2-rich brines formed either by dissolving bittern salts in the subsurface, or simply lost water in the subsurface after significant rock-fluid interaction had taken place. Water loss might be achieved by interaction with a gas phase at the elevated temperatures of deep burial or, alternatively, water may have been lost to clays. Both these mechanisms would have the effect of dehydrating (concentrating) the brine.

Calling upon a CaCl2 seawater source as an explanation for the origin of basinal brines was criticized also by Hanor & McIntosh (2006) who pointed out that no matter what the starting composition of a paleoseawater, significant diagenetic alteration must have occurred to produce the present major ion chemistry of Illinois and Michigan basin brines specifically, and basinal brines in general. In their view, the diagenetic mineral–brine interactions that occur during burial mask any original compositional variations in the starting seawater.

Hanor & McIntosh (2006) also argued that due to ongoing fluid escape and crossflow, it is difficult, if not impossible, to assign specific ages to basinal brines in a sedimentary basin. If the age of a basinal brine is not known, then the possible parent seawater, whether CaCl2 or MgSO4 type, cannot be determined. Hanor and McIntosh (2007) illustrated further complications in the interpretation of the timing of the origin of basinal brines. They showed that some brines in the Gulf of Mexico basin were not formed during the Middle Jurassic, contemporaneous with deposition of the Louann Salt, but formed during the Cenozoic from the dissolution of the Louann salt.

Interestingly, many marine potash deposit end-liquor brines have a high to medium–high lithium content, such as the Angara-Lena basin, Russia’s 1600–1900 ppm, the Paradox Basin’s 66–173 ppm Li, the Michigan Basin’s Sylvania Formation’s 36–72 ppm and the English Zechstein Formation’s 7– 65 ppm, etc. (Garrett, 2004)). However, some end-liquors have only a nominal lithium contents, such as from the Saskatchewan, Canada potash deposits. A few calcium chloride lakes also have medium–high values, such as the Don Juan Pond’s 235 ppm, Bristol Lake’s 30–108 ppm, Cadiz Lake’s 20–67 ppm, and Lake Vanda’s 27 ppm (Figure 1). We shall come back to this topic in a future article that will focus on lithium-rich brines.

Origin of CaCl2 brines

So, currently, there are two schools of thought used to explain the origin of CaCl2 basinal brines in evaporitic basins. One school assumes that the chemistry of the world’s ocean and its ionic proportions have remained near constant across the Phanerozoic. To form a CaCl2 enriched basinal brine then requires substantial subsurface rock-fluid interactions, utilising mechanisms and processes that include nonmarine parent waters, diagenetic alteration, pervasive dolomitization of carbonates, or bacterial sulphate reduction. All these mechanisms can reduce the proportion of Mg, HCO3 and SO4 relative to Ca in subsurface pore waters (Hanor and McIntosh, 2006). Proponents of this school tend to base their argument on basin-scale variations in the hydrogeochemistry of pore fluids.

The other school (mostly based on the micro-inclusion chemistry of chevron halite) argues for long-term changes in the major ion chemistry of seawater (Table 2). For example, Upper Jurassic, Cretaceous, and Cenozoic seawater records a systematic, long-term (>150 My) shift from the Ca2+ - rich, Mg2+ - and SO42- - poor seawater of the Mesozoic (“CaCl2 seas”) to the “MgSO4 seas” (with higher Mg2+ and SO42- > Ca2+) of the Cenozoic (Lowenstein and Timofeeff, 2008; Lowenstein et al., 2003, 2014). Over that period, the Mg/Ca ratio of seawater rose from 1 in the Early Cretaceous, to 2.3 in the Eocene, and 5.2 in present-day seawater.

Suggested drivers of long-term variation in the major ion chemistry of seawater include; fluctuations in the volume of discharge of hydrothermal waters from the global mid-ocean ridge system (Hardie, 1996), changes in the rates of volcanic activity and weathering processes, and variations in the amount of dolomite formed in the oceans (Holland and Zimmermann, 2000).

In my mind, much of the conflict between to two schools of thought as to the origin of CaCl2 basinal brines stems from the source of evidence. One approach utilises micro-inclusion chemistry in halite chevrons to define the evolution of Phanerozoic seawater. This data is extracted from an intra-salt textural association that, due to its long lack of permeability (‘locked up in halite’), likely preserves the chemical composition of the original depositional setting (e.g. Zambito et al.). The other school focuses on pore fluid hydrochemistry in subsurface waters, generally using water samples in boreholes, collected from pores and fractures in a carbonate, sandstone or shale host. The nature of fluids in these non-salt sediments, some which have been permeable since deposition, mean fluids experienced ongoing re-supply via crossflow and rock-fluid interaction as the ambient temperature, pressure and salinities evolved in the burial environment. This process shutdown once matrix permeability was lost (Warren et al., 2014).

In the next article, we shall expand our discussion of the significance of CaCl2 brines with a close look at where and how particular calcium chloride minerals can precipitate and be preserved and why some types of calcium chloride salts are more common in particular evaporitic settings.

References

Drever, J. I., 1997, The geochemistry of natural waters: Surface and groundwater environments: New Jersey, Prentice-Hall Inc., p. 327-351.

Garrett, D. E., 1995, Potash: Deposits, processing, properties and uses: Berlin, Springer, 752 p.

Garrett, D. E., 2004, Handbook of Lithium and atural Calcium Chloride; Their deposits, processing, uses and properties Amsterdam, Elsevier Academic Press, 476 p.

Hanor, J. S., 1994, Origin of saline fluids in sedimentary basins: Geological Society, London, Special Publications, v. 78, p. 151-174.

Hanor, J. S., and J. C. McIntosh, 2006, Are secular variations in seawater chemistry reflected in the compositions of basinal brines?: Journal of Geochemical Exploration, v. 89, p. 153-156.

Hardie, L. A., 1990, The roles of rifting and hydrothermal CaCl2 brines in the origin of potash evaporites: a hypothesis: American Journal of Science, v. 290, p. 43-106.

Hardie, L. A., 1996, Secular variation in seawater chemistry: an explanation for the coupled secular variation in the mineralogies of marine limestones and potash evaporites over the past 600 m.y.: Geology, v. 24, p. 279 - 283.

Holland, H. D., and H. Zimmermann, 2000, The Dolomite Problem Revisited: Int. Geol. Rev., v. 42, p. 481-490.

Houston, S., C. Smalley, A. Laycock, and B. W. D. Yardley, 2011, The relative importance of buffering and brine inputs in controlling the abundance of Na and Ca in sedimentary formation waters: Marine and Petroleum Geology, v. 28, p. 1242-1251.

Lowenstein, T., B. Kendall, and A. D. Anbar, 2014, Chapter 8.21. The Geologic History of Seawater, Treatise on Geochemistry (2nd Edition), Elsevier, p. 569-621.

Lowenstein, T. K., L. A. Hardie, M. N. Timofeeff, and R. V. Demicco, 2003, Secular variation in seawater chemistry and the origin of calcium chloride basinal brines: Geology, v. 31, p. 857-860.

Lowenstein, T. K., and M. N. Timofeeff, 2008, Secular variations in seawater chemistry as a control on the chemistry of basinal brines: test of the hypothesis: Geofluids, v. 8, p. 77-92.

Martini, A. M., 1979, Hydrogeochemistry of Saline Fluids and Associated Water and Gas, Michigan Basin: Doctoral thesis, University of Michigan, 236 p.

McIntosh, J. C., G. Garven, and J. S. Hanor, 2011, Impacts of Pleistocene glaciation on large-scale groundwater flow and salinity in the Michigan Basin: Geofluids, v. 11, p. 18-33.

Warren, J., C. Morley, T. Charoentitirat, I. Cartwright, P. Ampaiwan, P. Khositchaisri, M. Mirzaloo, and J. Yingyuen, 2014, Structural and fluid evolution of Saraburi Group sedimentary carbonates, central Thailand: A tectonically driven fluid system: Marine and Petroleum Geology, v. 55, p. 100-121.

Warren, J. K., 2015, Seawater chemistry (1 of 2): Potash bitterns and Phanerozoic marine brine evolution, Salty Matters blog, www.saltworkconsultants.com.

Warren, J. K., 2016, Evaporites: A Compendium (ISBN 978-3-319-13511-3): Berlin, Springer, 1854 p.

Wilson, T. P., and T. A. Hewett, 1992, Geochemistry and isotope chemistry of Michigan Basin brines: Devonian formations: Applied Geochemistry, v. 7, p. 81-100.

 


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