Salty Matters

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Brine evolution and origins of potash - primary or secondary. Ancient potash ores: Part 3 of 3

John Warren - Monday, December 31, 2018

Introduction

In the previous two articles in this series on potash exploitation, we looked at the production of either MOP or SOP from anthropogenic brine pans in modern saline lake settings. Crystals of interest formed in solar evaporation pans and came out of solution as: 1) Rafts at the air-brine interface, 2) Bottom nucleates or, 3) Syndepositional cements precipitated within a few centimetres of the depositional surface. In most cases, periods of more intense precipitation tended to occur during times of brine cooling, either diurnally or seasonally (sylvite, carnallite and halite are prograde salts). All anthropogenic saline pan deposits examples can be considered as primary precipitates with chemistries tied to surface or very nearsurface brine chemistry.

In contrast, this article discusses ancient potash deposits where the chemistries and ore textures are responding to ongoing alteration processes in the diagenetic realm. Unlike the modern brine pans where brines chemistries and harvested mineralogies are controllable, at least in part, these ancient deposits show ore purities and distributions related to ongoing natural-process overprints.



Table 1 lists some modern and ancient potash deposits and prospects by dividing them into Neogene and Pre-Neogene deposits (listing is extracted and compiled from SaltWork® database Version 1.7). The Neogene deposits are associated with a time of MgSO4-enriched seawaters while a majority of the Pre-Neogene deposits straddle times of MgSO4 enrichment and depletion in the ocean waters.

Incongruent dissolution in burial

Many primary evaporite salts dissolve congruently in the diagenetic realm; i.e., the composition of the solid and the dissolved solute stoichiometrically match, and the dissolving salt goes entirely into solution (Figure 1a). This situation describes the typical subsurface dissolution of anhydrous evaporite salts such as halite or sylvite. However, some evaporite salts, typically hydrated salts, such as gypsum or carnallite, dissolve incongruently in the diagenetic realm, whereby the composition of the solute in solution does not match that of the solid (Figure 1b). This solubilisation or mineralogical alteration is defined by the transformation of the "primary solid" into a secondary solid phase, typically an anhydrous salt, and the loss of water formerly held in the lattice structure. The resulting solution generally carries ions away in solution.


More than a century ago, van't Hoff (1912) suggested that much subsurface sylvite is the result of incongruent solution of carnallite yielding sylvite and a Mg-rich solution. According to Braitsch (1971, p. 120), the incongruent alteration (dissolution) of carnallite is perhaps the most crucial process in the alteration of subsurface potash salts and the formation of diagenetic (secondary) sylvite.

Widespread burial-driven incongruent evaporite reactions in the diagenetic realm include the burial transition of gypsum to anhydrite (reaction 1)

CaSO4.2H2O --> CaSO4 + 2 H2O ... (1)

and the in-situ conversion of carnallite to sylvite via the loss of magnesium chloride in solution (reaction 2)

KMgCl3.6H2O --> KCl + Mg++ + 2Cl- + 6H2O ...(2)

Typically, a new solid mineral remains, and the related complex solubility equilibrium creates a saline pore water that may, in turn, drive further alteration or dissolution as it leaves the reaction site (Warren, Chapters 2 and 8). Specifically for ancient potash, reaction 2 generates magnesium and chloride in solution and has been used to explain why diagenetic bischofite and dolomite can be found in proximity to newly formed subsurface sylvite. Bischofite is a highly soluble salt and so is metastable in many subsurface settings where incongruent dissolution is deemed to have occurred, including bischofite thermal pool deposits in the Dallol sump in the Danakhil of Ethiopia (Salty Matters, May 1, 2015). In many hydrologically active systems, solid-state bischofite is flushed by ongoing brine crossflow and so help drive the formation of various burial dolomites. Only at high concentrations of MgCl2 can carnallite dissolve without decomposition.

Laboratory determinations

In the lab, the decomposition of carnallite in an undersaturated aqueous solution is a well-documented example of incongruent dissolution (Emons and Voigt, 1981; Xia et al., 1993; Hong et al., 1994; Liu et al., 2007; Cheng et al., 2015, 2016). When undersaturated water comes into contact with carnallite, the rhombic carnallite crystals dissolve and, because of the common ion effect, small cubic KCl crystals form in the vicinity of the dissolving carnallite. As time passes, the KCl crystals grow into larger sparry subhedral forms and the carnallite disappears.

Carnallite’s crystal structure is built of Mg(H2O)6 octahedra, with the K+ ions are situated in the holes of chloride ion packing meshworks, with a structural configuration similar to perovskite lattice types (Voigt, 2015). Potassium in the carnallite lattice can be substituted by other large single-valence ions like NH4+, Rb+, Cs+ or Li(H2O)+, (H3O)+ and Cl- by Br- and I-. These substitutions change the lattice symmetry from orthorhombic in the original carnallite to monoclinic.

When interpreting the genesis of ancient potash deposits and solutions, the elemental segregation in the lattice means trace element contents of bromide, rubidium and caesium in primary carnallite versus sylvite daughter crystals from incongruent dissolution can provide valuable information. For example, in a study by Wardlaw, (1968), a trace element model was developed for sylvite derived from carnallite that gave for Br and Rb concentration ranges of 0.10–0.90 mg/g and 0.01–0.18 mg/g, respectively. In a later study of sylvite derived by fresh-water leaching of magnesium chloride under isothermal conditions at 25 °C. Cheng et al. (2016), defined a model whereby primary sylvites precipitated from MgSO4-deficient sea water, gave Br and Rb concentration ranges of 2.89–3.54 mg/g and 0.017–0.02 mg/g, respectively (no evaporation occurred at saturation with KCl). In general, they concluded sylvite derived incongruently from carnallite would contain less Br and more Rb than primary sylvite (Figure 2; Cheng et al., 2016).


Subsurface examples

The burial-driven mechanism widely cited to explain the incongruent formation of sylvite from carnallite is illustrated in Figure 3 (Koehler et al., 1990). Carnallite precipitating from evaporating seawater at time 1 forms from a solution at 30°C and atmospheric (1 bar) pressure, and so plots as point A, which lies within the carnallite stability field (that is, it sits above the dashed light brown line). With subsequent burial, the pressure increases so that the line defining carnallite-sylvite boundary (solid dark brown line) moves to higher values of K. By time 2, when the pressure is at 1 Kbar (corresponds to a lithostatic load equivalent to 2-3 km depth), the buried carnallite is thermodynamically unstable and so is converting to sylvite + solution (as the plot field now lies in the sylvite + solution field (Figure 3). If equilibrium is maintained the carnallite reacts incongruently to form further sylvite and MgCl2-solution. Thus, provided the temperature does not rise substantially, increasing pressure as a result of burial will favour the breakdown of carnallite to sylvite. However, as burial proceeds, the temperature may become high enough to favour once again the formation of carnallite from sylvite + solution (that is the solution plot point from A moves toward the right-hand side of the figure and back into the carnallite stability field).


Sylvite, interpreted to have formed from incongruent dissolution of primary carnallite, is reported from the Late Permian Zechstein Formation of Germany (Borchert and Muir, 1964), Late Permian Salado Formation of New Mexico (Adams, 1970), Early Mississippian Windsor Group of Nova Scotia (Evans, 1970), Early Cretaceous Muribeca Formation of Brazil and its equivalents in the Gabon Basin, West Africa (Wardlaw, 1972a, b; Wardlaw and Nicholls, 1972; Szatmari et al., 1979; de Ruiter, 1979), Late Cretaceous of the Maha Sarakham Formation, Khorat Plateau, Thailand and Laos (Hite and Japakasetr, 1979), Pleistocene Houston Formation, Danakil Depression, Ethiopia (Holwerda and Hutchinson, 1968), and Middle Devonian Prairie Formation of western Canada (Schwerdtner, 1964; Wardlaw, 1968) (See Table 1).

This well-documented literature base supports a long-held notion that there is a problem with sylvite as a primary (first precipitate) marine bittern salt, especially if the mother seawater had ionic proportions similar to those present in modern seawater (see Lowenstein and Spencer, 1990 for an excellent, if 30-year-old, review). We know from numerous evaporation experiments, that sylvite does not crystallise during the evaporation of modern seawater at 25°C, except under metastable equilibrium conditions (Braitsch, 1971; Valyashko, 1972; Hardie, 1984). The sequence of bitterns crystallising from modern seawater bitterns was illustrated in the previous Salty Matters article in this series (see Figure 1 in October 31 2018).

Across the literature documenting sylvite-carnallite associations in ancient evaporites, the dilemma of primary versus secondary sylvite is generally solved in one of three ways. Historically, many workers interpreted widespread sylvite as a diagenetic mineral formed by the incongruent dissolution of carnallite (Explanation 1). Then there is the interpretation that some sylvite beds, perhaps associated with tachyhydrite, were precipitated in the evaporite bittern part of a basin hydrology that was fed by CaCl2-rich basinal hydrothermal waters (Explanation 2: see Hardie, 1990 for a good discussion    of this mechanism). Then there is the third, and increasingly popular explanation of primary or syndepositional sylvite at particular times in the chemical evolution of the world oceans (MgSO4-depleted oceans).


Changes in the relative proportions of magnesium, sulphur and calcium in the world’s oceans are well supported by brine inclusion chemistry of co-associated chevron halite (Figure 4). Clearly, there are vast swathes of times in the earth’s past when the chemistry of seawater changed so that MgSO4 levels were lower than today and it was possible that sylvite was a primary marine bittern precipitate (see Lowenstein et al., 2014 for an excellent summary).

In my opinion, there is good evidence that all three explanations are valid within their relevant geological contexts but, if used exclusively to explain the presence of ancient sylvite, the argument becomes somewhat dogmatic. I would say that that, owing to its high solubility, the various textures and mineralogical associations of carnallite/sylvite and sulphate bitterns found in ancient potash ore beds reflect various and evolving origins. Ambient textures and mineralogies are dependent on how many times and how pervasively in a potash sequence’s geological burial history an evolving and reactive pore brine chemistry came into contact with parts or all of the extent of highly reactive potash beds (Warren, 2000; 2010; 2016).

In my experience, very few ancient examples of economic potash show layered textures indicating primary precipitation on a brine lake floor, instead, most ancient sylvite ores show evidence of at least one episode of alteration. That is, various forms and textures in potash may dissolve, recrystallise and backreact with each other from the time a potash salt is first precipitated until it is extracted. The observed textural and mineralogical evolution of a potash ore association depends on how open was the hydrology of the potash system at various stages during its burial evolution. The alteration can occur syndepositionally, in brine reflux, or later during flushing by compactional or thermobaric subsurface waters or during re-equilibration tied to uplift and telogenesis. Tectonism (extensional and compactional) during the various stages of a basin’s burial evolution acts as a bellows driving fluid flow within a basin, so forcing and speeding up the focused circulation of potash-altering waters.

 

A similar, but somewhat less intense, textural evolution tied to incongruent alteration is seen in the burial history of other variably hydrated evaporite salts. For example, CaSO4 can flip-flop from gypsum to anhydrite and back again depending on temperature, pore fluid salinity and the state of uplift/burial. Likewise, with the more complicated double salt polyhalite, there are mineralogical changes related to whether it formed in a MgSO4 enriched or depleted world ocean and the associated chemistry of the syndepositional reflux brines across extensive evaporite platforms (for a more detailed discussion of polyhalite see Salty Matters, July 31, 2018). Kainite-kieserite-carnallite also show evidence of ongoing incongruent interactions. This means that, as in gypsum/anhydrite/polyhalite or kain ite/kieserite sequences, there will be primary and secondary forms of both carnallite and sylvite that can alternate during deposition, during burial and any deep meteoric flushing and then again with uplift. In Quaternary brine factories these same incongruent chemical relationships are what facilitate the production of MOP (sylvite) from a carnallitite feed or SOP from kainite/kieserite/schoenite feed (see articles 1 and 2 in this series).

 

To document the three end-members of ancient sylvite-carnallite decomposition/precipitation we will look at three examples; 1) Oligocene potash in the Mulhouse Basin where primary sylvite textures are commonplace, 2) Devonian potash ores in western Canada, where multiple secondary stages of alteration are seen, and 3) Igneous-dyke associated sylvite in east Germany where thermally-driven volatisation (incongruent melting) forms sylvite from dehydrated carnallite.


Oligocene Potash, Mulhouse Basin France

Moving backwards into deep time, this 34 Ma deposit contains some of the first indications of well preserved primary marine-fed sylvinite (MOP) textures exemplified by laterally-continuous mm-scale alternations of potash and halite layers and lamina (Figure 5a-c). Interestingly, all solid-state potash deposits laid down in the post-Oligocene period contain increased proportions of MgSO4 salts, making them much more difficult to economically mine and process (see Table 1 and Salty Matters, May 12, 2015)

From 1904 until 2002, potash was conventionally mined in France from the Mulhouse Basin (near Alsace, France). With an area of 400 km2, the Mulhouse Basin is the southernmost of a number of Lower Oligocene evaporite basins that occupied the upper Rhine Graben, which at that time was a narrow adiabatic-arid rift valley (Figure 6a). The graben was a consequence of the collision between European and African plates during the Paleogene. It is part of a larger intracontinental rift system across Western Europe that extended from the North Sea to the Mediterranean Sea, stretching some 300 km from Frankfurt (Germany) in the north, to Basel (Switzerland) in the south, with an average width of 35 km (Cendon et al., 2008). The southern extent of the graben is limited by a system of faults that place Hercynian massifs and Triassic materials into contact with the Paleogene filling. Across the north, a complex system of structures (including salt diapirs) put the basin edges in contact with Triassic, Jurassic and Permian materials. In the region of the evaporite basins, the Paleogene fill of the graben lies directly on the Jurassic basement. The sedimentary filling of this rift sequence is asymmetrical with the deeper parts located at the southwestern and northeastern sides of the Graben (Rouchy, 1997).


Palaeogeographical reconstructions place the potential marine seaway seepage feed to the north or perhaps also southeast of the Mulhouse Basin, while marginal continental conglomerates tend to preclude any contemporaneous hydrographic connection with Oligocene ocean water (Blanc-Valleron, 1991; Hinsken et al., 2007; Cendon et al., 2008). At the time of its hydrographic isolation, some 34 Ma, the basin was located 40° north of the equator. Total fill of Oligocene lacustrine/marine-fed sediments in the graben is some 1,700m thick. The saline stage is dominated by anhydrite, halite and mudstone. The main saline sequence is underlain by non-evaporitic Eocene continental mudstones, with lacustrine fossils and local anhydrite beds. Evaporite bed continuity in the northern part of the basin is disturbed by (Permian-salt cored) diapiric and or erosional/fault movement. Consequently, these northern basins are not considered suitable for conventional potash mining (Figure 6a).

The Paleogene fill of the basin is divided into 6 units; a pre-evaporitic series, Lower Salt Group (LSG), Middle Salt Group (MSG), an Upper Salt Group (USG - with potash), Grey Marls Fm., and the Niederroedern Fm (Figure 7; Cendon et al., 2008). The LSG and lower section of the MSG are interpreted as lacustrine in origin, based on the limited palaeontologic and geochemical data. However, based on the presence of Cenozoic marine nannoplankton, shallow water benthic foraminifera, and well-diversified dinocyst assemblages in the fossiliferous zone below Salt IV, Blanc-Valleron (1991) favours a marine influence near the top of the MSG, while recognising the ambiguity of marine proportions with brackish faunas. Many marine-seepage fed brine systems have salinities that allow halotolerant species to flourish in marine-fed basins with no ongoing marine hydrographic connection (Warren, 2011). According to Blanc-Valleron and Schuler (1997), the region experienced a Mediterranean climate with long dry seasons during Salt IV member deposition.


In detail, the Salt IV member is made up of some 210 m of evaporitic sequence, with two relatively thin potash levels (Ci and Cs). The stratigraphy associated with this potash zone is, from base to top (Figure 7):

S2 Unit: 11.5 m thick with distinct layers of organic-rich marls, often dolomitic, with dispersed anhydrite layers.

S1 Unit: 19 m thick, evenly-bedded and made up of alternating metre-scale milky (inclusion-rich) halite layers, with much thinner marls and anhydrite layers. Marls show a sub-millimetric lamination formed by micritic carbonate laminae alternating with clay, quartz, and organic matter-rich laminae. Hofmann et al. (1993a, b) interpreted these couplets as reflecting seasonal variations. Anhydrite occasionally displays remnant swallowtail ghost textures, which suggest that at least part of the anhydrite first precipitated as subaqueous gypsum. Halite shows an abundance of growth-aligned primary chevron textures, along with fluid-inclusion banding suggesting halite was subaqueous and deposited beneath shallow brine sheets (Lowenstein and Spencer, 1990).

S Unit: Is 3.7 m thick and consists of thin marl layers and anhydrite, similar to the S2 Unit, with a few thin millimetric layers of halite.

Mi Unit: With a thickness of 6 m, it is mostly halite with similar characteristics to the S1 Unit. Sylvite was detected in one sample, but its presence is probably related to the evolution of interstitial brines (Cendon et al., 2008).

Ci Unit (“Couche inférieure”): Is formed by 4 m of alternating marls/anhydrite, halite, and sylvite beds (Figure 7).

The Ti unit consists of alternating beds of halite, marl and anhydrite. The top of the interval is the T unit, which is similar to the S unit and consists of alternating beds of marl and anhydrite. Above this is the Ms or upper Marl, near identical to the lower marl Mi. The Mi is overlain by the upper potash bed (Cs), a thinner, but texturally equivalent, bed compared to the sylvinitic Ci unit.

Thus, the Oligocene halite section includes two thin, but mined, potash zones: the Couche inferieure (Ci; 3.9m thick), and Couche superieure (Cs; 1.6m thick), both occur within Salt IV of the Upper Salt group (Figures 5, 7).

Both potash beds are made up of stacked, thin, parallel-sided cm-dm-thick beds (averaging 8 cm thickness), which are in turn constructed of couplets composed of grey-coloured halite overlain by red-coloured sylvite (Figure 5b). Each couplet has a sharp base that separates the basal halite from the sylvite cap of the underlying bed. In some cases, the separation is also marked by bituminous partings. The bottom-most halite in each dm-thick bed consists of halite aggregates with cumulate textures that pass upward into large, but delicate, primary chevrons and cornets. Clusters of this chevron halite swell upward to create a cm-scale hummocky boundary with the overlying sylvite (Figure 5c; Lowenstein and Spencer, 1990).

The sylvite member of a sylvinite couplet consists of granular aggregates of small transparent halite cubes and rounded grains of red sylvite (with some euhedral sylvite hoppers) infilling the swales in the underlying hummocky halite (Figure 5b,c). The sylvite layer is usually thick enough to bury the highest protuberances of the halite, so that the top of each sylvite layer, and the top of the couplet, is flat. Dissolution pipes and intercrystalline cavities are noticeably absent, although some chevrons show rounded coigns. Intercalated marker beds, formed during times of brine pool freshening, are composed of a finely laminated bituminous shale, with dolomite and anhydrite.

The sylvite-halite couplets record combinations of unaltered settle-out and bottom-nucleated growth features, indicating primary chemical sediment accumulating in shallow perennial brine pools (Lowenstein and Spencer, 1990). Based on the crystal size, the close association of halites with sylvite layers, their lateral continuity and the manner in which sylvite mantles overlie chevron halites, the sylvites are interpreted as primary precipitates. Sylvite first formed at the air-brine surface or within the uppermost brine mass and then sank to the bottom to form well-sorted accumulations. As sylvite is a prograde salt it, like halite, probably grew during times of cooling of the brine mass (Figure 8a). These times of cooling could have been diurnal (day/night) or weather-front induced changes in the above-brine air temperatures. Similar cumulate sylvite deposits form as ephemeral bottom accumulations on the floor of modern Lake Dabuxum in China during its more saline phases.


The subsequent mosaic textural overprint seen in many of the Mulhouse sylvite layers was probably produced by postdepositional modification of the crystal boundaries, much in the same way as mosaic halite is formed by recrystallisation of raft and cumulate halite during shallow burial. Temperature-based inclusion studies in both the sylvite and the halites average 63°C, suggesting solar heating of surface brines as precipitation took place (Figure 8b; Lowenstein and Spencer, 1990). Similar high at-surface brine temperatures are not unusual in many modern brine pools, especially those subject to periodic density stratification and heliothermometry (Warren 2016; Chapter 2).

Mineralogically, potash evaporites in the Mulhouse Basin in the Rhine Graben (also known as the Alsatian (Alsace) or Wittelsheim Potash district) contain sylvite with subordinate carnallite, but lack the abundant MgSO4 salts characteristic of the evaporation of modern seawater. The Rhine graben formed during the Oligocene, via crustal extension, related to mantle upwelling. It was, and is, a continental graben typified by high geothermal gradients along its rift axis. In depositional setting, it is not dissimilar to pree-120,000-year potash fill stage in the Quaternary Danakil Basin or the Dead Sea during deposition of potash salts in the Pliocene Sedom Fm. The role of a high-temperature geothermal inflow in defining the CaCl2 nature of the potash-precipitating brines, versus a derivation from a MgSO4-depleted marine feed, is considered significant in the Rhine Graben deposits, but is poorly understood and still not resolved (Hardie, 1990; Cendón et al., 2008). World ocean chemistry in the Oligocene is on a shoulder between the MgSO4-depleted CaCl2-rich oceans of the Cretaceous and the MgSO4-enriched oceans of the Neogene (Figure 4).


Cendón et al. (2008) conclude brine reaction processes were the most important factors controlling the major-ion (Mg, Ca, Na, K, SO4, and Cl) evolution of Mulhouse brines (Figure 9a-d). A combined analysis of fluid inclusions in primary textures by Cryo-SEM-EDS with sulphate- d34S, d18O and 87Sr/86Sr isotope ratios revealed likely hydrothermal inputs and recycling of Permian evaporites, particularly during the more advanced stages of evaporation that laid down the Salt IV member. Bromine levels imply an increasingly concentrated brine at that time (Figure 9a). The lower part of the Salt IV (S2 and S1) likely evolved from an initial marine input (Figure 9b-d).

Throughout, the basin was disconnected from direct marine hydrographic connection and was one of a series of sub-basins formed in an active rift setting, where tectonic variations influenced sub-basin interconnections and chemical signatures of input waters. Sulphate-d34S shows Oligocene marine-like signatures at the base of the Salt IV member (Figure 9c, d). However, enriched sulphate-d18O reveals the importance of synchronous re-oxidation processes.

As evaporation progressed, other non-marine or marine-modified inputs from neighbouring basins became more important. This is demonstrated by increases in K concentrations in brine inclusions and Br in halite, sulphate isotopes trends, and 87Sr/86Sr ratios (Figure 9b, c). The recycling (dissolution) of previously precipitated evaporites of Permian age was increasingly important with ongoing evaporation. In combination, this chemistry supports the notion of a connection of the Mulhouse Basin with basins situated north of Mulhouse. The brine evolution eventually reached sylvite precipitation. Hence, the chemical signature of the resulting brines is not 100% compatible with global seawater chemistry changes. Instead, the potash phase is tied to a hybrid inflow, with significant but decreasing marine input.

There was likely an initial marine source, but this occurred within a series of rift-valley basin depressions for which there was no direct hydrographic connection to the open ocean, even at the time the Middle Salt Member (potash-entraining) was first deposited (Cendon et al., 2008). That is, the general hydrological evolution of the primary textured evaporites in the Mulhouse basin sump is better explained as a restricted sub-basin with an initial marine-seepage stage. This gradually changed to ≈ 40% marine source near the beginning of evaporite precipitation, with the rest of hydrological inputs being non-marine. There was a significant contribution of solutes from recycled, in part diapiric, Permian evaporites, likely remobilised by the tectonics driving the formation of the rift valley (Hinsken et al., 2007; Cendon et al., 2008). The general proportion of solutes did not change substantially over the time of evaporite precipitation. However, as the basin restriction increased, the formerly marine inputs changed to continental, diapiric or marine-modified inputs, perhaps fed from neighbouring basins north of Mulhouse basin. As in the Ethiopian Danakhil potash-rift, it is likely brine interactions occurred both during initial and early post-depositional reflux overprinting of the original potash salt beds.


West Canadian potash (Devonian)

The Middle Devonian (Givetian) Prairie Evaporite Formation is a widespread potash-entraining halite sequence deposited in the Elk Point Basin, an early intracratonic phase of the Western Canada Sedimentary Basin (WCSB; Chipley and Kyser, 1989). Today, it is the world’s predominant source of MOP fertiliser (Warren, 2016). The flexure that formed the basin and its subsealevel accommodation space was a distal downwarp to, and driven by, the early stages of the Antler Orogeny (Root, 2001). Texturally and geochemically the potash layers in the basin show the effects of multiple alterations and replacements of its potash minerals, especially interactions between sylvite and carnallite in a variably recrystallised halite host.

Regionally halite constitutes a large portion of the four formations that make up the Devonian Elk Point Group (Figure 10): 1) the Lotsberg (Lower and Upper Lotsberg Salt), 2) the Cold Lake (Cold Lake Salt), 3) the Prairie Evaporite (Whitkow and Leofnard Salt), and 4) the Dawson Bay (Hubbard Evaporite). Today the remnants of the Middle Devonian Prairie Evaporite Formation constitute a bedded unit some 220 metres thick, which lies atop the irregular topography of the platform carbonates of the Winnipegosis Fm. Extensive solutioning of the various salts has given rise to an irregular thickness to the formation and the local absence of salt (Figure 11a).


The Elk Point Group was deposited within what is termed the Middle Devonian “Elk Point Seaway,” a broad intracratonic sag basin extending from North Dakota and northeastern Montana at its southern extent north through southwestern Manitoba, southern and central Saskatchewan, and eastern to northern Alberta (Figure 11a). Its Pacific coast was near the present Alberta-British Columbia border, and the basin was centred at approximately 10°S latitude. To the north and west the basin was bound by a series of tectonic ridges and arches; but, due to subsequent erosion, the true eastern extent is unknown (Mossop and Shetsen, 1994). In northern Alberta, the Prairie Evaporite is correlated with the Muskeg and Presqu’ile formations (Rogers and Pratt, 2017).

Hydrographic isolation of the intracratonic basin from its marine connection resulted in the deposition of a drawndown sequence of basinwide (platform-dominant) evaporites with what is a uniquely high volume of preserved potash salts deposited within a clayey halite host. The potash resource in this basin far exceeds that of any other known potash basin in the world.


Potash geology

Potash deposits mined in Saskatchewan are all found within the upper 60-70 m of the Prairie Evaporite Formation, at depths of more than 400 to 2750 metres beneath the surface of the Saskatchewan Plains. Within the Prairie Evaporite, there are four main potash-bearing members, in ascending stratigraphic order they are: Esterhazy, White Bear, Belle Plaine and Patience Lake members (Figure 11b). Each member is composed of various combinations of halite, sylvite, sylvinite, and carnallitite, with occurrences of sylvite versus carnallite reliably definable using wireline signatures (once the wireline is calibrated to core or mine control - Figure 12; Fuzesy, 1982).

The Patience Lake Member is the uppermost Prairie Evaporite member and is separated from the Belle Plaine by 3-12 m of barren halite (Holter, 1972). Its thickness ranges from 0-21 m and averages 12 m, its top 7-14 m is made up halite with clay bands and stratiform sylvite. This is the targeted ore unit in conventional mines in the Saskatoon and Lanigan areas and is the solution-mined target, along with the underlying Belle Plaine Member, at the Mosaic Belle Plaine potash facility. The Belle Plaine member is separated from the Esterhazy by the White Bear Marker beds made up of some 15 m of low-grade halite, clay seams and sylvinite. The Belle Plaine Member is more carnallite-prone than the Patience Lake member (Figure 12). It is the ore unit in the conventional mines at Rocanville and Esterhazy (Figure 11b) where its thickness ranges from 0-18 m and averages around 9 m. In total, the Prairie Evaporite Formation does not contain any significant MgSO4 minerals (kieserite, polyhalite etc.) although some members do contain abundant carnallite. This mineralogy indicates precipitation from a Devonian seawater/brine chemistry somewhat different from today’s, with inherently lower relative proportions of sulphate and lower Mg/Ca ratios (Figure 4).

The Prairie Evaporite Fm. is nonhalokinetic throughout the basin, it is more than 200 m thick in the potash mining district in Saskatoon and 140 m thick in the Rocanville area to the southeast (Figure 11a; Yang et al., 2009). The Patience Lake member is the main target for conventional mining near Saskatoon. The Esterhazy potash member rises close to the surface in the southeastern part of Saskatchewan near Rocanville and on into Manitoba. This is a region where the Patience Lake Member is thinner or completely dissolved (Figure 11b). Over the area of mineable interest in the Patience Lake Member, centred on Saskatoon, the ore bed currently slopes downward only slightly in a westerly direction, but deepens more strongly to the south at a rate of 3-9 m/km. Mines near Saskatoon are at depths approaching a kilometre and so are nearing the limits of currently economic shaft mining.

The main shaft for the Colonsay Mine, which took IMC Global Inc. more than five years to complete through a water-saturated sediment column, finally reached the target ore body at a depth of 960 metres. Such depths and a southerly dip to the ore means that the conventional shaft mines near Saskatoon define a narrow WNW-ESE band of conventional mining activity (Figure 11c). To the south potash is recovered from greater depths by solution mining; for example, the Belle Plaine operation leaches potash from the Belle Plaine member at a depth of 1800m.

The Prairie Evaporite typically thins southwards in the basin; although local thickening occurs where carnallite, not sylvite, is the dominant potash mineral (Worsley and Fuzesy, 1979). The Patience Lake member is mined at the Cory, Allan and Lanigan mines, and the Esterhazy Member is mined in the Rocanville area (Figure 11c). Ore mined from the 2.4 m thick Esterhazy Member in eastern Saskatchewan contain minimal amounts of insolubles (≈1%), but considerable quantities of carnallite (typically 1%, but up to 10%) and this reduces the average KCl grade value to an average of 25% K2O. The converse is true for ore mined from the Patience Lake potash member in western Saskatchewan near Saskatoon, where carnallite is uncommon in the Cory and Allan mines. The mined ore thickness is a 2.74-3.35 metre cut off near the top of the 3.66-4.57metre Prairie Lake potash member. Ore grade is 20-26% K2O and inversely related to thickness (Figure 12). The insoluble content is 4-7%, mostly clay and markedly higher than in the Rocanville mines.


A typical sylvinite ore zone in the Patience Lake member can be divided into four to six units, based on potash rock-types and clay seams (Figures 12, 13a; M1-M6 of Boys, 1990). Units are mappable and have been correlated throughout the PCS Cory Mine with varying degrees of success, dependent on partial or complete loss of section from dissolution. Potash deposition appears to have been early and related to short-term brine seaway cooling and syndepositional brine reflux. So the potash layering (M1-M6) is cyclic, expressed in the repetitive distribution of hematite and other insoluble minerals (Figure 13). Desiccation polygons, desiccation cracks, subvertical microkarst pits and chevron halite crystals indicate that the Patience Lake member that encompasses the potash ore was deposited in and just beneath a shallow-brine, salt-pan environment (Figure 13b; Boys, 1990; Lowenstein and Spencer, 1990; Brodlyo and Spencer, 1987; pers. obs).

Clay seams form characteristic thin stratigraphic segregations throughout the potash ore zone(s) of the Prairie Evaporite, as well as disseminated intervals, and constitute about 6% of the ore as mined. For example, the insoluble minerals found in the PCS Cory samples are, in approximate order of decreasing abundance: dolomite, clay [illite, chlorite (including swelling-chlorite/chlorite), and septechlorite, quartz, anhydrite, hematite, and goethite. Clay minerals make up about one-third of the total insolubles: other minor components include: potassium feldspar, hydrocarbons, and sporadic non-diagnostic palynomorphs (Figure 13; Boys, 1990).

In all mines, the clays tend to occur as long continuous seams or marker layers between the potash zones and are mainly composed of detrital chlorite and illite, along withauthigenic septechlorite, montmorillonite and sepiolite (Mossman et al., 1982; Boys, 1990). Of the two chlorite minerals, septechlorite is the more thermally stable. The septechlorite, sepiolite and vermiculite very likely originated as direct products of settle-out, syndepositional dissolution or early diagenesis under hypersaline conditions from a precursor that was initially eolian dust settling to the bottom of a vast brine seaway. The absence of the otherwise ubiquitous septechlorite from Second Red Beds west of the zero-edge of the evaporite basin supports this concept (Figure 9, 10).


Potash Textures

Texturally, at the cm-scale, potash salt beds in the Prairie Evaporite (both carnallitite and sylvinite) lack the lateral continuity seen in primary potash textures in the Oligocene of the Mulhouse Basin (Figure 14). Prairie potash probably first formed as syndepositional secondary precipitates and alteration products at very shallow depths just beneath the sediment surface. These early prograde precipitates were then modified to varying degrees by ongoing fluid flushing in the shallow burial environment. The cyclic depositional distribution of disseminated insolubles as the clay marker beds was possibly due to a combination of source proximity, periodic enrichment during times of brine freshening and the strengthening of the winds blowing detritals out over the brine seaway. Possible intra-potash disconformities, created by dissolution of overlying potash-bearing salt beds, are indicated by an abundance of residual hematite in clay seams with some cutting subvertically into the potash bed. Except in, and near, dissolution levels and collapse features, the subsequent redistribution of insolubles, other than iron oxides, is not significant.

In general, halite-sylvite (sylvinite) rocks in the Prairie Evaporite ore zones generally show two end member textures; 1) the most common is a recrystallised polygonal mosaic texture with individual crystals ranging from millimetres to centimetres and sylvite grain boundaries outlined by concentrations of blood-red halite (Figure 14a). 2) The other end member texture is a framework of euhedral and subhedral halite cubes enclosed by anhedral crystals of sylvite (Figure 14b). This is very similar to ore textures in the Salado Formation of New Mexico interpreted as early passive precipitates in karstic voids.

Petrographically, the halite-carnallite (carnallitite) rocks display three distinct textures. Most halite-carnallite rocks contain isolated centimetre-sized cube mosaics of halite enclosed by poikilitic carnallite crystals (Figure 14c); 1) Individual halite cubes are typically clear, with occasional cloudy crystal cores that retain patches of syndepositional growth textures (Lowenstein and Spencer, 1990). 2) The second texture is coarsely crystalline halite-carnallite with equigranular, polygonal mosaic textures. In zones where halite overlies bedded anhydrite, most of the halite is clear with only the occasional crystal showing fluid inclusion banding.

Bedded halite away from the ore zones generally retains a higher proportion of primary depositional textures typical of halite precipitation in shallow ephemeral saline pans (Figure 14d; Brodylo and Spencer, 1987). Crystalline growth fabrics, mainly remnants of vertically-elongate halite chevrons, are found in 50-90% of the halite from many intervals in the Prairie Evaporite. Many of the chevrons are truncated by irregular patches of clear halite that formed as early diagenetic cements in syndepositional karst.

In contrast, the halite hosting the potash ore layers lacks well-defined primary textures but is dominated by intergrown mosaics. From the regional petrology and the lower than expected Br levels in halite in the Prairie Evaporite Formation, Schwerdtner (1964), Wardlaw and Watson (1966) and Wardlaw (1968) postulated a series of recrystallisation events forming sylvite after carnallite as a result of periodic flushing by hypersaline solutions. This origin as a secondary precipitate (via incongruent dissolution) is supported by observations of intergrowth and overgrowth textures (McIntosh and Wardlaw, 1968), collapse and dissolution features at various scales and timings (Gendzwill, 1978; Warren 2017), radiometric ages (Baadsgaard, 1987) and palaeomagnetic orientations of the diagenetic hematite linings associated with the emplacement of the potash (Koehler, 1997; Koehler et al., 1997).

Dating of clear halite crystals in void fills within the ore levels shows that some of the exceptionally coarse and pure secondary halites forming pods in the mined potash horizons likely precipitated during early burial, while other sparry halite void fills formed as late as Pliocene-Pleistocene (Baadsgard, 1987). Even today, alteration and remobilisation of the sylvite and carnallite and the local precipitation of bischofite are ongoing processes, related to the encroachment of the contemporary dissolution edge or the ongoing stoping of chimneys fed by deep artesian circulation (pers obs.).


Fluid inclusion studies support the notion of primary textures (low formation temperatures in chevron halite in the Prairie evaporite and an associated thermal separation of non-sylvite and sylvite associated halite (Figure 15; Chipley et al., 1990). Most fluid inclusions found in primary, fluid inclusion-banded halite associated with the Prairie potash salts contain sylvite daughter crystals at room temperature or nucleate them on cooling (e.g. halite at 915 and 945 m depth in the Winsal Osler well; Lowenstein and Spencer, 1990). In contrast, no sylvite daughter crystals have been observed in fluid inclusions outlining primary growth textures from chevron halites away from the potash deposits.

The data illustrated as Figure 15 clearly show that inclusion temperatures in primary halite chevrons are cooler than those in halites collected in intervals nearer the potash levels. Sylvite daughter crystal dissolution temperatures from fluid inclusions in the cloudy centres of halite crystals associated with potash salts are generally warmer (Brodlyo and Spencer, 1987; Lowenstein and Spencer, 1990). Sylvite and carnallite daughter crystal dissolution temperatures from fluid inclusions in fluid inclusion banded halite from bedded halite-carnallite are the hottest. This mineralogically-related temperature schism establishes that potash salts occur in stratigraphic intervals in the halite where syndepositional surface brines were warmer. In the 50° - 70°C temperature range there could be overlap with heliothermal brine lake waters. Even so, these warmer potash temperatures imply parent brines would likely be moving via a shallow reflux drive and are not the result of primary bottom nucleation (in contrast to primary sylvite in the Mulhouse Basin). Whether the initial Prairie reflux potash precipitate was sylvite or carnallite is open to interpretation (Lowenstein and Hardie, 1990).


Fluid evolution from mineral and isotope chemistry

Analysis of subsurface waters from various Canadian potash mines and collapse anomalies in the Prairie Evaporite suggest that, after initial potash precipitation, a series of recrystallising fluids accessed the evaporite levels at multiple times throughout the burial history of the Prairie Formation (Chipley, 1995; Koehler, 1997; Koehler et al., 1997). Likewise, the isotope systematics and K-Ar ages of sylvite in both halite and sylvite layers indicate that the Prairie Evaporite was variably recrystallised during fluid overprint events (Table 2; Figure 16). These event ages are all younger than original deposition (≈390Ma) and likely correspond to ages of various tectonic events that influenced subsurface hydrology along the western margin of North America.


Chemical compositions of inclusion fluids in the Prairie Evaporite, as determined by their thermometric properties, reveal at least two distinct waters played a role in potash formation: a Na-K-Mg-Ca-Cl brine, variably saturated with respect to sylvite and carnallite; and a Na-K-Cl brine (Horita et al., 1996). That is, contemporary inclusion water chemistry is a result in part of ongoing fluid-rock interaction. The ionic proportions in some halite samples are not the result of simple evaporation of seawater to the sylvite bittern stage (Figure 17a; Horita et al., 1996). There is a clear separation of values from chevron halites in samples from the Lanigan and Bredenbury (K-2 area) mines, which plot closer to the concentration trend seen in halite from modern seawater and values from clear or sparry halite. The latter encompass much lower K and higher Br related to fractionation tied to recrystallisation. Likewise, the influence of ongoing halite and potash salt dissolution is evident in the chemistry of shaft and mine waters with mine level waters showing elevated Mg and K values, (Figure 17b; Wittrup and Kyser, 1990; Chipley, 1995). What is more the mine waters of today show  substantial overlap with waters collected more than thirty years ago (Jensen et al., 2006)


This notion of ongoing fluid-rock interaction controlling the chemistry of mine waters is supported by dD and d18O values of inclusion fluids in both halite and sylvite, which range from -146 to 0‰ and from -17.6 to -3.0‰, respectively (Figure 18). Most of the various preserved isotope values are different from those of evaporated seawater, which should have dD and d18O values near 0‰.

Furthermore, the dD and d18O values of inclusion fluids are probably not the result of precipitation of the evaporite minerals from a brine that was a mixture of seawater and meteoric water. The low latitude position of the basin during the Middle Devonian (10-15° from the equator), the required lack of meteoric water to precipitate basinwide evaporites, and the expected dD and d18O values of any meteoric water in such a setting, make this an unlikely explanation. Rather, the dD and d18O values of inclusion fluids in the halites reflect ambient and evolving brine chemistries as the fluids in inclusions in the various growth layers were intermittently trapped during the subsurface evolution of the Prairie Formation in the Western Canada Sedimentary Basin. They also suggest that periodic migration of nonmarine subsurface water was a significant component of the crossflowing basinal brines throughout much of the recrystallisation history (Chipley, 1995).

Prairie carnallite-sylvite alteration over time

Ongoing alteration of carnallite to sylvite and the reverse reaction means a sylvite-carnallite bed must be capable of gaining or losing fluid at the time of alteration. That is, any reacting potash beds must be permeable at the time of the alteration. By definition, there must be fluid egress to drive incongruent alteration of carnallite to sylvite or fluid ingress to drive the alteration of sylvite to carnallite. There can also be situations in the subsurface where the volume of undersaturated fluid crossflow was sufficient to remove (dissolve) significant quantities of the more soluble evaporite salts. Many authors looking at the Prairie evaporite argue that the fluid access events during the alteration of carnallite to sylvite or the reverse, or the complete leaching of the soluble potash salts was driven by various tectonic events (Figure 16). In the early stages of burial alteration (few tens of metres from the landsurface) the same alteration processes can be driven by varying combinations of brine reflux, prograde precipitation and syndepositional karstification, all driven by changes in brine level and climate, which in turn may not be related to tectonism (Warren, 2016; Chapters 2 and 8 for details).

In the potash areas of the Western Canada Sedimentary Basin, the notion of 10-100 km lateral continuity is a commonly stated precept for both sylvinite and carnallitite units across the extent of the Prairie Evaporite. But when the actual distribution and scale of units are mapped based on mined intercepts, there are numerous 10-100 metre-scale discontinuities (anomalies) present indicating fluid ingress or egress (Warren, 2017).


Sometimes ore beds thin and alteration degrades the ore level (Section A-A1-A2), other times these discontinuities can locally enrich sylvite ore grade (B-B1; Figure 19). Discontinuities or salt anomalies are much more widespread in the Prairie evaporite than mentioned in much of the potash literature (Figure 19). Mining for maintenance of ore grade shows that unexpectedly intersecting an anomaly in a sylvite ore zone can have a range of outcomes ranging from the inconsequential to the catastrophic, in part because there is more than one type of salt anomaly or “salt horse" (Warren, 2017).


Figure 20 summarises what are considered the three most common styles of salt anomaly in the sylvite ore beds of the Prairie Evaporite, namely 1) Washouts, 2) Leach anomalies, 3) Collapse anomalies. These ore bed disturbances and their occurrence styles are in part time-related. Washouts are typically early (eogenetic) and defined as... “salt-filled V- or U-shaped structures, which transect the normal bedded sequence and obliterate the stratigraphy” (Figure 20a; Mackintosh and McVittie, 1983, p. 60). They are typically enriched in, or filled by, insoluble materials in their lower one-third and medium-coarse-grained sparry halite in the upper two thirds. Up to several metres across, when traced laterally they typically pass into halite-cemented paleo-sinks and cavern networks (e.g. Figure 20b). Most washouts likely formed penecontemporaneous to the potash beds they transect, that is, they are preserved examples of synkarst, with infilling of the karst void by a slightly later halite cement. They indicate watertable lowering in a potash-rich saline sump. This leaching was followed soon after by a period of higher watertables and brine saturations, when halite cements occluded the washouts and palaeocaverns. Modern examples of this process typify the edges of subcropping and contemporary evaporite beds, as about the recently exposed edges of the modern Dead Sea. As such, “washouts” tend to indicate relatively early interactions of the potash interval with undersaturated waters, they may even be a part of the syndepositional remobilisation hydrology that focused, and locally enriched, potash ore levels.

In a leach anomaly zone, the stratabound sylvinite ore zone has been wholly or partially replaced by barren halite, without significantly disturbing the normal stratigraphic sequence (clay marker beds) which tend to continue across the anomaly (Figure 20b). Some loss of volume or local thinning of the stratigraphy is typical in this type of salt anomaly. Typically saucer-shaped, they have diameters ranging from a few metres up to 400m. Less often, they can be linear features that are up to 20 m wide and 1600m long. Leach zones can form penecontemporaneously due to depressions and back-reactions in the ore beds, or by later low-energy infiltration of Na-saturated, K-undersaturated brines. The latter method of formation is also likely on the margins of collapse zones, creating a hybrid situation typically classified as a leach-collapse anomaly (Mackintosh and McVittie, 1983; McIntosh and Wardlaw, 1968).

Of the three types of salt anomaly illustrated, leach zone processes are the least understood. Historically, when incongruent dissolution was the widely accepted interpretation for loss of unit thickness in the Prairie Evaporite, many leach anomalies were considered metasomatic. Much of the original metasomatic interpretation was based on decades of detailed work in the various salt mines of the German Zechstein Basin. There, in an endemic halokinetic terrane, evaporite textures were considered more akin to metamorphic rocks, and the term metasomatic alteration was commonly used when explaining leach anomalies (Bochert and Muir, 1964, Braitsch, 1971). In the past two decades, general observations of the preservation of primary chevron halite in most bedded evaporites away from the potash layers in the Prairie Evaporite have led to reduced use of notions of widespread metamorphic-like metasomatic or solid-state alteration processes in bedded evaporites. There is just too much preserved primary texture in the bedded salt units adjacent to potash beds to invoke pervasive burial metasomatism of the Prairie Evaporite.


So how do leach anomalies, as illustrated in Figure 20b, occur in nonhalokinetic settings? One possible explanation is given by the depositional textures documented in anomalies in the Navarra Potash Province (Figure 21). There, the underlying and overlying salt stratigraphy is contiguous, while the intervening sylvite passed laterally into a syndepositional anomaly or “salt horse” created by an irregular topography on the salt pan floor prior to the deposition of onlapping primary sylvinite layers (see Warren 2016, 2017 for detailed discussion)

On the other hand, in halokinetic situations (which characterises much Zechstein salt) solid-state alteration via inclusion related migration in flowing salt beds is a well-documented set of texture-altering processes (diffusion metasomatism). Most workers in such halokinetic systems would agree that there must have been an original stratiform potassium segregation present during or soon after deposition related to initial precipitation, fractional dissolution and karst-cooling precipitation. But what is controlling potassium distribution now in the Zechstein salts is a recrystallised and remobilised set of textures, which preserve little or no crystal-scale evidence of primary conditions (Warren, 2016; Chapter 6). The complex layering in such deposits may preserve a broad depositional stratigraphy, but the decimetre to metre scale mineral distributions are indications of complex interactions of folds, overfolds, and disaggregation with local flow thickening. We shall return to this discussion of Zechstein potash textures in the next section dealing with devolatisation of hydrated salts such as carnallite. in zones of local heating

Collapse zones in the Prairie Evaporite are characterized by a loss of recognizable sylvinite ore strata, which is replaced by less saline brecciated, recemented and recrystallized material, with the breccia blocks typically made of the intrasalt or roof lithologies (Figure 20c), so angular fragments of the Second Red beds and dolostones of the Dawson Bay Formation are the most conspicuous components of the collapse features in the Western Canada Sedimentary Basin. When ore dissolution is well developed, all the halite can dissolve, along with the potash salts, and the overlying strata collapse into the cavity (these are classic solution collapse features). Transitional leached zones typically separate the collapsed core from normal bedded potash. Such collapse structures indicate a breach of the ore layers by unsaturated waters, fed either from below or above. For example, in the Western Canada Sedimentary Basin, well-developed collapse structures tend to occur over the edges and top Devonian mud mounds, while in the New Mexico potash zone the collapse zones are related to highs in the underlying Capitan reef trend (Warren, 2017). Leaching fluids may have come from below or above to form collapse structures at any time after initial deposition. When connected to a water source, these are the subsurface features that when intersected can quickly move the mining operation out of the salt into an adjacent aquifer system, a transition that led to flooding in most of the mine-lost operations listed earlier.

Identifying at the mine scale the set of processes that created a salt anomaly in a sylvite bed also has implications in terms of its likely influence on mine stability whatever decision is made on how to deal with it as part of the ongoing mine operation (Warren, 2016, 2017). Syndepositional karst fills and leach anomalies are least likely to be problematic if penetrated during mining, as the aquifer system that formed them is likely no longer active. In contrast, penetration or removal of the region around a salt-depleted collapse breccia may lead to uncontrollable water inflows and ultimately to the loss of the mine.

Unfortunately, in terms of production planning, the features of the periphery of a leach anomaly can be similar if not identical to those in the alteration halo that typically forms about the leached edge a collapse zone. The processes of sylvite recrystallisation that define the edge of collapse anomaly can lead to local enrichment in sylvite levels, making these zones surrounding the collapse core attractive extraction targets (Boys 1990, 1993). Boundaries of any alteration halo about a collapse centre are not concentric, but irregular, making the prediction of a feature’s geometry challenging, if not impossible. The safest course of action is to avoid mining salt anomalies, but longwall techniques make this difficult and so they must be identified and dealt with (see Warren 2017).


Cooking sylvite: Dykes & sills in potash salts

 

In addition to; 1) primary sylvite and 2) sylvite/carnallite alteration via incongruent transformation in burial, there is a third mode of sylvite formation related to 3) igneous heating driving devolatisation of carnallitite, which can perhaps be considered a form of incongruent melting (Warren, 2016). And so, at a local scale (measured in metres to tens of metres) in potash beds cut by igneous intrusions, there are a number of documented thermally-driven alteration styles and thermal haloes. Most are created by the intrusion of hot doleritic or basaltic dykes and sills into cooler salt masses, or the outflow of extrusive igneous flows over cooler salt beds (Knipping, 1989; Grishina et al, 1992, 1998; Gutsche, 1988; Steinmann et al., 1999; Wall et al., 2010). Hot igneous material interacts with somewhat cooler anhydrous salt masses to create narrow, but distinct, heat and mobile fluid-release envelopes, also reflected in the resulting salt textures. At times, relatively rapid magma emplacement can lead to linear breakout trends outlined by phreatomagmatic explosion craters, as imaged in portions of the North Sea (Wall et al., 2010) and the Danakhil/Dallol potash beds in Ethiopia (Salty Matters, May 1, 2015).

Based on studies of inclusion chemistry and homogenization temperatures in fluid inclusions in bedded halite near intrusives, it seems that the extent of the influence of a dolerite sill or dyke in bedded salt is marked by fluid-inclusion migration, evidenced by the disappearance of chevron structures and consequent formation of clear halite with a different set of higher-temperature inclusions. Such a migration envelope is well documented in bedded Cambrian halites intruded by end-Permian dolerite dykes in the Tunguska region of Siberia (Grishina et al., 1992).

Defining h as the thickness of the dolerite intrusion in these salt beds, and d as the distance of the halite from the edge of the intrusion, then the disappearance of chevrons occurs at greater distances above than below the intrusive sill. For d/h < 0.9 below the intrusion, CaCl2, CaCl2, KCl and nCaCl2, mMgCl2 solids occur in association with water-free and liquid-CO2 inclusions, with H2S, SCO and orthorhombic or glassy S8. For a d/h of 0.2-2 above the intrusion, H2S-bearing liquid-CO2 inclusions are typical, with various amounts of water. Thus, as a rule of thumb, an alteration halo extends up to twice the thickness of the dolerite sill above the sill and almost the thickness of the sill below (Figure 22).

In a series of autoclavation laboratory experiments, Fabricius and Rose-Hampton (1988) found that; 1) at atmospheiric pressure carnallite melts incongruently to sylvite and hydrated MgCl2 at a temperature of 167.5°C. 2) the melting/transformation temperature increase to values in excess of 180°C as the pressure increases (Figure 23).


A similar situation occurs in the dyke-intruded halite levels exposed in the mines of the Werra-Fulda district of Germany (Steinmann et al., 1999; Schofield, et al., 2014). There the Herfa-Neurode potash mine is located in the Werra-Fulda Basin in the Hessian district of central Germany (Figure 24a). The targeted ore levels consist of the carnallite-rich Kaliflöz Hessen (K1H) and Kaliflöz Thüringen (K1Th) intervals, which form part of the Zechstein 1 (Z1) bedded Werra salt succession (Warren, 2016). In the mine the K1H and K1Th units range in thickness from 2 m to 10 m, are generally subhorizontal and occur at a depth of 650–710 m below the present-day surface.


In the later Tertiary, basaltic melts intruded these Zechstein evaporites as numerous sub-vertical dykes, but only a few dykes attained the Miocene landsurface. Basaltic melt production was related to regional volcanic activity some 10 to 25 Ma. Basalts exposed in the mine walls, where it cuts non-hydrous units of halite or anhydrite, are typically subvertical dykes, rather than subhorizontal sills. The basalts are phonolitic tephrites, limburgites, basanites and olivine nephelinites. Dyke margins are usually vitrified, forming a microlitic limburgite glass along dyke edges in contact with halite (Figure 24b; Knipping, 1989). At the contact on the evaporite side of the glassy rim, there is a cm-wide carapace of high-temperature salts (mostly anhydrite and ferroan carbonates). Further out, the effect of the high-temperature envelope is denoted by transitions to clear halite, with higher temperature fluid inclusions (Knipping 1989). All of this metre-scale alteration is an anhydrous alteration halo, the halite did not melt (melting temperature of 804°C), rather than migrating, the fluid driving recrystallisation was mostly from entrained brine/gas inclusions. The dolerite/basalt interior of the basaltic dyke is likewise altered and salt soaked, with clear, largely inclusion-free halite typically filling vesicles in the basalt.

Heating of hydrated (carnallitic) salt layers, adjacent to a dyke or sill, tends to drive off the water of crystallisation (chemical or hydration thixotropy) at much lower temperatures than that at which anhydrous salts, such as halite or anhydrite, thermally melt (Figure 24c; Table 3). For example, in the Fulda region, the thermally-driven release of water of crystallisation within carnallitic beds creates thixotropic or subsurface “peperite” textures as carnallitite alters to sylvinite layers. These are layers where heated water of crystallisation escaped from the hydrated-salt lattice. Dehydration-driven loss of mechanical strength focuses zones of magma entry into particular subhorizontal horizons in the salt mass, wherever hydrated salt layers were present. In contrast, dyke and sill margins are much sharper and narrower in zones of contact with anhydrous salt intervals and the intrusive is sub-vertical to steeply dipping (Figure 24b versus 24c).

Accordingly, away from the immediate vicinity of the direct thermal aureole, heated and overpressured dehydration waters can enter carnallite halite bed, and drive the creation of extensive soft sediment deformation and peperite textures in hydrated layer (Figure 24c). Mineralogically, sylvite and coarse recrystallised halite dominate the salt fraction in the peperite intervals of the Herfa-Neurode mine. Sylvite in the altered zone is a form of dehydrated carnallite, not a primary-textured salt. Across the Fulda region, such altered zones and deformed units can extend along former carnallite layer to tens or even a hundred or more metres from the dyke feeder. Ultimately, the deformed potash bed passes back out into the unaltered bed, which retains abundant inclusion-rich halite and carnallite (Schofield et al., 2014).

That is, nearer the basalt dyke, the carnallite is largely transformed into inclusion-poor halite and sylvite, the result of incongruent flushing of warm saline fluids mobilised from the hydrated carnallite crystal lattice as it was heated by dyke emplacement. During Miocene salt alteration/thermal metamorphism in the Fulda region, NaCl-fluids were mixed with fluids and gases originating from thermally-mobilised crystallisation water in the carnallite, as it converted to sylvite. This brine/gas mixture altered the basalts during post-intrusive cooling, an event which numerical models suggest was quite rapid (Knipping, 1989): a dyke of less than 0.5 m thickness probably cooled to temperatures less than 200°C within 14 days of dyke emplacement.

The contrast in alteration extent between anhydrous and hydrous salt layers shows alteration effects are minimal wherever the emplacement temperature of the magma is below that of the anhydrous salt body as it is next to a basalt dyke. If this is the mechanism driving entry of igneous-related volatiles (gases and liquids) into a salt body, then the distribution of products (including CO2) will be highly inhomogeneous and related to the minerally of the salt unit adjacent to the intrusive. Worldwide, dykes intersecting salt beds tend to widen to become sills in two zones: 1) along evaporite units within the halite mass that contain hydrated salts, such as carnallite or gypsum (Figure 24c) and, 2) where rising magma has ponded and so created laccoliths at the upper or lower halite contact with the adjacent nonsalt strata or against a salt wall (Figure 22 vs 24). The first is a response to a pulse of released water as dyke-driven heating forces the dehydration of hydrated salt layers. The second is a response to the mechanical strength contrast at the salt-nonsalt contact.

In summary, sylvite formed from a carnallite precursor during Miocene salt alteration/thermal metamorphism in the Fulda region, NaCl-fluids were mixed with fluids originating from thermally-mobilised crystallisation water in the carnallite, as it converted to sylvite. This brine mixture altered the basalts during post-intrusive cooling, an event which numerical models suggest was quite rapid (Knipping, 1989): a dyke of less than 0.5 m thickness probably cooled to temperatures less than 200°C within 14 days of dyke emplacement.

How do we produce potash salts?

 

Over this series of three articles focused on current examples of potash production, we have seen there are two main groups of potash minerals currently utilised to make fertiliser, namely, muriate of potash (MOP) and sulphate of potash (SOP). MOP is both mined (generally from a Pre-Neogene sylvinite ore) or produced from brine pans (usually via processing of a carnallitite slurry). In contrast, large volumes of SOP are today produced from brine pans in China and the USA but with only minor production for solid-state ore targets. Historically, SOP was produced from solid-state ores in Sicily, the Ukraine, and Germany but today there are no conventional mines with SOP as the prime output in commercial operation (See Salty Matters, May 12, 2015).

The MgSO4-enriched chemistry of modern seawater makes the economic production of potash bitterns from a seawater-feed highly challenging. Today, there is no marine-fed plant anywhere in the world producing primary sylvite precipitates. However, sylvite is precipitating from a continental brine feed in salt pans on the Bonneville salt flat, Utah. There, a brine field, drawing shallow pore waters from saltflat sediments, supplies suitably low-MgSO4 inflow chemistry to the concentrator pans. Sylvite also precipitates in solar evaporator pans in Utah that are fed brine circulated through the abandoned workings of the Cane Creek potash mine (Table 1).

Large-scale production of MOP fertiliser from potash precipitates created in solar evaporation pans is taking place in perennially subaqueous saline pans of the southern Dead Sea and the Qaidam Basin. In the Dead Sea, the feed brine is pumped from the waters of the northern Dead Sea basin, while in the Qaidam sump the feed is from a brine field drawing pore brines with an appropriate mix of river and basinal brine inputs. In both cases, the resulting feed brine to the final concentrators is relatively depleted in magnesium and sulphate. These source bitterns have ionic proportions not unlike seawater in times of ancient MgSO4-depleted oceans. Carnallitite slurries, not sylvinite, are the MOP precipitates in pans in both regions. When feed chemistry of the slurry is low in halite, then the process to recover sylvite is a cold crystallisation technique. When halite impurity levels in the slurry are higher, sylvite is manufactures using a more energy intensive, and hence more expensive, hot crystallisation technique. Similar sulphate-depleted brine chemistry is used in Salar Atacama, where MOP and SOP are recovered as byproducts of the production of lithium carbonate brines.

Significant volumes of SOP are recovered from a combination of evaporation and cryogenic modification of sulfate-enriched continental brines in pans on the edge of the Great Salt Lake, Utah, and Lop Nur, China. When concentrated and processed, SOP is recovered from the processing of a complex series of Mg-K-SO4 double salts (schoenitic) in the Odgden pans fed brines from the Great Salt Lake. The Lop Nur plant draws and concentrates pore waters from a brine field drawing waters from glauberite-polyhalite-entraining saline lake sediments.

All the Quaternary saline lake factories supply less than 20% of the world's potash; the majority comes from the conventional mining of sylvinite ores. The world's largest reserves are held in Devonian evaporites of the Prairie Evaporite in the Western Canada Sedimentary Basin. Textures and mineral chemistry show that the greater volume of bedded potash salts in this region is not a primary sylvite precipitate. Rather the ore distribution, although stratiform and defined by a series of clay marker beds, actually preserves the effects of multiple modifications and alterations tied to periodic egress and ingress of basinal waters. Driving mechanisms for episodes of fluid crossflow range from syndepositional leaching and reflux through to tectonic pumping and uplift (telogenesis). Ore distribution and texturing reflect local-scale (10-100 metres) discontinuities and anomalies created by this evolving fluid chemistry. Some alteration episodes are relatively benign in terms of mineralogical modification and bed continuity. Others, generally tied to younger incidents (post early Cretaceous) of undersaturated crossflow and karstification, can have substantial effects on ore continuity and susceptibility to unwanted fluid entry. In contrast, ore textures and bed continuity in the smaller-scale sylvinite ores in the Oligocene Mulhouse Basin, France, indicate a primary ore genesis.

What makes it economic?

Across the Quaternary, we need a saline lake brine systems with the appropriate brine proportions, volumes and climate to precipitate the right association of processable potash salts. So far, the price of potash, either MOP or SOP, and the co-associated MgSO4 bitterns, precludes industrial marine-fed brine factories.

In contrast, to the markedly nonmarine locations of potash recovery from the Quaternary sources, almost all pre-Quaternary potash operations extract product from marine-fed basinwide ore hosts during times of MgSO4-depleted and MgSO4-enriched oceans (Warren, 2016; Chapter 11). This time-based dichotomy in potash ore sources with nonmarine hosts in the Quaternary deposits and marine evaporite hosted ore zones in Miocene deposits and older, reflects a simple lack of basinwide marine deposits and appropriate marine chemistry across the Neogene (Warren, 2010). As for all ancient marine evaporites, the depositional system that deposited ancient marine-fed potash deposits was one to two orders of magnitude larger and the resultant deposits were typically thicker stacks than any Quaternary potash settings. The last such “saline giant” potash system was the Solfifera series in the Sicilian basin, deposited as part of the Mediterranean “salinity crisis,” but these potential ore beds are of the less economically attractive MgSO4- enriched marine potash series.

So, what are the factors that favour the formation of, and hence exploration for, additional deposits of exploitable ancient potash? First, large MOP solid-state ore sources are all basinwide, not lacustrine deposits. Within the basinwide association, it seems that intracratonic basins host significantly larger reserves of ore, compared to systems that formed in the more tectonically-active plate-edge rift and suture association. This is a reflection of: 1) accessibility – near the shallow current edge of a salt basin, 2) a lack of a halokinetic overprint and, 3) the setup of longterm, stable, edge-dissolution brine hydrologies that typify many intracratonic basins. Known reserves of potash in the Devonian Prairie evaporite in West Canadian Sedimentary Basin (WCSB) are of the order of 50 times that of next largest known deposit, the Permian of the Upper Kama basin, and more than two orders of magnitude larger than any other of the other known exploited deposits (Table 1).

Part of this difference in the volume of recoverable reserves lies in the fact that the various Canadian potash members in the WCSB are still bedded and flat-lying. Beds have not been broken up or steepened, by any subsequent halokinesis. The only set of processes overprinting and remobilising the various potash salts in the WCSB are related to multiple styles and timings of aquifer encroachment on the potash units, and this probably took place at various times since the potash was first deposited, driven mainly by a combination of hinterland uplift and subrosion. In contrast, most of the other significant potash basins listed in Table 10 have been subjected to ongoing combinations of halokinesis and groundwater encroachments, making these beds much less laterally predictable. In their formative stages, the WCSB potash beds were located a substantial distance from the orogenic belt that drove flexural downwarp and creation of the subsealevel sag depression. Like many other intracratonic basins, the WCSB did not experience significant syndepositional compression or rift-related loading.

References

Adamo, S., 1992, The Sicilian rock salt and potash mines: Mining Magazine, v. 166, p. 277-283.

Adams, S. S., 1970, Ore controls, Carlsbad potash district, southeast New Mexico, in J. L. Rau, and L. F. Dellwig, eds., Third Symposium on Salt, v. 1: Cleveland, Ohio, Northern Ohio Geological Society, p. 246-257.

Baadsgaard, H., 1987, Rb-Sr and K-Ca isotope systematics in minerals from potassium horizons in the Prairie Evaporite Formation, Saskatchewan, Canada: Chemical Geology, v. 66, p. 1-15.

Baar, C. A., 1974, Geological problems in Saskatchewan potash mining due to peculiar conditions during deposition of Potash Beds, in A. H. Coogan, ed., Fourth Symposium on Salt, v. 1: Cleveland, Ohio, North Ohio Geological Society, p. 101-118.

Bastow, I. D., A. D. Booth, G. Corti, D. Keir, C. Magee, C. A.-L. Jackson, J. Warren, J. Wilkinson, and M. Lascialfari, 2018, The development of late-stage continental breakup: Seismic reflection and borehole evidence from the Danakil Depression, Ethiopia: Tectonics, v. 37.

Bingham, C. P., 1980, Solar production of potash from brines of the Bonneville Salt Flats, in J. W. Gwynn, ed., Great Salt Lake; a scientific, history and economic overview. , v. 116, Bulletin Utah Geological and Mineral Survey, p. 229-242.

Blanc-Valleron, M.-M., and M. Schuler, 1997, The Salt Basins of Alsace (Southern Rhine Graben), in G. Busson, and B. C. Schreiber, eds., Sedimentary Deposition in Rift and Foreland Basins in France and Spain (Paleogene and Lower Neogene): New York, Columbia University Press, p. 95–135.

Blanc-Valleron, M. M., 1991, Les formations paléogènes évaporitiques du bassin potassique de Mulhouse et des bassins plus septentrion aux d'Alsace (Document BRGM, 204), Université Louis Pasteur, Paris, 350 p.

Borchert, H., and R. O. Muir, 1964, Salt deposits-The origin, metamorphism and deformation of evaporites: London, D. Van Nostrand Co., Ltd., 338 p.

Boys, C., 1990, The geology of potash deposits at PCS Cory Mine, Saskatchewan: Master's thesis, University of Saskatchewan; Saskatoon, SK; Canada, 225 p.

Boys, C., 1993, A geological approach to potash mining problems in Saskatchewan, Canada: Exploration & Mining Geology, v. 2, p. 129-138.

Braitsch, O., 1971, Salt Deposits: Their Origin and Compositions: New York, Springer-Verlag, 297 p.

Brodylo, L. A., and R. J. Spencer, 1987, Depositional environment of the Middle Devonian Telegraph Salts, Alberta, Canada: Bulletin Canadian Petroleum Geology, v. 35, p. 186-196.

Cendon, D. I., C. Ayora, J. J. Pueyo, and C. Taberner, 2003, The geochemical evolution of the Catalan potash subbasin, South Pyrenean foreland basin (Spain): Chemical Geology, v. 200, p. 339-357.

Cendon, D. I., C. Ayora, J. J. Pueyo, C. Taberner, and M. M. Blanc-Valleron, 2008, The chemical and hydrological evolution of the Mulhouse potash basin (France): Are "marine" ancient evaporites always representative of synchronous seawater chemistry?: Chemical Geology, v. 252, p. 109-124.

Cendon, D. I., C. Ayora, and J. P. Pueyo, 1998, The origin of barren bodies in the Subiza potash deposit, Navarra, Spain - Implications for sylvite formation: Journal of Sedimentary Research Section A-Sedimentary Petrology & Processes, v. 68, p. 43-52.

Cheng, H. D., Q. Y. Hai, H. Z. Ma, X. Y. Zhang, Q. L. Tang, Q. S. Fan, Y. S. Li, and W. L. Miao, 2016, Implications for the origin of secondary sylvite from a simulation of carnallite dissolution: Journal of Geochemical Exploration, v. 165, p. 189-198.

Cheng, H. D., H. Z. Ma, Q. Y. Hai, Z. H. Zhang, L. M. Xu, and G. F. Ran, 2015, Model for the decomposition of carnallite in aqueous solution: Int. J. Miner. Process., v. 139, p. 36-42.

Chipley, D., and T. K. Kyser, 1991, Large scale fluid movement in the Western Canadian sedimentary basin as recorded by fluid inclusions in evaporites, in J. E. Christopher, and F. M. Haidl, eds., Sixth international Williston Basin symposium, v. 6, Special Publication Saskatchewan Geological Society, p. 265-269.

Chipley, D., T. K. Kyser, and T. Danyluk, 1990, Fluid flow events in the Elk Point Baain of western Canada as recorded in evaporite minerals: Summary of Investigations 1990, Saskatchewan Geological Survey; Saskatchewan Energy and Mines, Miscellaneous Report, p. 211-217.

Chipley, D. B. L., 1995, Fluid history of the Saskatchewan sub-basin of the western Canada sedimentary basin: Evidence from the geochemistry of evaporites: Doctoral thesis, University of Saskatchewan.

Chipley, D. B. L., and T. K. Kyser, 1989, Fluid inclusion evidence for the deposition and diagenesis of the Patience Lake Member of the Devonian Prairie Evaporite Formation, Saskatchewan, Canada: Sedimentary Geology, v. 64, p. 287-295.

de Ruiter, P. A. C., 1979, The Gabon and Congo basins salt deposits: Economic Geology, v. 74, p. 419-431.

Dong, Z., P. Lv, G. Qian, X. Xia, Y. Zhao, and G. Mu, 2012, Research progress in China's Lop Nur: Earth-Science Reviews, v. 111, p. 142-153.

Duan, Z. H., and W. X. Hu, 2001, The accumulation of potash in a continental basin: the example of the Qarhan Saline Lake, Qaidam Basin, West China: European Journal of Mineralogy, v. 13, p. 1223-1233.

Eatock, W. H., 1987, The Big Quill Lake sulphate of potash project, in C. F. Gilboy, and L. W. Vigrass, eds., Economic Minerals of Saskatchewan, Proceedings of a Symposium Held in Regina, Saskatchewan 17 & 18 November 1986, : Saskatchewan Geological Society Special Publication Number 8, p. 206–210.

El Tabakh, M., C. Utha-Aroon, and B. C. Schreiber, 1999, Sedimentology of the Cretaceous Maha Sarakham evaporites in the Khorat Plateau of northeastern Thailand: Sedimentary Geology, v. 123, p. 31-62.

Emons, H., and H. Voigt, 1981, Untersvchungen zur kalten zersetzunung von Carnallit.: Freiberg Forschungsher, v. A628, p. 69-78.

Evans, R., 1970, Genesis of sylvite- and carnallite-bearing rocks from Wallace, Nova Scotia: Third Symposium on Salt, v. 1, p. 239-245.

 

Fabricius, J., and Rose-Hansen, J., 1988, Pressure-dependent melting curve of natural carnallite, KMgCl3.6H2O, in a closed system where evaporation is prevented. IX Symposium on Fluid Inclusions, 4-6 May, 1987, Oporto, Portugal.

 

Fuzesy, A., 1982, Potash in Saskatchewan: Report, Saskatchewan Department of Mineral Resources, v. 181, 45 p.

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

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

Gendzwill, D. J., 1978, Winnipegosis mounds and Prairie Evaporite Formation of Saskatchewan – seismic study: Bulletin American Association Petroleum Geologists, v. 62, p. 73-86.

Grishina, S., J. Dubessy, A. Kontorovich, and J. Pironon, 1992, Inclusions in salt beds resulting from thermal metamorphism by dolerite sills (eastern Siberia, Russia): European Journal of Mineralogy, v. 4, p. 1187-1202.

Grishina, S., J. Pironon, M. Mazurov, S. Goryainov, A. Pustilnikov, G. Fonderflaas, and A. Guerci, 1998, Organic inclusions in salt - Part 3 - Oil and gas inclusions in Cambrian evaporite deposits from east Siberia - A contribution to the understanding of nitrogen generation in evaporite: Organic Geochemistry, v. 28, p. 297-310.

Gutsche, A., 1988, Mineralreaktionen und Sto€transporte an einem Kontakt Basalt-Hartsalz in der Werra-Folge des Werkes Hattorf: Unpubl. diploma thesis, thesis, Georg-August-Universita, Gottingen.

Hardie, L. A., 1984, Evaporites: Marine or non-marine?: American Journal of Science, v. 284, p. 193-240.

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

Hinsken, S., K. Ustaszewski, and A. Wetze, 2007, Graben width controlling syn-rift sedimentation: the Palaeogene southern Upper Rhine Graben as an example: International Journal of Earth Sciences, v. 96, p. 979-1002.

Hite, R. J., 1961, Potash-bearing evaporite cycles in the salt anticlines of the Paradox Basin, Colorado and Utah; Article 337: U. S. Geological Survey Professional Paper. p. D323-D327.

Hite, R. J., and T. Japakasetr, 1979, Potash deposits of the Khorat Plateau, Thailand and Laos: Economic Geology, v. 74, p. 448-458.

Hofmann, P., A. Y. Huc, B. Carpentier, P. Schaeffer, P. Albrecht, B. Keely, J. R. Maxwell, D. J. S. Sinninghe, L. J. W. de, and D. Leythaeuser, 1993a, Organic matter of the Mulhouse Basin, France; a synthesis: Organic Geochemistry, v. 20, p. 1105-1123.

Hofmann, P., D. Leythaeuser, and B. Carpentier, 1993b, Palaeoclimate controlled accumulation of organic matter in Oligocene evaporite sediments of the Mulhouse Basin: Organic Geochemistry, v. 20, p. 1125-1138.

Holser, W. T., 1979, Trace elements and isotopes in evaporites in R. G. Burns, ed., Marine Minerals, v. 6, Reviews in Mineralogy, p. 295-346.

Holt, N. M., J. García-Veigas, T. K. Lowenstein, P. S. Giles, and S. Williams-Stroud, 2014, The major-ion composition of Carboniferous seawater: Geochimica et Cosmochimica Acta, v. 134, p. 317-334.

Holter, M., 1972, Geology of the Prairie Evaporite Formation of Saskatchewan, Canada, Geology of saline deposits (Geologie des depots salins), v. 7, UNESCO Earth Sci. Ser., p. 183-189.

Holwerda, J. G., and R. W. Hutchinson, 1968, Potash-bearing evaporites in the Danakil area, Ethiopia: Economic Geology, v. 63, p. 124-150.

Hong, X. L., S. P. Xia, and S. Y. Gao, 1994, Dissolution kinetics of carnallite (in Chinese with English abstract). Chin. J. Appl. Chem., v. 11, p. 26-31.

Horita, J., A. Weinberg, N. Das, and H. Holland, 1996, Brine inclusions in halite and the origin of the Middle Devonian Prairie evaporites of western Canada: Journal of Sedimentary Research Section A-Sedimentary Petrology & Processes, v. 66, p. 956-954.

Hryniv, S. P., B. V. Dolishniy, O. V. Khmelevska, A. V. Poberezhskyy, and S. V. Vovnyuk, 2007, Evaporites of Ukraine: a review: Geological Society, London, Special Publications, v. 285, p. 309-334.

Jensen, G. K. S., B. J. Rostron, M. J. M. Duke, and C. Holmden, 2006, Bromine and stable isotopic profiles of formation waters from potash mine-shafts, Saskatchewan, Canada: Journal of Geochemical Exploration, v. 89, p. 170-173.

Knipping, B., 1989, Basalt intrusions in evaporites: Lecture Notes in Earth Sciences (Springer-Verlag), v. 24, p. 132 pp.

Koehler, G., T. K. Kyser, R. Enkin, and E. Irving, 1997, Paleomagnetic and isotopic evidence for the diagenesis and alteration of evaporites in the Paleozoic Elk Point Basin, Saskatchewan, Canada: Canadian Journal of Earth Sciences, v. 34, p. 1619-1629.

Koehler, G. D., 1997, The Geochemistry and Petrogenesis of Carnallite and its Relationship to the Diagenesis of the Devonian Prairie Formation: PhD thesis, University of Saskatchewan.

Koehler, G. D., T. K. Kyser, and T. Danyluk, 1990, Stable Isotope evidence for the petrogenesis of carnallite In the Middle Devonian Prairie Evaporile Formation, Saskatchewan: Summary of Investigations 1990, Saskatchewan Geological Survey; Saskatchewan Energy and Mines, Miscellaneous Report 90-04.

Liu, C., Y. Ji, Y. Bai, F. Cheng, and X. Lu, 2007, Formation of porous crystals by coupling of dissolution and nucleation process in fractional crystallization: Fluid Phase Equilib, v. 261, p. 300-305.

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., 1988, Origin of depositional cycles in a Permian ''saline giant''; the Salado (McNutt Zone) evaporites of New Mexico and Texas: Geological Society of America Bulletin, v. 100, p. 592-608.

Lowenstein, T. K., and R. J. Spencer, 1990, Syndepositional origin of potash evaporites; petrographic and fluid inclusion evidence: American Journal of Science, v. 290, p. 43-106.

Ma, L., T. K. Lowenstein, B. Li, P. Jiang, C. Liu, J. Zhong, J. Sheng, H. Qiu, and H. Wu, 2010, Hydrochemical characteristics and brine evolution paths of Lop Nor Basin, Xinjiang Province, Western China: Applied Geochemistry, v. 25, p. 1770-1782.

Mackintosh, A. D., and G. A. McVittie, 1983, Geological anomalies observed at the Cominco Ltd. Saskatchewan potash mine: Potash '83; Potash technology; mining, processing, maintenance, transportation, occupational health and safety, environment., p. 59-64.

Matthews, R. D., and G. C. Egleson, 1974, Origin and Implications of a Mid-Basin Potash Facies in the Salina Salt of Michigan, Fourth International Symposium on Salt, v. 1, Northern Ohio Geological Society, p. 15-34.

McIntosh, R. A., and N. C. Wardlaw, 1968, Barren halite bodies in the sylvinite mining zone at Esterhazy, Saskatchewan: Canadian Journal of Earth Sciences, v. 5, p. 1221-1238.

Mossman, D. J., R. N. Delabio, and A. D. Mackintosh, 1982, Mineralogy of clay marker seams in some Saskatchewan potash mines: Canadian Journal of Earth Sciences, v. 19, p. 2126-2140.

Mossop, G., and I. Shetsen, 1994, Geological Atlas of the Western Canada Sedimentary Basin: Canadian Society of Petroleum Geologists and Alberta Research Council, 504 p.

Prud'homme, M., and S. T. Krukowski, 2006, Potash, in J. E. Kogel, N. C. Trivedi, J. M. Barker, and S. T. Krukowski, eds., Industrial Minerals and Rocks, SME (Soc. Mining Metallurgy and Exploration), p. 723-742.

Richter-Bernburg, G., 1986, Zechstein 1 and 2 anhydrites; facts and problems of sedimentation, in G. M. Harwood, and D. B. Smith, eds., The English Zechstein and related topics, v. 22: London, UK, Geological Society Special Publication, p. 157-163.

Rogers, M. B., and B. Pratt, 2017, Stratigraphy of the Middle Devonian Keg River and Prairie Evaporite formations, northeast Alberta, Canada: Bulletin of Canadian Petroleum Geology, v. 65, p. 5-63.

Root, K. G., 2001, Devonian Antler Fold and Thrust Belt and Foreland Basin Development in the Southern Canadian Cordillera: Implications for the Western Canada Sedimentary Basin: Bulletin of Canadian Petroleum Geology, v. 49, p. 7-36.

Rosell, L., and F. Ortí, 1981, The saline (potash) formation of the Navarra basin (Upper Eocene, Spain). Petrology: Revista Instituto Investigaciones Geologicas, v. 35, p. 71-121.

Rouchy, J.-M., 1997, Paleogene Continental Rift System of Western Europe: locations of basins, paleogeographic and structural framework, and the distribution of evaporites: In: Busson, G., Schreiber, B.C. (Eds.), Sedimentary Deposition in Rift and Foreland Basins in France and Spain (Paleogene and Lower Neogene). Columbia University Press, New York, pp. 45–94.

Schofield, N., I. Alsop, J. Warren, J. R. Underhill, R. Lehné, W. Beer, and V. Lukas, 2014, Mobilizing salt: Magma-salt interactions: Geology, v. 42, p. 599-602.

Schwerdtner, W. M., 1964, Genesis of potash rocks in Middle Devonian Prairie Evaporite Formation of Saskatchewan: Bulletin American Association Petroleum Geologists, v. 48, p. 1108-1115.

Schwerdtner, W. M., 1964, Genesis of potash rocks in Middle Devonian Prairie Evaporite Formation of Saskatchewan: Bulletin American Association Petroleum Geologists, v. 48, p. 1108-1115.

Smith, D. B., 1996, Deformation in the late Permian Boulby Halite (EZ3Na) in Teesside, NE England: Geological Society, London, Special Publications, v. 100, p. 77-87.

Smith, D. B., and A. Crosby, 1979, The regional and stratigraphical context of Zechstein 3 and 4 potash deposits in the British sector of the southern North Sea and adjoining land areas: Economic Geology, v. 74, p. 397-408.

Steinmann, M., P. Stille, W. Bernotat, and B. Knipping, 1999, The corrosion of basaltic dykes in evaporites: Ar-Sr-Nd isotope and rare earth elements evidence: Chemical Geology, v. 153, p. 259-279.

Szatmari, P., R. S. Carvalho, and I. A. Simoes, 1979, A comparison of evaporite facies in the late Paleozoic Amazon and the Middle Cretaceous South Atlantic salt basins: Economic Geology, v. 74, p. 432-447.

Valyashko, M. G., 1972, Playa lakes, a necessary stage in the development of a salt-bearing basin [with discussion]: Geology of saline deposits, Unesco Earth Sci. Ser., p. 41-51.

van't Hoff, J. H., 1912, Untersuchungen Uber die Bildungsurhältnisse der ozeanischen Salzablangerungen, insbesondere das Stassfurter Salzlagers: Leipzig.

Voigt, W., 2015, What we know and still not know about oceanic salts: Pure Appl. Chem., v. 87, p. 1099-1026.

Volozh, Y., C. J. Talbot, and A. Ismail-Zadeh, 2003, Salt structures and hydrocarbons in the Pricaspian basin: Bulletin American Association Petroleum Geologists, v. 87, p. 313-334.

Wall, M., J. Cartwright, R. Davies, and A. McGrandle, 2010, 3D seismic imaging of a Tertiary Dyke Swarm in the Southern North Sea, UK: Basin Research, v. 22, p. 181-194.

Wardlaw, N. C., 1968, Carnallite-sylvite relationships in the middle Devonian Prairie evaporite formation, Saskatchewan: Geological Society America Bulletin, v. 79, p. 1273-1294.

Wardlaw, N. C., 1972a, Unusual marine evaporites with salts of calcium and magnesium chloride in Cretaceous basins of Sergipe, Brazil: Economic Geology, v. 67, p. 156-168.

Wardlaw, N. C., 1972b, Syn-sedimentary folds and associated structures in Cretaceous salt deposits of Sergipe, Brazil: J. Sediment. Petrol., v. 42, p. 572-577.

Wardlaw, N. C., and G. D. Nicholls, 1972, Cretaceous Evaporites of Brazil and West Africa and their Bearing on the Theory of Continent Separation.: 24th Inter. Geol. Congr., v. 6, p. 43-55.

Wardlaw, N. C., and D. W. Watson, 1966, Middle Devonian salt formations and their bromide content, Elk Point area, Alberta: Canadian Journal of Earth Sciences, v. 3, p. 263-275.

Warren, J. K., 2000, Geological controls on the quality of potash, in R. M. Geertmann, ed., 8th World Salt Symposium, v. 1: Amsterdam, Elsevier, p. 173-180.

Warren, J. K., 2010, Evaporites through time: Tectonic, climatic and eustatic controls in marine and nonmarine deposits: Earth-Science Reviews, v. 98, p. 217-268.

Warren, J. K., 2011, Evaporitic source rocks: mesohaline responses to cycles of “famine or feast” in layered brines, Doug Shearman Memorial Volume, (Wiley-Blackwell) IAS Special Publication Number 43, p. 315-392.

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

Warren, J. K., 2017, Salt usually seals, but sometimes leaks: Implications for mine and cavern stabilities in the short and long term: Earth-Science Reviews, v. 165, p. 302-341.

Williams-Stroud, S. C., 1994, Solution to the Paradox? Results of some chemical equilibrium and mass balance calculations applied to the Paradox Basin evaporite deposit: American Journal of Science, v. 294, p. 1189-1228.

Wittrup, M. B., and T. K. Kyser, 1990, The petrogenesis of brines in Devonian potash deposits of western Canada: Chemical Geology, v. 82, p. 103-128.

Woods, P. J. E., 1979, The geology of Boulby Mine: Economic Geology, v. 74, p. 409-418.

Worsley, N., and A. Fuzesy, 1979, The potash-bearing members of the Devonian Prairie Evaporite of southeastern Saskatchewan, south of the mining area: Economic Geology, v. 74, p. 377-388.

Xia, S. P., X. L. Hong, and S. Y. Gao, 1993, Study on the dissolution kinetics and mechanism of carnallite and KC (in Chinese with English abstract): Journal Salt Lake Research, v. 1, p. 52-60.

Yang, C., G. Jensen, and J. Berenyi, 2009, The Stratigraphic Framework of the Potash-rich Members of the Middle Devonian Upper Prairie Evaporite Formation, Saskatchewan: Summary of Investigations 2009, Saskatchewan Geological Survey; Misc. Rep. 2009-4.1, 28 p.

Zak, I., 1997, Evolution of the Dead Sea brines, in T. M. Niemi, Z. Ben-Avraham, and J. R. Gat, eds., The Dead Sea, The Lake and Its Setting, v. 36: Oxford, Oxford University Press; Monographs on Geology and Geophysics, p. 133-144.

Zharkov, M. A., 1984, Paleozoic salt bearing formations of the world: Berlin, Springer Verlag, 427 p.

 

Salt as a Fluid Seal: Article 4 of 4: When and where it leaks - Implications for waste storage

John Warren - Thursday, March 24, 2016

 

In the three preceding articles on salt leakage, we have seen that most subsurface salt in the diagenetic realm is a highly efficient seal that holds back large volumes of hydrocarbons in salt basins worldwide (Article 3). When salt does leak or transmit fluid, it does so in one of two ways: 1) by the entry of undersaturated waters (Article 1 in this series) and; 2) by temperature and pressure-induced changes in its dihedral angle, which in the diagenetic realm is often tied to the development of significant overpressure and hydrocarbon migration (Article 2). The other implication linked to the two dominant modes of salt leakage is the source of the fluid entering the leaking salt. In the first case, the fluid source is external to the salt ("outside the salt"). In the second case, it can be internal to the main salt mass ("inside the salt"). However, due to dihedral angle changes at greater depths and pressures, a significant portion of leaking fluid passing through more deeply-buried altering salt is external. By the onset of greenschist facies metamorphism, this is certainly the case (Chapter 14 in Warren, 2016) 

Diagenetic fluids driving salt leakage are external to the salt mass

Within a framework of fluids breaching a subsurface salt body, the breached salt can be a bed of varying thickness, or it can have flowed into a variety of autochthonous and allochthonous salt masses. Autochthonous salt structures are still firmly rooted in the stratigraphic level of the primary salt bed. Allochthonous salt structurally overlies parts of its (stratigraphically younger) overburden and is often no longer connected to the primary salt bed (mother-salt level).

Breaches in bedded (non-halokinetic) salt

The principal documented mechanism enabling leakage across bedded salt in the diagenetic realm is dissolution, leading to breaks or terminations in salt bed continuity. Less often, leakage across a salt unit can occur where bedded salt has responded in a brittle fashion and fractured or faulted (Davison, 2009). In hydrocarbon-producing basins with widespread evaporite seals, significant fluid leakage tends to occur near the edges of the salt bed. For example, in the Middle East, the laterally continuous Hith Anhydrite (Jurassic) acts as a regional seal to underlying Arab Cycle reservoirs and carbonate-mudstone source rock. The high efficiency of the Hith seal creates many of the regions giant and supergiant fields, including Ghawar in Saudi Arabia, which is the largest single oil-filled structure in the world. Inherent maintenance of the evaporite's seal capacity also prevents vertical migration from mature sub-Hith source rocks into potential reservoirs in the overlying Mesozoic section across much of Saudi Arabia and the western Emirates. However, toward the Hith seal edge are a number of large fields supra-Hith fields, hosted in Cretaceous carbonates, and a significant portion of the hydrocarbons are sourced in Jurassic carbonate muds that lie stratigraphically below the anhydrite level (Figure 1).

 

The modern Hith Anhydrite edge is not the depositional margin of the laterally extensive evaporite bed. Rather, it is a dissolution edge, where rising basinal brines moving up and out of the basin have thinned and altered the past continuity of this effective seal.

The process of ongoing dissolution allowing vertical leakage near the edge of a subsurface evaporite interval, typifies not just the edge of bedded salts but also the basinward edges of salt units that are also halokinetic. The dissolution edge effect of the Ara Salt and its basinward retreat over time are clearly seen along the eastern edge of the South Oman Salt Basin where the time of filling of the Permian-hosted reservoir structures youngs toward the west (Figure 2).


 

Leakages associated with the margins of discrete diapiric structures

Once formed, salt diapirs tend to focused upward escape of basinal fluid flows: as evidenced by: (1) localized development of mud mounds and chemosynthetic seeps at depopod edges above diapirs in the Gulf of Mexico (Figure 3a); (2) shallow gas anomalies clustered around and above salt diapirs in the North Sea and (Figure 3b); (3) localized salinity anomalies around salt diapirs, offshore Louisiana and with large pockmarks above diapir margins in West Africa (Cartwright et al., 2007). Likewise, in the eastern Mediterranean region, gas chimneys in the Tertiary overburden are common above regions of thinned Messinian Salt, as in the vicinity of the Latakia Ridge (Figure 4).



Leakage of sub-salt fluids associated with salt welds and halokinetic touchdowns

Whenever a salt weld or touchdown occurs, fluids can migrate vertically across the level of a now flow-thinned or no-longer-present salt level. Such touchdowns or salt welds can be in basin positions located well away from the diapir edge and are a significant feature in the formation of many larger base-metal and copper traps, as well as many depopod-hosted siliciclastic oil and gas reservoirs (Figure 5: Warren 2016).


Caprocks are leaky

Any caprock indicates leakage and fractional dissolution have occurred along the evaporite boundary (Figure 5). Passage of an undersaturated fluid at or near the edge of a salt mass creates a zone of evaporite dissolution residues, which in the case of diapiric occurrences is called usually called a “caprock,” although such diagenetic units do not only form a “cap” or top to a salt structure.

Historically, in the 1920s and 30s, shallow vuggy and fractured caprocks to salt diapirs were early onshore exploration targets about topographic highs in the Gulf of Mexico (e.g. Spindletop). Even today, the density of drilling and geological data derived from these onshore diapiric features means many models of caprock formation are mostly based on examples in Texas and Louisiana. Onshore in the Gulf of Mexico, caprocks form best in dissolution zones at the outer, upper, edges of salt structures, where active cross-flows of meteoric waters are fractionally dissolving the salt. However, rocks composed of fractional dissolution residues, with many of the same textural and mineralogical association as classic Gulf of Mexico caprocks, are now known to mantle the deep sides of subvertical-diapirs in the North Sea (e. g., lateral caprock in the Epsilon Diapir) and define the basal anhydrite (basal caprock) that defines the underbelly of the Cretaceous Maha Sarakham halite across the Khorat Plateau in NE Thailand (Figure 5; Warren, 2016).


All “caprocks” are fractionally-dissolved accumulations of diapir dissolution products and form in zones of fluid-salt interaction and leakage, wherever a salt mass is in contact with undersaturated pore fluids (Figure 6). First to dissolve is halite, leaving behind anhydrite residues, that cross-flushing pore waters can then convert to gypsum and, in the presence of sulphate-reducing bacteria, to calcite. If the diapir experiences another growth pulse the caprock can be broken and penetrated by the rising salt. This helps explain fragments of caprock caught up in shale sheaths or anomalous dark-salt zones, as exemplified by less-pure salt-edge intersection units described as dark and anomalous salt zones in the Gulf of Mexico diapirs (as documented in Article 1).

2. Fluids that are internal to the salt mass

Fluid entry in relation to changes in the dihedral angle of halite is well documented (Article 2). It was first recorded by Lewis and Holness (1996) who postulated, based on their static-salt laboratory experiments;

"In sedimentary basins with normal geothermal gradients, halite bodies at depths exceeding 3 km will contain a stable interconnected brine-filled porosity, resulting in permeabilities comparable to those of sandstones". Extrapolating from their static halite pressure experiments they inferred that halite, occurring at depths of more than ≈3 km and temperatures above 200 °C, has a uniform intrasalt pore system filled with brine, and therefore relatively high permeabilities.

In the real world of the subsurface, salt seals can hold back significant hydrocarbon columns down to depths of more than 6-7 km (see case studies in Chapter 10 in Warren, 2016 and additional documentation the SaltWork database). Based on a compilation of salt-sealed hydrocarbon reservoirs, trans-salt leakage across 75-100 metres or more of pure salt does not occur at depths less than 7-8 km, or temperatures of less than 150°C. In their work on the Haselbirge Formation in the Alps, Leitner et al. (2001) use a temperature range >100 °C and pressures >70 MPa as defining the onset of the dihedral transition.

It seems that across much of the mesogenetic realm, a flowing and compacting salt mass or bed can maintain seal integrity to much greater depths than postulated by static halite percolation experiments. In the subsurface, there may be local pressured-induced changes in the halite dihedral angle within the salt mass, as seen in the Ara Salt in Oman, but even there, there is no evidence of the total km-scale salt mass transitioning into a leaky aquifer via changes in the halite dihedral angle (Kukla et al., 2011). But certainly, as we move from the diagenetic into the metamorphic realm, even thick pure salt bodies become permeable across the whole salt mass. Deeply buried and pressured salt ultimately dissolves as it transitions into various meta-evaporite indicator minerals and zones (Chapter 14, Warren, 2016).

When increasing pressure and temperature changes the halite dihedral angle in the diagenetic realm, then supersaturated hydrocarbon-bearing brines can enter salt formations to create naturally-hydrofractured "dark-salt". As we discussed in Article 2, pressure-induced changes in dihedral angle in the Ara Salt of Oman create black salt haloes that penetrate, from the overpressured salt-encased carbonate sliver source, up to 50 or more meters into the adjacent halite (Schoenherr et al. 2007). Likewise, Kettanah, 2013 argues Argo Salt of eastern Canada also has leaked, based on the presence of petroleum-fluid inclusions (PFI) and mixed aqueous and fluid inclusions (MFI) in the recrystallised halite (Figure 7 - see also Ara “black salt” core photos in Article 2 of this series).


Both these cases of dark-salt leakage (Ara and Argo salts) occur well within the salt mass, indicating the halokinetic salt has leaked or transmitted fluids within zones well away from the salt edge. In the case of the Argo salt, the study is based on drill cuttings collected across 1500 meters of intersected salt at depths of 3-4 km. Yet, at the three km+ depths in the Argo Salt where salt contains oil and bitumen, the total salt mass still acts a seal, implying it must have regained or retained seal integrity, after it leaked. Not knowing the internal fold geometries in any deeply buried salt mass, but knowing that all flowing salt masses are internally complex (as seen in salt mines and namakiers), means we cannot assume how far the hydrocarbon inclusions have moved within the salt mass, post-leakage. Nor can we know if, or when, any salt contact occurred with a possible externally derived hydrocarbon-bearing fluid source, or whether subsequent salt flow lifted the hydrocarbon-inclusion-rich salt off the contact surface as salt flowed back into the interior of the salt mass.

Thus, with any hydrocarbon-rich occurrence in a halokinetic salt mass, we must ask the question; did the salt mass once hydrofracture (leak) in its entirety, or did the hydrocarbons enter locally and then as the salt continued to flow, that same hydrocarbon-inclusion-rich interval moved into internal drag and drape folds? In the case of the Ara Salt, the thickness of the black salt penetration away from its overpressured source is known as it is a core-based set of observations. In the Ara Salt at current depths of 3500-4000 m, the fluid migration zones extend 50 -70 meters out from the sliver source in salt masses that are hundreds of metres thick (Kukla et al., 2011; Schoenherr et al., 2007).

So how do we characterize leakage extent in a buried salt mass without core?

Dark salt, especially if it contains hydrocarbons, clearly indicates fluid entry into a salt body in the diagenetic realm. Key to considerations of hydrocarbon trapping and long-term waste storage is how pervasive is the fluid entry, where did the fluid come from, and what are the likely transmission zones in the salt body (bedded versus halokinetic)?

In an interesting recent paper documenting and discussing salt leakage, Ghanbarzadeh et al., 2015 conclude:

“The observed hydrocarbon distributions in rock salt require that percolation occurred at porosities considerably below the static threshold due to deformation-assisted percolation. Therefore, the design of nuclear waste repositories in salt should guard against deformation-driven fluid percolation. In general, static percolation thresholds may not always limit fluid flow in deforming environments.”

Their conclusions are based on lab experiments on static salt and extrapolation to a combination of mud log and wireline data collected from a number of wells that intersected salt allochthons in Louann Salt in the Gulf of Mexico. Their lab data on changing dihedral angles inducing leakage or percolation in static salt confirms the experiments of Holness and Lewis (1996 – See Article 2). But they took the implications of dihedral angle change further, using CT imagery to document creation of interconnected polyhedral porosity in static salt at higher temperatures and pressures (Figure 8). They utilise Archies Law and resistivity measures to calculate inferred porosity, although it would be interesting what values they utilise for cementation exponent (depends on pore tortuosity) Sw and saturation exponent. Assuming the standard default values of m = 2 and n =2 when applying Archies Law to back calculate porosity spreads in halite of assumed Sw are likely incorrect.  


They then relate their experimental observations to wireline measurements and infer the occurrence of interconnected pores in Gulf of Mexico salt based on this wireline data. Key to their interpretation is the deepwater well GC8 (Figure 9), where they use a combination of a resistivity, gas chromatograms, and mud log observations to infer that hydrocarbons have entered the lower one km of a 4 km thick salt section, via dihedral-induced percolation.

 

I have a problem in accepting this leap of faith from laboratory experiments on pure salt observed at the static decimeter-scale of the lab to the dynamic km-scale of wireline-inferred observations in a salt allochthon in the real world of the offshore in deepwater salt Gulf of Mexico. According to Ghanbarzadeh et al., 2015, the three-part gray background in Figure 9 corresponds to an upper no-percolation zone (dark grey), a transition zone (moderate grey) and a lower percolation zone (light grey). This they then infer to be related to changes in dihedral angle in the halite sampled in the well (right side column). Across the data columns, what the data in the GC8 well show is:  A) Gamma log; allochthon salt has somewhat higher API values at depths shallower than 5000 m; B) Resistivity log, a change in resistivity to higher values (i.e., lower conductivity) with a change in the same cross-salt depth range as seen in the gamma log, beginning around 5100 m; C) Gas (from sniffer), shows a trend of decreasing gas content from the base of salt (around 6200 m) up to a depth around 4700 m, then relatively low values to top salt, with an interval that is possibly shalier interval (perhaps a suture - see below)  that also has a somewhat higher gas content ; D) Gas chromatography, the methane (CH4) content mirrors the total gas trends, as do the other gas phases, where measured; E) Mud Log (fluorescence response), dead oil is variably present from base of salt up to 5000 m, oil staining, oil cut and fluorescence (UV) are variably present from base salt up to a depth of 4400 m.

On the basis of the presented log data, one can infer the lower kilometer of the 4 km salt section contains more methane, more liquid hydrocarbons, and more organic material/kerogen compared to the upper 3 km of salt. Thus, the lower section of the salt intersected in the GC8 well is likely to be locally rich in zones of dark or anomalous salt, compared with the overlying 3 km of salt. What is not given in figure 9 is any information on likely levels of non-organic impurities in the salt, yet this information would have been noted in the same mud log report that listed hydrocarbon levels in the well. In my opinion, there is a lack of lithological information on the Gulf of Mexico salt in the Ghanbarzadeh et al. paper, so one must ask; "does the lower kilometer of salt sampled in the GC8 well, as well as containing hydrocarbons also contain other impurities like shale, pyrite, anhydrite, etc. If so, potentially leaky intervals could be present that were emplaced by sedimentological processes unrelated to changes in the dihedral angle of the halite (see next section).


Giving information that is standard in any mud-log cuttings description (such as the amount of anhydrite, shale, etc that occur in drill chips across the salt mass), would have added a greater level of scientific validity to to Ghanbarzadeh et al.'s inference that observed changes in hydrocarbon content up section, was solely facilitated by changes in dihedral angle of halite facilitating ongoing leakage from below the base of salt and not due to the dynamic nature of salt low as the allochthon or fused allochthons formed.  Lithological information on salt purity is widespread in the Gulf of Mexico public domain data. For example, Figure 10 shows a seismic section through the Mahogany field and the intersection of the salt by the Phillips No. 1 discovery well (drilled in 1991). This interpreted section, tied to wireline and cuttings information, was first published back in 1995 and re-published in 2010. It shows intrasalt complexity, which we now know typifies many sutured salt allochthon and canopy terrains across the Gulf of Mexico salt province. Internally, Gulf of Mexico salt allochthons, like others worldwide, are not composed of pure halite, just as is the case in the onshore structures discussed in the context of dark salt zones in article 1. Likely, a similar lack of purity and significant structural and lithological variation typifies most if not all of the salt masses sampled by the Gulf of Mexico wells listed in the Ghanbarzadeh et al. paper, including the key GC8 well (Figure 9). This variation in salt purity and varying degrees of local leakage is inherent to the emplacement stage of all salt allochthons world-wide. It is set up as the salt flow (both gravity spreading and gravity gliding) occurs at, or just below the seafloor, fed by varying combinations of extrusion or thrusting, which moves salt out and over the seabed (Figure 11).

 


 

Salt, when it is flowing laterally and creating a salt allochthon, is in a period of rapid breakout (Figure 11; Hudec and Jackson, 2006, 2007; Warren 2016). This describes the situation when a rising salt sheet rolls out over its base, much in the same way a military tank moves out over its track belt. As the salt spreads, the basal and lateral salt in the expanding allochthon mass, is subject to dissolution, episodic retreat, collapse and mixing with seafloor sediment, along with the entry of compactional fluids derived from the sediments beneath. Increased impurity levels are particularly obvious in disturbed basal shear zones that transition downward into a gumbo zone (Figure 12a), but also mantle the sides of subvertical salt structures, and can evolve by further salt dissolution into lateral caprocks and shale sheaths (Figure 6).

In expanding allochthon provinces, zones of non-halite sediment typically define sutures within (autosutures; Figure 12b) or between salt canopies (allosutures; Figure 12c). These sutures are encased in halite as locally leaky, dark salt intervals, and they tend to be able to contribute greater volumes of fluid and ongoing intrasalt dissolution intensity and alteration where the suture sediment is in contact with outside-the-salt fluids. Allochthon rollout, with simultaneous diagenesis and leakage, occurs across intrasalt shear zones, or along deforming basal zones. In the basal part of an expanding allochthon sheet the combination of shearing, sealing, and periodic leakage creates what is known as “gumbo,” a term that describes a complex, variably-pressured, shale-rich transition along the basal margin of most salt allochthons in the Gulf of Mexico (Figure 12a). Away from suture zones, as more allochthon salt rolls out over the top of earlier foot-zones to the spreading salt mass, the inner parts of the expanding and spreading allochthon body tend toward greater internal salt purity (less non-salt and dissolution residue sediment, as well as less salt-entrained hydrocarbons and fluid inclusion).

At the salt's upper contact, the spreading salt mass may carry its overburden with it, or it may be bare topped (aka open-toed; Figure 11). In either case, once salt movement slows and stops, a caprock carapace starts to form that is best developed wherever the salt edge is flushed by undersaturated pore waters (Figure 6). Soon after its emplacement, the basal zone of a salt allochthon acts a focus for rising compactional fluids coming from sediments beneath. So, even as it is still spreading, the lower side of the salt sheet is subject to dissolution, and hydrocarbon entry, often with remnants of the same hydrocarbon-entraining brines leaking to seafloor about the salt sheet edge. As the laterally-focused subsalt brines escape to the seafloor across zones of thinned and leaky salt or at the allochthon edge, they can pond to form chemosynthetic DHAL (Deepsea Hypersaline Anoxic Lake) brine pools (Figure 3a). Such seep-fed brine lakes typify the deep sea floor in the salt allochthon region of continental slope and rise in the Gulf of Mexico and the compressional salt ridge terrain in the central and eastern Mediterranean. If an allochthon sheet continues to expand, organic-rich DHAL sediments and fluids become part of the basal shear to the salt sheet (Figure 12a).


Unfortunately, Ghanbarzadeh et al., 2015 did not consider the likely geological implications of salt allochthon emplacement mechanisms and how this likely explains much of the geological character seen in wireline signatures across wells intersecting salt in the Gulf of Mexico. Rather, they assume the salt system and the geological character they infer as existing in the lower portions of Gulf of Mexico salt masses, are tied to post-emplacement changes in salt's dihedral angle in what they consider as relatively homogenous and pure salt masses. They modeled the various salt masses in the Gulf of Mexico as static, with upward changes in the salt purity indicative of concurrent hydrocarbon leakage into salt and facilitated by altered dihedral angles in the halite. A basic tenet of science is "similarity does not mean equivalence." Without a core from this zone, one cannot assume hydrocarbon occurrence in the lower portions of Gulf of Mexico salt sheets is due to changes in dihedral angle. Equally, if not more likely, is that the wireline signatures they present in their paper indicate the manner in which the lower part of a salt allochthon has spread. To me, it seems that the Ghanbarzadeh et al. paper argues for caution in the use of salt cavities for nuclear waste storage for the wrong reasons.

Is nuclear waste storage in salt a safe, viable long-term option?

Worldwide, subsurface salt is an excellent seal, but we also know that salt does fail, that salt does leak, and that salt does dissolve, especially in intrasalt zones in contact with "outside" fluids. Within the zone of anthropogenic access for salt-encased waste storage (depths of 1-2km subsurface) the weakest points for potential leakage in a salt mass, both natural and anthropogenic, are related to intersection with, or unplanned creation of, unexpected fluid transmission zones and associated entry of undersaturated fluids that are sourced outside the salt (see case histories in Chapter 7 and 13 in Warren, 2016). This intersection with zones of undersaturated fluid creates zones of weakened seal capacity and increases the possibility of exchange and mixing of fluids derived both within and outside the salt mass. In the 1-2 km depth range, the key factor to be discussed in relation to dihedral angle change inducing percolation in the salt, will only be expressed as local heating and fluid haloes in the salt about the storage cavity. Such angle changes are tied to a thermal regime induced by long-term storage of medium to high-level radioactive waste.  

I use an ideal depth range of 1-2 km for storage cavities in salt as cavities located much deeper than 2 km are subject to compressional closure or salt creep during the active life of the cavity (active = time of waste emplacement into the cavity). Cavities shallower than 1 km are subject to the effects of deep phreatic circulation. Salt-creep-induced partial cavity closure, in a salt diapir host, plagued the initial stages of use of the purpose-built gas storage cavity known as Eminence in Mississippi. In the early 1970s, this cavity was subject to a creep-induced reduction in cavity volume until gas storage pressures were increased and the cavern shape re-stabilised. Cavities in salt shallower than 1 km are likely to be located in salt intervals that at times have been altered by cross flows of deeply-circulating meteoric or marine-derived phreatic waters. Problematic percolation or leakage zones (aka anomalous salt zones), which can occur in some places in salt masses in the 1-2 km depth range, are usually tied to varying combinations of salt thinning, salt dissolution or intersection with unexpected regions of impure salt (relative aquifers). In addition to such natural process sets, cross-salt leakage can be related to local zones of mechanical damage, tied to processes involved in excavating a mine shaft, or in the drilling and casing of wells used to create a purpose-built salt-solution cavity. Many potential areas of leakage in existing mines or brine wells are the result of poorly completed or maintained access wells, or intersections with zones of “dark salt,” or with proximity to a thinned salt cavity wall in a diapir, as documented in articles 1 and 2 (and detailed in various case studies in Chapters 7 and 13 in Warren 2016).

In my opinion, the history of extraction, and intersections with leakage zones, during the life of most of the world’s existing salt mines means conventional mines in salt are probably not appropriate sites for long-term radioactive waste storage. Existing salt mines were not designed for waste storage, but to extract salt or potash with mining operations often continuing in a particular direction along an ore seam until the edge of the salt was approached or even intersected. When high fluid transmission zones are unexpectedly intersected during the lifetime of a salt mine, two things happen; 1) the mine floods and operations cease, or the flooded mine is converted to a brine extraction facility (Patience Lake) or, 2) the zone of leakage is successfully grouted and in the short term (tens of years) mining continues (Warren, 2016).

For example, in the period 1906 to 1988, when Asse II was an operational salt mine, there were 29 documented water breaches that were grouted or retreated from. Over the long term, these same water-entry driven dissolution zones indicate a set of natural seep processes that continued behind the grout job. This is true in any salt mine that has come “out of the salt” and outside fluid has leaked into the mine. “Out-of-salt” intersections are typically related to fluids entering the salt mass via dark-salt or brecciated zones or shale sheath intersections (these all forms of anomalous salt discussed in article 1 and documented in the case studies discussed in Chapter 13 in Warren 2016).

I distinguish such “out-of-salt” fluid intersections from “in-salt” fluid-filled cavities. When the latter is cut, entrained fluids drain into the mine and then flow stops. Such intersections can be dangerous during the operation of a mine as there is often nitrogen, methane or CO2 in an "in-the-salt” cavity, so there is potential for explosion and fatalities. But, in terms of long-term and ongoing fluid leakage “in-salt” cavities are not a problem.

Ultimately, because “out-of-salt” fluid intersections are part of the working life of any salt mine, seal integrity in any mine converted to a storage facility will fail. Such failures are evidenced by current water entry problems in Asse II Mine, Germany (low-medium level radioactive waste storage) and the removal of the oil formerly stored in the Weeks Island strategic hydrocarbon facility, Texas. Weeks Island was a salt mine converted to oil storage. After the mine was filled with oil, expanding karst cavities were noticed forming at the surface above the storage area. Recovery required a very expensive renovation program that ultimately removed more than 95% of the stored hydrocarbons. And yet, during the active life of the Weeks Island Salt Mine, the mine geologists had mapped “black salt” occurrences and tied them to unwanted fluid entries that were then grouted. Operations to block or control the entry of fluids were successful, and salt extraction continued apace.  This information on fluid entry was available well before the salt mine was purchased and converted to a federal oil storage facility. However, in the 1970s when the mine was converted, our knowledge of salt properties and salt's stability over the longer term was less refined than today.

Worldwide, the biggest problem with converting existing salt mines to low to medium level nuclear waste storage facilities is that all salt mines are relatively shallow, with operating mine depth controlled by temperatures where humans can work (typically 300-700 m and always less than 1.1 km). This relatively shallow depth range, especially at depths above 500 m, is also where slowly-circulating subsurface or phreatic waters are dissolving halite to varying degrees, This is where fluids can enter the salt from outside and so create problematic dark-salt and collapse breccia zones within the salt. In the long-term (hundreds to thousands of years) these same fluid access regions have the potential to allow stored waste fluids to escape the salt mass,

Another potential problem with long-term waste storage in many salt mines, and in some salt cavity hydrocarbon storage facilities excavated in bedded (non-diapiric) salt, is the limited thickness of a halite beds across the depth range of such conventional salt mines and storage facilities. Worldwide, bedded ancient salt tends to be either lacustrine or intracratonic, and individual halite units are no more than 10-50 m thick in stacks of various saline lithologies. That is, intracratonic halite is usually interlayered with laterally extensive carbonate, anhydrite or shale beds, that together pile into bedded saline successions up to a few hundred metres thick (Warren 2010). The non-halite interlayers may act as potential long-term intrasalt aquifers, especially if connected to non-salt sediments outside the halite (Figure 13). This is particularly true if the non-salt beds remain intact and hydraulically connected to up-dip or down-dip zones where the encasing halite is dissolutionally thinned or lost. Connection to such a dolomite bed above the main salt bed, in combination with damaged casing in an access well, explains the Hutchison gas explosion (Warren, 2016). Also, if there is significant local heating associated with longer term nuclear waste storage in such relatively thin (<10-50 m) salt beds, then percolation, related to heat-induced dihedral angle changes, may also become relevant over the long-term (tens of thousands of years), even in bedded storage facilities in 1-2 km depth range.


Now what?

Creating a purpose-built mine for the storage of low-level waste in a salt diapir within the appropriate depth range of 1-2 km is the preferred approach and a much safer option, compared to the conversion of existing mines in diapiric salt, but is likely to be prohibitively expensive. To minimise the potential of unwanted fluid ingress, the entry shaft should be vertical, not inclined. The freeze-stabilised “best practice” vertical shaft currently being constructed by BHP in Canada for its new Jansen potash mine (bedded salt) is expected to cost more than $1.3 billion. If a purpose-built mine storage facility were to be constructed for low to medium level waste storage in a salt diapir, then the facility should operate at a depth of 800-1000m. Ideally, such a purpose-built mine should also be located hundreds of metres away from the edges of salt mass in a region that is not part of an area of older historical salt extraction operations. At current costings, such a conventionally-mined purpose-built storage facility for low to medium level radioactive waste is not economically feasible.

This leaves purpose-built salt-solution cavities excavated within thick salt domes at depths of 1-2 km; such purpose-built cavities should be located well away from the salt edge and in zones with no nearby pre-existing brine-extraction cavities or oil-field exploration wells. This precludes most of the onshore salt diapir provinces of Europe and North America as repositories for high-level nuclear waste, all possible sites are located in high population areas and can have century-long histories of poorly documented salt and brine extraction and petroleum wells. Staying "in-the-salt" over the long-term would an ongoing problem in these regions (see case histories in chapters 7 and 13 in Warren, 2016 for a summary of some problems areas).

References

Alsharhan, A. S., and C. G. S. C. Kendall, 1994, Depositional setting of the Upper Jurassic Hith Anhydrite of the Arabian Gulf; an analog to Holocene evaporites of the United Arab Emirates and Lake MacLeod of Western Australia: Bulletin-American Association of Petroleum Geologists, v. 78, p. 1075-1096.

Andresen, K. J., M. Huuse, N. H. Schodt, L. F. Clausen, and L. Seidler, 2011, Hydrocarbon plumbing systems of salt minibasins offshore Angola revealed by three-dimensional seismic analysis: AAPG Bulletin, v. 95, p. 1039-1065.

Bowman, S. A., 2011, Regional seismic interpretation of the hydrocarbon prospectivity of offshore Syria: GeoArabia, v. 16, p. 95-124.

Cartwright, J., M. Huuse, and A. Aplin, 2007, Seal bypass systems: American Association Petroleum Geologists - Bulletin, v. 91, p. 1141-1166.

Davison, I., 2009, Faulting and fluid flow through salt: Journal of the Geological Society, v. 166, p. 205-216.

Dooley, T. P., M. R. Hudec, and M. P. A. Jackson, 2012, The structure and evolution of sutures in allochthonous salt: Bulletin American Association Petroleum Geologists, v. 96, p. 1045-1070.

Ghanbarzadeh, S., M. A. Hesse, M. Prodanović, and J. E. Gardner, 2015, Deformation-assisted fluid percolation in rock salt: Science, v. 350, p. 1069-1072.

Gillhaus, A., 2010, Natural gas storage in salt caverns - Summary of worldwide projects and consequences of varying storage objectives and salt formations, in Z. H. Zou, H. Xie, and E. Yoon, eds., Underground Storage of CO2 and Energy, CRC Press, Boca Raton, Fl., p. 191-198.

Harrison, H., and B. Patton, 1995, Translation of salt sheets by basal shear: Proceedings of GCS-SEPM Foundation 16th Annual Research Conference, Salt Sediment and Hydrocarbons, Dec 3-6, 1995, p. 99-107.

Holly Harrison, Dwight ‘Clint’ Moore, and P. Hodgkins, 2010, A Geologic Review of the Mahogany Subsalt Discovery: A Well That Proved a Play (The Mahogany Subsalt Discovery: A Unique Hydrocarbon Play, Offshore Louisiana): Search and Discovery Article #60049 Posted April 28, 2010, Adapted from presentation at AAPG Annual Convention, 1995, and from an extended abstract prepared for presentation at GCS-SEPM Foundation 16th Annual Research Conference, “Salt, Sediment and Hydrocarbons,” December 3-6, 1995.

Hudec, M. R., and M. P. A. Jackson, 2006, Advance of allochthonous salt sheets in passive margins and orogens: American Association Petroleum Geologists - Bulletin, v. 90, p. 1535-1564.

Hudec, M. R., and M. P. A. Jackson, 2007, Terra infirma: Understanding salt tectonics: Earth-Science Reviews, v. 82, p. 1-28.

Jackson, C. A. L., and M. M. Lewis, 2012, Origin of an anhydrite sheath encircling a salt diapir and implications for the seismic imaging of steep-sided salt structures, Egersund Basin, Northern North Sea: Journal of the Geological Society, v. 169, p. 593-599.

Kettanah, Y. A., 2013, Hydrocarbon fluid inclusions in the Argo salt, offshore Canadian Atlantic margin: Canadian Journal of Earth Sciences, v. 50, p. 607-635.

Kukla, P., J. Urai, J. K. Warren, L. Reuning, S. Becker, J. Schoenherr, M. Mohr, H. van Gent, S. Abe, S. Li, Desbois, G. Zsolt Schléder, and M. de Keijzer, 2011, An Integrated, Multi-scale Approach to Salt Dynamics and Internal Dynamics of Salt Structures: AAPG Search and Discovery Article #40703.

Leitner, C., F. Neubauer, J. L. Urai, and J. Schoenherr, 2011, Structure and evolution of a rocksalt-mudrock-tectonite: The haselgebirge in the Northern Calcareous Alps: Journal of Structural Geology, v. 33, p. 970-984.

Lewis, S., and M. Holness, 1996, Equilibrium halite-H2O dihedral angles: High rock salt permeability in the shallow crust: Geology, v. 24, p. 431-434.

Schoenherr, J., J. L. Urai, P. A. Kukla, R. Littke, Z. Schleder, J.-M. Larroque, M. J. Newall, N. Al-Abry, H. A. Al-Siyabi, and Z. Rawahi, 2007, Limits to the sealing capacity of rock salt: A case study of the infra-Cambrian Ara Salt from the South Oman salt basin: Bulletin American Association Petroleum Geologists, v. 91, p. 1541-1557.

Terken, J. M. J., N. L. Frewin, and S. L. Indrelid, 2001, Petroleum systems of Oman: Charge timing and risks: Bulletin-American Association of Petroleum Geologists, v. 85, p. 1817-1845.

Thrasher, J., A. J. Fleet, S. J. Hay, M. Hovland, and S. Düppenbecker, 1996, Understanding geology as the key to using seepage in exploration: the spectrum of seepage styles, in S. D., and M. A. Abrams, eds., Hydrocarbon migration and its near-surface expression, AAPG Memoir 66, p. 223-241.

Warren, J. K., 2010, Evaporites through time: Tectonic, climatic and eustatic controls in marine and nonmarine deposits: Earth-Science Reviews, v. 98, p. 217-268.

Warren, J. K., 2016, Evaporites: A Compendium (ISBN 978-3-319-13511-3) Released Feb. 22 2016: Berlin, Springer, 1854 p.


 

Salt as a Fluid Seal: Article 3 of 4: When it doesn't leak - Seals to hydrocarbons

John Warren - Saturday, March 12, 2016

This, the third article in the series of four on salt leakage, discusses how and when salt acts as a seal. The fourth article will place this discussion in real world situations where the various salt units (especially “dark” salt) have lost long-term seal integrity and what this means in terms of CO2 geosequestration and waste storage.

Evaporite seal character

Unlike thick shales, subsurface evaporites in the diagenetic realm better fit Hunt’s (1990) definition of an actual pressure seal, which he defined as an impermeable rock with zero transmissivity maintained over long periods of geologic time. Very little subsalt fluid can escape through a salt mass that, until breached, tends to hold back all the compactional and thermohaline waters, gases or liquid hydrocarbons rising from below. In contrast, shale-seals consistently leak all these fluids to varying degrees.


In the realm of subsurface hydrocarbon exploration and development, salts (especially halite) are second only to clathrates in ability to form an effective seal to circulating pore waters and hydrocarbons, including methane. (Figure 1; Warren, 2016). Natural methane clathrates (methane-ice mixtures) are more efficient seals, but in the diagenetic realm, clathrate occurrence is limited by the inherent low-temperature stability requirement. This means clathrates act as hydrocarbon seals onshore in permafrost regions, such as some Siberian gas fields, or below clathrate layers down to depths of a hundred meters or so beneath the modern deep-sea floor, as occurs below the cold waters of the slope and rise across the halokinetic Gulf of Mexico or the non-halokinetic sediment of offshore Brunei (Warren, 2016; Warren et al., 2011a).

Like clathrates, evaporite layers can generate overpressures at very shallow burial depths, unlike clathrates they do not dissolve and dissipate in response to rising temperatures of the diagenetic burial realm. Evaporites create the highest and sharpest depth-related pressure differentials known in sedimentary basins in both overpressured and underpressured settings (Fertl 1976). Salt-sealed overpressured intervals can be as shallow as a few hundred meters below the surface or deeper than 6,000 m.


Unlike the low temperatures requirements for a clathrate seal, evaporite seals, with their extremely high entry pressures, ductility, very low permeabilities and large lateral extents, can maintain seal integrity over wide areas, even when exposed to a wide range of subsurface temperature and pressure conditions. A typical shale seal has permeability ≈ 10-1 to 10-5 md, with extreme values as low as 10-8 md (Figure 2). Quantitative measurement of evaporite permeability is beyond the capacity of standard instruments used in the oil industry and is mostly a topic of study for engineers working with waste-storage caverns. Their work shows the permeability of undisturbed halite is a nanodarcy or less, that is, undamaged subsurface salt has measured permeabilities that are less than 10-21 m2 (10-6md) with some of the tighter halite permeabilities ≈10-7 to 10-9 md. In contrast, typical massive anhydrites ≈10-5 md (Beauheim and Roberts, 2002). This explains a general “rule of thumb” used in the oil industry that a halite bed should be at least 2 m thick to be considered a possible seal, while and anhydrite bed should be at least 10 m thick. Equally important is the reliability of the geological model of the evaporite that is used to extrapolate lateral continuity in the seal (Warren, 2016). Pore pressures in thick sealing halites can approach lithostatic (Ehgartner et al., 1998) and when exceeded salt can locally fracture and leak (as discussed in the previous article).

Massive thick bedded pure halite units in the diagenetic realm usually contain few, if any, interconnected pore throats. The distance between NaCl lattice units is 2.8 x 10-10 m, while the smallest molecular diameter of a hydrocarbon molecule (methane) is 3.8 x 10-10 m. The most frequent way that hydrocarbons migrate through an unfractured undissolved halite bed is if the halite contains impurities that render it locally porous and make it brittle during deformation.

 


 

Seal capacity in flowing pure salt

Halite’s very high ductility and its ability to flow, re-anneal and re-establish lattice bonding by solution creep when subject to stress give it a low susceptibility to fracturing even when it is deforming (Figure 3). This is why cross-salt fault and fracture patterns, as seen in most salt-entraining basins, make the industry considers salt a “crack-stopper” (Figure 4). Worldwide, seismic imaging of halokinetic realms shows that the salt has flowed, while adjacent carbonate and siliciclastics sequences fractured. Halite’s ability to maintain seal integrity under stress, and so prevent the escape of hydrocarbons, reflects a combination of an ability to flow and re-anneal, and the small size of molecular interspaces in its ionically-bonded NaCl crystal lattice (Figure 5; see detailed discussion see Warren, 2016, chapters 6 and 10).


 

This propensity to flow under stress (tendency toward Newtonian flow) is why many laboratory tests and measurements consistently under-represent salt’s flow and subsurface seal integrity responses. Inherently any lab experiment is tied to short time frames of up to weeks or a few years. However, such laboratory tests are likely more relevant to real-world subsurface situations where salt in the vicinity of any wellbore is damaged by the nearby passage of the drill bit and its associated fluids. The applicability of laboratory measurements to real-world subsurface situations is a philosophical quandary inherent to many natural science experiments with a time-related possible-error component. By putting equipment into a natural subsurface salt region, or by removing salt samples from their natural deep subsurface environment to take measures in the lab, or by growing salt crystals in the lab to work on, we always alter things and so get outcomes that can never be 100% accurate with respect to the original unaltered subsurface salt setting. That is, within observational errors, how do we quantify random versus systematic errors when we are always altering the samples and the surrounds via the process of gaining access?

Whether, during catagenesis, buried halite beds that enclose organic intrabeds can release volatiles to sediments outside the salt mass is still a matter of some discussion among organic geochemists. The long-term lack of fracture or pore throats in buried salt beds is why organic-rich intrasalt carbonate or shale laminites tend to be inefficient source rocks in style 1a source rocks (Warren et al., 2011a). Likewise, possible flushing and maturation effects are poorly understood in subsurface situations where encased organic-rich beds are in contact with hydrated salts converting to their anhydrous equivalents (such as gypsum to anhydrite or carnallite to sylvite, mirabilite to thenardite). Loss of water of crystallisation in shallow burial (<0.5km) has the potential to allow organic-rich fluids to escape early as the hydrated salts transform to their anhydrous forms. Usually, such burial transformations are near complete in the first kilometre of burial and so may only allow immature hydrocarbons to escape into adjacent more porous sediments (Hite and Anders, 1991). There they must be stored, mature and remigrate during later burial if they are to act as hydrocarbon source rocks (Warren, 1986). Many intrasalt organic-rich beds survive well into the metamorphic realm and evolve into graphitic quartzites and marbles encased in meta-evaporitic albitites and scapolites.

As a general rule, even as a halite bed fractures, its inherent lack of strength and the consequent ability to flow means any microscale intercrystalline fractures quickly re-anneal by a combination of flow and pressure-solution induced recrystallisation. (Figure 5). Current consensus in the oil and gas industry is that some thin impurity-rich salt beds, interlayered with carrier beds, do leak small amounts of volatiles, but much less efficiently than thicker organic-rich mudstones and shales; whereas organics encased in thicker salt beds probably cannot leak from the unit until the enclosing salt dissolves or natural hydrofracturing occurs (as in the Ara Salt of Oman). Evaporite beds and salt allochthons constitute some of the strongest long-term subsurface barriers to the vertical migration of hydrocarbons in a sedimentary basin both as a seal to hydrocarbons and in COsequestration.

The next and final article in this series on salt leakage will consider; how and where does a salt seal leak in the real world of the subsurface?

References

Beauheim, R. L., and R. M. Roberts, 2002, Hydrology and hydraulic properties of a bedded evaporite formation: Journal of Hydrology, v. 259, p. 66-88.

Downey, M. W., 1984, Evaluating seals for hydrocarbon accumulations: Bulletin American Association of Petroleum Geologists, v. 68, p. 1752-1763.

Ehgartner, B. L., J. T. Neal, and T. E. Hinkebein, 1998, Gas Releases from Salt: SAND98-1354, Sandia National Laboratories, Albuquerque, NM, June 1998.

Fertl, W. H., 1976, Abnormal Formation Pressures: Amsterdam, Elsevier Scientific, 382 p.

Hite, R. J., and D. E. Anders, 1991, Petroleum and evaporites, in J. L. Melvin, ed., Evaporites, petroleum and mineral resources, v. 50: Amsterdam, Elsevier Developments in Sedimentology, p. 477-533.

Hunt, J. M., 1990, Generation and migration of petroleum from abnormally pressured fluid compartments: Bulletin American Association of Petroleum Geologists, v. 74, p. 1-12.

Ter Heege, J. H., J. H. P. De Bresser, and C. J. Spiers, 2005, Dynamic recrystallisation of wet synthetic polycrystalline halite: dependence of grain size distribution on flow stress, temperature and strain: Tectonophysics, v. 396, p. 35-57.

Urai, J. L., Z. Schléder, C. J. Spiers, and P. A. Kukla, 2008, Flow and Transport Properties of Salt Rocks, in R. Littke, ed., Dynamics of complex intracontinental basins: The Central European Basin System, Elsevier, p. 277-290.

Warren, J. K., 1986, Shallow water evaporitic environments and their source rock potential: Journal Sedimentary Petrology, v. 56, p. 442-454.

Warren, J. K., 2011b, Evaporitic source rocks: mesohaline responses to cycles of “famine or feast” in layered brines, Doug Shearman Memorial Volume, (Wiley-Blackwell) IAS Special Publication Number 43, p. 315-392.

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

Warren, J. K., A. Cheung, and I. Cartwright, 2011a, Organic Geochemical, Isotopic and Seismic Indicators of Fluid Flow in Pressurized Growth Anticlines and Mud Volcanoes in Modern Deepwater Slope and Rise Sediments of Offshore Brunei Darussalam; Implications for hydrocarbon exploration in other mud and salt diapir provinces (Chapter 10), in L. J. Wood, ed., Shale Tectonics, v. 93: Tulsa OK, AAPG Memoir 93 (Proceedings of Hedberg Conference), p. 163-196.

 

 

 

 

 

 

Salt as a Fluid Seal: Article 1 of 4: External fluid source

John Warren - Saturday, December 19, 2015

 

Introduction

In the next few articles, I plan to discuss salt’s ability to act as a fluid seal in a variety of halokinetic settings, as well as looking at the nature of the sealing salt. Of particular interest are formative mechanisms driving textural and permeability variations in zones that typify the salt side of the sealing boundaries in sub-vertical salt stems versus the lower contact transitions in sub-horizontal allochthons. In the first few articles, we shall focus on local-scale scenarios and salt seal textures, including situations where salt has leaked, and the intercrystalline or tetrahedral/polyhedral pores contain fluid or mineralogical evidence of leakage and crystal boundary dissolution. Within the salt mass, this is usually indicated by occurrences of “black” or “dark” salt in anomalous salt zones, some of which are intersected by workings in a number of salt mines. In contrast, in most oil exploration scenarios we only have wireline signatures to interpret the deeper and typically offshore seal horizons. Following on from that discussion, we shall look at more regional examples of cross-formational leakage. Finally, we will discuss implications of possible leakage in terms of understanding and predicting outcomes with respect to both waste storage and hydrocarbon sealing

“Black” or “dark” salt in anomalous salt zones

The geological term “black salt” covers a variety of salt textures and associated mechanisms of formation. The term “black” salt also has a non-technical culinary association (kala namak[1]) but, other than in the footnote, I will not discuss it further in this series of articles. The geological descriptor “black” or “dark” salt is widely used in the US salt mining industry as a pointer to possible zones of current or past natural fluid entry into the salt mass. Colouring fluids can be brine, oil or gas, often with solid impurities dominated by shale, anhydrite or calcite-dolomite. These intrasalt “black” or “dark” salt zones in a mine were also referred to as “shear” zones and considered pointers to what are often unstable regions, liable to fluid entry, gassy outbursts and roof or wall collapse. “Shear”, “black” and “dark” salt zones are better described under the broader term “anomalous salt” zones, many of which were or are  in fluid contact with the enclosing non-salt sediment mass (Kupfer, 1990).

In a somewhat related fashion, the term “black salt” is used by the oil industry in Oman and Europe to indicate subsurface zones of overpressured salt, where natural hydrofracturing has occurred, and hydrocarbons have penetrated up to 100 m into the sealing salt mass. Hence its dark color (naturally hydrofractured salt and its textures are the focus of the second article in this series on salt leakage). Fluid entry in this type of “black’ salt is ascribed to temperature-related changes in the dihedral angle of the halite crystals in “black” salt zones. In a similar fashion, the term “black” salt was used in a recent paper in Science by Ghanbarzadeh et al. (2015) and the dihedral angle changes are ascribed to temperature increases in halokinetic salt intervals in the offshore Gulf of Mexico. There the authors argue temperature increases have changed the intercrystalline dihedral angle in a salt mass, and so facilitated the entry of fluids from adjacent strata into the salt body.

So, the term “black” salt is used in the geological community without reference to geological criteria that can separate what I consider are at least two distinct styles of “black” or “dark” salt formation and leakage. One type of salt leakage occurs when the salt is relatively shallow and subject to dissolution driven by the entry of meteoric and other near-surface undersaturated waters into folded and refolded shear (anomalous) salt zones in and about salt stems and décollements. This typically occurs when the flowing salt crest is relatively shallow and tends to occur in regions where the leaking “black” salt zone is in contact with the nonsalt boundary edges of the halokinetic salt mass. This process set ultimately leads to an accumulation of insoluble residues (clays, anhydrite, gypsum, calcite, etc.) that define a unit called a caprock. The term “cap” is somewhat of a misnomer as “caprock” units also form on the sides and undersides of a salt mass, wherever the salt unit is in contact with undersaturated cross-flowing formational waters (Warren, 2016). The other type of “black salt, exemplified by the Ara salt in Oman is related to deeper salt burial, salt flow and an association with intrasalt pressurized fluids (a focus of next article in this series on salt leakage). Accordingly, if we are not to confuse styles of “black” salt genesis (meteoric or undersaturated fluid entry versus intrasalt overpressures) then a better non genetic term should be used to describe zones of "black" or "dark" salt. Although less euphonious, the better term is “anomalous” salt. This describes all zones within halite-dominant intervals with features that are not typical of the bulk of the main diapiric salt mass (Kupfer, 1990).

In this first article we look at various types of anomalous salt in salt mines, largely related to the entry of, or interaction with, undersaturated relatively shallow formation waters. The next article focuses on salt leakage and "black" salt related to overpressure. Then, as we shall see in the third article on salt leakage, there are significant implications of occurrences of anomalous salt with respect to practicalities of safe intrasalt storage and fluid contamination with respect to separating the two types of black salt. This is especially so when working in the subsurface without the luxury of core or mine wall exposures. Ignoring the origins of “black” or “dark” salt, and the associated implications for wireline interpretation, means any conclusions in terms of waste storage outcomes and/or hydrocarbon seal potential, by generalizing lab-based experimental results on leaking salt to all “black” salt occurrences in halokinetic settings, will be somewhat confused (e. g. Ghanbarzadeh et al., 2015).

Black salt (dark salt) in anomalous salt in response to undersaturated fluid entry

Intervals of “black” or dark salt are described in US Gulf Coast salt mines in publications by Balk (1953), Kupfer (1976, 1990) and Looff et al., (2010), the following observations are largely based on their work. Nearsurface (<1-2 km) portions of mined or cored diapirs with “black” salt zones in the Gulf Coast USA and Germany are segmented into a number of intradiapir zones showing differential movement between adjacent salt spines or flowing masses. The more homogenous intervals of consistently mineable salt ore are separated by anomalous zones, formerly called “shear” zones. This association of homogenous spines separated by narrower shear or anomalous zones was first mapped in mine walls in the Jefferson Island salt dome by Balk (1953). His work was one of a series of classic papers mapping the internal structural complexities and shears in various mined salt diapirs in the US Gulf Coast and the Zechstein of Germany. Subsequent work by Kupfer (1976) on the same US Gulf Coast Five-Island salt mines (Jefferson Island, Avery Island, Weeks Island, Cote Blanche and Belle Isle) further refined notions of internal shear and occurrences of “black” or “dark” salt in diapirs. Today, only the Cote Blanche and Avery Island salt mines are still in operation along the Five Island Salt Dome Trend (Figure 1)

A shear zone in a diapiric structure forms where adjacent parts of a salt structure are moving (rising or falling) at different rates. Such zones tend to dominate the perimeter of a salt structure across which salt mass is rising or falling with respect to the adjacent sediment and so grade outward from the salt spine into a boundary “shale sheath”. Older shear zones and shale sheaths also are commonplace in re-folded intervals within a salt stem. Mapping of these zones by Balk (1953), Muehlberger and Claubaugh (1968) and Kupfer (1976) across many salt mines showed salt in a diapir must flow at different rates at different times. Otherwise, the complex and highly variable internal refolded drape and napkin folds seen in diapirs in all the world’s salt mines could not form. Figure 2 illustrates some internal complexities the diapir scale typifying various diapiric salt structures across the world and the dominantlyvertical flow fabrics in diapir stems and subhorizonatal flow textures in overhangs and salt tongues. Figure 3 shows that same vertical dominance (biaxial elongation) of salt crystals from cores collected in diapir stems cored various salt mines, while Figure 4 shows the typical vertical banding fold style that typifies diapir stems.



Walden and Jacoby (1963) were the first to call attention to a Gulf Coast anomalous salt zone. They documented a fault zone in the Avery Island salt mine that separated the region of salt being mined, across an anomalous zone, from the domal core. To call attention to the zonal ductile, not brittle, nature of intradiapir salt flow, Kupfer, 1974 changed the description of such anomalous zones from "fault” zones to "shear” zones and concluded most intradiapir shear zones were not faulted zones (defined by brittle fracture offset). In a later paper, he suggested abandoning of the genetic and misleading term "shear zone" and proposed replacement with the broader nongenetic term "anomalous salt zone" (Kupfer, 1990).


The term “anomalous salt,” as defined by Kupfer (1990), is based on his then more than twenty years experience in various salt mines in the US Gulf Coast. An anomalous salt zone is defined broadly as a zone of anomalous features in salt of whatever origin. He noted that typical anomalous salt zone features are different to the majority of features in the adjacent salt and involve varying combinations of anomalous features that include:

Textures--Coarse-grained, piokiloblastic, friable

Inclusions--Sediments, hydrocarbons, brine, gases

Structures--Sheared salt, gas outbursts, brine leaks, undue roof and wall slabbing, jointing, voids, and slight porosity development

Compositions--Potash/magnesium, high anhydrite content, very black salt (made up of disseminated fluid and solid impurities.

The terms “anomalous salt” and “anomalous zones” as defined by Kupfer (1990), are based on observations across the various Five Island salt mines of South Louisiana (Figure 1). As later refined in Kupfer et al. (1998), anomalous salt is a rocksalt zone that deviates from what are considered typical domal salt. Typical Gulf Coast rocksalt according to Kupfer is reasonably pure halite (97%+/- 2%), with minor amounts of disseminated anhydrite (CaSO4) being the primary non-halite impurity. Grainsize is considered to be uniform with grain diameters of 3 – 10 mm (0.12 – 0.39 inches). With continued mapping of Five Island mines, Kupfer et al. (1998) and Looff et al. (2010) documented an even wider variety of anomalous salt zone characteristics and concluded that the creation of anomalous zones need not be related to faulting or shearing, but also can be related to fluid entry and salt dissolution (Figure 5). Anomalous salt can be defined by impurity content, structure, colour, or other features. Anomalous features may not have sharp contacts or uniform thickness, and most are not continuous over long distances. Individual anomalous features commonly disappear for tens of metres (hundreds of feet) only to appear over some horizontal distance. The internal salt fabric of a salt dome is always composed of both typical (volumetrically dominant) and anomalous salt. Kupfer (op. cit.) noted that other salt deposits, including horizontally bedded nonhalokinetic salt deposits in the Permian of West Texas and the Devonian of Western Canada, all have anomalous zones of various origins.


Further work in both the salt mines and salt cavern storage industry has increasingly invoked the concept of anomalous features, anomalous zones and boundary shear zones although there is still a significant confusion over the appropriate use of the terminology (Looff et al., 2010). Because of the flow experienced by diapiric salt, most anomalous salt features parallel the near vertical internal banding of the salt. Many anomalous salt features may create zones of differing creep, strength, or dissolution characteristics that can impact the solution mining and operation of a salt storage cavern and some are tied to zones of problematic fluid entry in a mine. An anomalous zone is any zone in a salt diapir that contains 3 or more dissimilar anomalous features (Kupfer, 1990). The term “anomalous” implies nothing regarding the genesis of the zone. While many anomalous zones may extend laterally over hundreds of metres in length, they are variable in nature, near vertical, and parallel to layering (Figure 5). Typical widths are poorly known but are commonly in the order of 30-50m; however individual structures or anomalous features within the anomalous zone may be as thin as millimetres.

Boundary Shear Zones (BSZ) and Edge Zones (EZ) are the two types of anomalous zones that have a genetic interpretation (Looff et al., 2010). Boundary shear zones are those zones that bound an active salt spine where the salt experiences increased shear stress due to differential salt movement. An edge zone is similar to a boundary shear zone except, instead of being internal within the dome, it is confined to the periphery of the salt stock. Anomalous salt is not restricted to shear zones, however within and about as diapir edge one can expect most anomalous salt to be associated with shear zones (Kupfer, 1990; Looff, 2000).

Anomalous zones within a salt spine are in many cases the remnants of relict BSZ’s from older spines incorporated into younger active salt spines and this especially obvious with those boundary zones associated with clastic impurities (Figure 6). Boundary shear zones and edge zones around the dome tend to be more problematic for storage caverns as they are likely to contain greater occurrences of anomalous salt, higher impurity content (including gas and brine) and structural features that may degrade salt quality and enable leakage. Thus salt caverns can be constructed within boundary salt zones, but if possible, they should be avoided as they can result in non-optimal operating conditions, long-term operational difficulties and in the most severe cases contribute to the loss of cavern integrity (Looff et al., 2010). In the case of edge zones, additional distance to the edge of the salt dome needs to be maintained not only to cover any uncertainty regarding the placement of the edge of salt with respect of mine workings but also to account for the potential for degraded salt quality and to provide a sufficient pillar of good quality salt between the mine or cavern wall and the edge of dome.


A top-of-salt boundary between aggradational and dissolutional components atop diapirs in the Five Islands salt landscape typically coincides with underlying anomalous zones of differential shear within the underlying diapir typically indicated by “black” or “dark” salt zones in the various diapirs (Kupfer, 1976; Lock, 2000). Where such interior anomalous “black” salt zones have intersected the edge of the salt mass, they tend to create intervals with a greater propensity for water entry or gas outbursts and unstable roof zone liable to slabbing and collapse (Figure 6). Such anomalous zones can leak water into a mine, and over the longer term create stability problems, as illustrated by problems in; the now abandoned Weeks Island oil storage facility, the Avery Island Salt Mine, and the likely association of a subvertical zone with anomalous salt, and the enhanced fluid entry that occurred during the Lake Peigneur collapse, which was tied to 1980 flooding of the former Jefferson Island Salt Mine. Today, only two of the former mines in the Five Island Salt Dome trend remain unflooded. For a more detailed discussion of these and other salt leakage scenarios tied to undersaturated fluid entry into salt mines and caverns, see case histories in Chapter 13, Warren 2016.

“Black” or “Dark” Salt zones and leakage into the former Weeks Island storage facility

In the walls of the now-flooded Weeks Island salt mine, Kupfer (1976) noted that wide black beds of the internal “shear” zone are unusual and not found over most of the rest of the mine where salt was extracted. In places, the anomalous zone beds contain black clay (Room J-21), orange sandstone (S-20), and other fragments of clastic material (Paine et al., 1965). These clastic remnants typically occur as balls or roundish blebs ranging in size up to tens of cm in diameter. Petroleum leaked out of seams in this black salt zone and seams in the surrounding salt; the escaping fluid ranged from yellow grease and heavy, blue oil to very light, straw-yellow distillate. Methane and carbon dioxide were also common. The width (surmised) and structural complexity of the anomalous zone suggest that internal salt movement continued after a clastic boundary sheath-zone was incorporated into the salt stock (Figure 7).


The cause of the drainage and abandonment of the Weeks Island oil storage facility was an active subsidence sinkhole some 10 metres across and 10 metres deep, first noted near the edge of the SPR facility in May 1992, and perhaps reaching the surface about a year earlier. The growing doline depression was located on the south-central portion of the island, directly over a subsurface trough, which was obvious in the top-of-salt contours based on former mine records before conversion to a hydrocarbon storage facility (Figure7; Neal and Myers, 1995). Earlier shallow exploratory drilling around the Department of Energy service and production shafts in 1986 had identified the presence of irregularities and brine-filled voids along the top of salt mass across this region. A second, much smaller sinkhole was noticed in early February 1995, but it did not constitute a serious threat as it lay outside the area of cavern storage.

The first sinkhole occurs in a position of sharp change in landform slope (transition from high island to gully fill) and lies atop the projected alignment of what is known as Shear Zone E (a dark salt zone) in the underlying salt (Autin and McCulloh, 1995). Neal (1994) pointed out that Kupfer’s 1976 map of that part of the Weeks Island salt mine, located beneath the first sinkhole, was defined by black salt (also shown as Figure 8 which is based on the more recent Kupfer et al. (1998) map). Miners always avoided such “black” salt or “dark” salt zones in the various subsurface workings and the lateral extent of workings in many of the Five Island mines extended only as far as intersections with significant “black” or “dark” salt regions (Figure 6 & 7).


The volume of the first Weeks Island sinkhole (estimated as 650 m3 when first noted), its occurrence over a trough in the top of salt, and its position directly above the oil-filled mine caverns, meant it was of urgent concern to the SPR authorities, especially in terms of the stability of the roof of the storage cavern. This feature did not form overnight; it lies atop a shear zone that formed during the diapiric rise of the salt and capped by a rockhead valley containing Pleistocene sediment fill. Salt extraction during mine operations probably created tension across the shear zone, thereby favouring fracture enlargement in the anomalous salt zone, as early perhaps as 1970 (Figure 6; Waltham et al., 2005). Eventually, an incursion of undersaturated groundwater traversed the fracture zone across some 107 m, from a level equivalent to the rockhead down to the mine where it emerged. Over time, ongoing dissolution enlarged a void at the top of the anomalous salt zone, creating the collapse environment for the sinkhole first noted at the land surface in 1991. Investigations were undertaken in 1994 and 1995 into the cause of active at-surface sinkholes verified that water from the aquifer above the Weeks Island salt dome was seeping into the underground oil storage chamber at the first sinkhole site (Figures 7& 8; Neal and Myers, 1995; Neal et al., 1995, 1997). Drainage and decommissioning of the Weeks Island facility followed.

Beginning in 1994, and continuing until the abandonment of the facility, saturated brine was injected directly into the throat of the first sinkhole, which lay some 75 metres beneath the surface. This essentially arrested further dissolution and bought time for DOE (Department of Energy) to prepare for the safe and orderly transfer of crude oil to another storage facility. To provide added insurance during the oil transfer stage, a “freeze curtain” was constructed in 1995. It consisted of a 54 well installation around the principal sinkhole, which froze the overburden and uppermost salt to a depth of 67 metres (Figure 9; Martinez et al., 1998). Until the mine was filled with brine and its hydrocarbons removed, this freeze wall prevented groundwater flow into the mine via the region of black salt around the sinkhole. Dealing with this sinkhole was costly. Mitigation and the removal and transfer of oil, including the dismantling of infrastructure (pipelines, pumps, etc.), cost a total of nearly US$100 million; the freeze curtain itself cost nearly $10 million.


Following oil fill in 1980-1982, the Weeks Island facility had stored some 72.5 million BBL of crude oil in abandoned mine chambers. Then in November 1995, the Department of Energy (DOE) initiated oil drawdown procedures, along with brine refill and oil skimming, plus numerous plugging and sealing activities. In 1999, at the end of this recovery operation, about 98% of the crude oil had been recovered and transferred to other SPR facilities in Louisiana and Texas; approximately 1.47 MMBL remains in the now plugged and abandoned mine workings. In hindsight, based on an earlier leak into the mine, while it was an operational mine, and the noted presence of black salt in a shear zone in the mined salt, one might fault the initial DOE decision to select this mine for oil storage. In 1978 groundwater had already leaked into a part of the mine adjacent to the sinkhole and this was forewarning of events to come (Martinez et al., 1998). Injection of cement grout into the flow path controlled the leak into the operation mine at that time, but it could just as easily have become uncontrollable and formed a sinkhole then.


Black salt zones in the now-flooded Jefferson Island Salt Mine and the 1980 Lake Peigneur collapse

The most recently risen part of the Jefferson Island stock crest is now 250 m (800 ft) higher than the adjacent flat-topped salt mass, which is also overlain by a cap rock (Figure 10). The boundary separating the spine from the less active portion of the crest is a finer-grained and a “shale-rich” anomalous zone, penetrated by the former Jefferson Island mine workings. It defined a limit to the extent of salt mining in the diapir, which was focused on extracting the purer salt within the Jefferson Island spine. The spine and its boundary “shear” are reflected in the topography of the Jefferson Island landscape, with a solution lake, called Lake Peigneur, defining the zone of shallower salt created by the active spine. There on November 20, 1980, one of the most spectacular sinkhole events associated with oilwell drilling occurred atop the Jefferson Island dome just west of New Iberia. Lake Peigneur disappeared as it drained into an underlying salt mine cavern and a collapse sinkhole, some 0.91 km2 in area, developed in the SE portion of the lake (Figure 11; Autin, 2002; Warren 2016). In the 12 hours following the first intersection the underlying mine had flooded and the lake was completely drained. The lake is about 2.4 km in diameter, has a bean-shaped configuration, with a topographic promontory along the southeast shore of the lake rising to more than 23 m above sea level and the surrounding delta plain (Figure 10).

Drainage and collapse of the lake began when a Texaco oilrig, drilling from a pontoon in the lake, breached an unused section of the salt mine some 1000 feet (350 metres) below the lake floor (Figure 11). Witnesses working below ground described how a wave of water instantly filled an old sump in the mine measuring some 200 ft across and 24 feet deep. This old sump was in contact with a zone of anomalous “black” (shear zone) salt. The volume of floodwater engulfing the mine corridors couldn’t be drained by the available pumps. At the time of flooding the mine had four working levels and one projected future level. The shallowest was at 800 feet, it was the first mined level and had been exploited since 1922. The deepest part of the mine at the time of flooding was the approach rampways for a planned 1800 foot level. Some 23-28 million m3 of salt had been extracted in the preceding 58 years of mine life. The rapid flush of lake water into the mine, probably augmented by the drainage of natural solution cavities in the anomalous salt zone and associated collapse grabens below the lake floor, meant landslides and mudflows developed along the perimeter of the Peigneur sinkhole, so that post flooding the lake was enlarged by 28 ha.


With water filling the mine workings, the surface entry hole in the floor of Lake Peigneur quickly grew into a half-mile-wide crater. Eyewitnesses all agreed that the lake drained like a giant unplugged bathtub—taking with it trees, two oil rigs (worth more than $5 million), eleven barges, a tugboat and a sizeable part of the Live Oak Botanical Garden. It almost took local fisherman Leonce Viator Jr. as well. He was out fishing with his nephew Timmy on his fourteen-foot aluminium boat when the disaster struck. The water drained from the lake so quickly that the boat got stuck in the mud, and they were able to walk away! The drained lake didn’t stay dry for long, within two days it was refilled to its normal level by Gulf of Mexico waters flowing backwards into the lake depression through a connecting bayou (Delcambre Canal, aka Carline Bayou) former what was a waterfall with the highest drop in the Stat of Louisiana. Since parts of the lake bottom had slumped into the sinkhole during the collapse, the final water level in some sections of the lake was higher than before relative to previous land features. This ground movement and subsidence left one former lakefront house aslant under 12 feet of water.

Implications for other salt mines with anomalous salt zone intersections.

The Peigneur disaster had wider resource implications as it detrimentally affected the profitability of other salt mines in the Five Islands region (Autin, 2002). Even as the legal and political battles at Lake Peigneur subsided, safe mining operations at the nearby Belle Isle salt mine came into contention with public perceptions questioning the structural integrity of the salt dome roof. During ongoing operations, horizontal stress on the mineshaft near the level where the Louann Salt contacts the overlying Pleistocene Prairie Complex across a zone of anomalous salt had caused some mine shaft deterioration. Broad ground subsidence over the mine area was well documented and monitored, as was near continuous ground water leakage into the mine workings. The Peigneur disaster meant an increased perception of continued difficulty with mine operations and an increased risk of catastrophic collapse was considered a distinct possibility. In 1985, a controlled flooding of the Belle Isle Salt m\Mine was completed as part of a safe closure plan.

Subsidence over the nearby Avery Island salt mine (operated by Cargill Salt) has been monitored since 1986 when small bead-shaped sinkholes were initially noticed in the above mine region. Subsidence monitoring post-1986 defined a broad area of bowl-shaped subsidence, within associated areas of gully erosion (Autin, 2002). Avery mine is today the oldest operating salt mine in the United States and has been in continual operation since the American Civil War. The mine underwent a major reconstruction and a improved safety workover after the Lake Peigneur disaster. Subsidence is still occurring today along the active mine edge, which coincides with a topographic saddle above an anomalous salt zone, which is located inside the mined salt area. At times, ground water has seeped into the mine, and there are a number of known soil gas anomalies and solution dolines on the island. These are natural features that predate mining. Much of the subsidence on Avery Island is a natural process as differential subsidence occurs atop any shallow salt structure with the associated creation of zones of anomalous salt (Warren, 2016). Dating of middens and human artifacts around salt-solution induced, water-filled depressions atop the dome, shows dissolution-induced subsidence is a natural process, as are short episodes of lake floor collapse, slumping and the creation of water-filled suprasalt dolines (circular lakes). Such landscape events and their sedimentary signatures have histories that extend back well beyond the 3,000 years of human occupation documented on Avery Island (Autin, 2002).

Compared to the other salt domes of the Five Islands region of Louisiana, the Cote Blanche Island salt mine has benefited from a safe, stable salt mine operation throughout the mine life (Autin, 2002). Reasons for this success to date are possibly; (i) mining operations have not been conducted as long at Cote Blanche Island as other nearby domes, (ii) the Cote Blanche salt dome may have better natural structural integrity than other islands, thus allowing for greater mine stability (although it too has anomalous salt zones, a salt overhang, and other structural complexities), and (iii) the Cote Blanche Salt Mine is surrounded by more clayey (impervious) sediments than the other Five Islands diapirs, all with sandier surrounds, perhaps allowing for lower rates of undersaturated fluid crossflow and greater hydrologic stability.

Significance

And so, today, we know that anomalous salt zones near diapirs crests are often tied to subvertical fault or shear zones, and that many are also associated with the presence of past crossflows of undersaturated waters. Across the various US Gulf Coast mines (present and past) the anomalous (“shear”) salt zones within diapirs are known to be potential problematic leakage zones and so are avoided, if possible, during mining operations. This style of black salt distribution and the potential for intrasalt leakage must be taken into account when near-crestal and shallower portions of domes are to be utilised for any fluid or waste storage. Without an understanding of the significance of such “black” salt or anomalous salt layers, there are potential undefined leakage problems within some salt structures (Looff et al., 2010; Warren 2016).

References

 

Autin, W. J., 2002, Landscape evolution of the Five Islands of south Louisiana: scientific policy and salt dome utilization and management: Geomorphology, v. 47, p. 227-244.

Autin, W. J., and R. P. McCulloh, 1995, Quaternary geology of the Weeks and Cote Blanche islands salt domes: Gulf Coast Association of Geological Societies Transactions, v. 45, p. 39-46.

Balk, R., 1953, Salt Structure of Jefferson Island Salt Dome, Iberia and Vermilion Parishes, Louisiana: Bulletin American Association Petroleum Geologists, v. 37, p. 2455-2474.

Ghanbarzadeh, S., M. A. Hesse, M. Prodanović, and J. E. Gardner, 2015, Deformation-assisted fluid percolation in rock salt: Science, v. 350, p. 1069-1072.

Kupfer, D., 1976, Shear zones inside Gulf Coast salt stocks help to delineate spines of movement: Bulletin American Association of Petroleum Geologists, v. 60, p. 1434-1447.

Kupfer, D., 1980, Problems associated with anomalous zones in Louisiana salt stocks, USA, in A. H. Coogan, and H. Lukas, eds., Fifth Symposium on Salt (Hamburg, Germany, June 1978), v. 1: Cleveland OH, Northern Ohio Geological Society, p. 119-134.

Kupfer, D. H., 1974, Boundary shear zones in salt stocks: in Fourth Symposium on Salt. Northern Ohio Geological survey, v. 1, p. 215-225.

Kupfer, D. H., 1990, Anomalous features in the Five Islands salt stocks, Louisiana: Gulf Coast Association of Geological Societies Transactions, v. 40, p. 425-437.

Kupfer, D. H., B. E. Lock, and P. R. Schank, 1998, Anomalous Zones Within the Salt at Weeks Island, Louisiana: Gulf Coast Association of Geological Societies Transactions, v. 48, p. 181-191.

Lock, B. E., 2000, Geologic Mapping of Salt Mines in Salt Diapirs: Approaches and Examples from South Louisiana: Gulf Coast Association of Geological Societies Transactions, v. 50, p. 567-582.

Looff, K. M., 2000, Geologic and Microstructural Evidence of Differential Salt Movement at Weeks Island Salt Dome, Iberia Parish, Louisiana: Gulf Coast Association of Geological Societies Transactions, v. 50, p. 543-555.

Looff, K. M., K. M. Looff, and C. Rautman, 2010, Salt spines, boundary shear zones and anomalous salts: Their characteristics, detection and influence on salt dome storage caverns: Paper presented at Solution Mining Research Institute Spring 2010 Technical Conference, Grand Junction, Colorado, USA, 26-27 April 2010, 23 p.

Martinez, J. D., K. S. Johnson, and J. T. Neal, 1998, Sinkholes in Evaporite Rocks: American Scientist, v. 86, p. 38.

Muehlberger, W. R., and P. S. Clabaugh, 1968, Internal Structure and Petrofabrics of Gulf Coast Salt Domes: AAPG Memoir, v. 8, p. 90-98.

Neal, J. T., 1994, Surface features indicative of subsurface evaporite dissolution: Implications for storage and mining: Solution Mining Research Institute, Meeting paper, 1994 Spring meeting, Houston Texas.

Neal, J. T., S. Ballard, S. J. Bauer, B. L. Ehgartner, T. E. Hinkebein, E. L. Hoffman, J. K. Linn, M. A. Molecke, and A. R. Sattler, 1997, Mine-Induced Sinkholes Over the U.S. Strategic Petroleum Reserve (SPR) Storage Facility at Weeks Island, Louisiana: Geologic Mitigation Prior to and During Decommissioning, SAND96-2387A.: Presented at 6th Multidisciplinary Conference on Sinkholes and the Engineering & Environmental Impacts of Karst, Springfield, Missouri, April 6-9, 1997. Sandia National Laboratories, Albuquerque, NM.

Neal, J. T., S. J. Bauer, and B. L. Ehgartne, 1995, Sinkhole Progression at the Weeks Island, Louisiana, Strategic Petroleum Reserve (SPR) Site: Solution Mining Research Institute, Fall Meeting, San Antonio, Texas, October 1995. Sandia National Laboratories, Albuquerque, NM.

Neal, J. T., and R. E. Myers, 1995, Origin, Diagnostics, and Mitigation of a Salt Dissolution Sink-hole at the U,S. Strategic Petroleum Reserve Storage Site, Weeks Island Louisiana,: Sandia National Laboratories, Albuquerque, NM. Report Sandia SAND95-0222C Paper presented at the Fifth International Symposium on Land Subsidence, The Hague, October 1995. Proceedings of the Fifth International Symposium on Land Subsidence, IAHS Publ. No. 234.

Paine, W. R., M. W. Mitchell, R. R. Copeland Jr., and L. d. A. Gimbrede, 1965, Frio and Anahuac Sediment Inclusions, Belle Isle Salt Dome, St. Mary Parish, Louisiana: American Association Petroleum Geologists - Bulletin, v. 49, p. 616-620.

Walden, W., and C. H. Jacoby, 1963, Exploration by horizon­tal drilling at Avery Island, Louisiana, in A. C. Bersticker, ed., Symposium on Salt (First): Cleveland, OH, Northern Ohio Geo­logical Society, p. 367-376.

Waltham, T., F. Bell, and M. Culshaw, 2005, Sinkholes and Subsidence: Karst and Cavernous Rocks in Engineering and Construction: Berlin Heidelberg, Springer Praxis Books, 382 p.

Warren, J. K., 2016, Evaporites: A compendium (ISBN 978-3-319-13511-3) Released Jan-Feb. 2015: Berlin, Springer, 1854 p.

 

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[1] Pungent-smelling condiment Kala Namak (black salt) is widely used in South Asia, it consists primarily of sodium chloride with trace impurities of sodium sulphate, sodium bisulphate, sodium bisulphite, sodium sulphide. Kala Namak is also known as Himalayan Black Salt, Sulemani Namak, Bit Lobon , Kala Noon or as Bire Noon in Nepal. Its characteristic smell and taste is mainly due to its elevated sulfur content, which to a western nose is reminiscent of rotten eggs, largely due to the presence of greigite. The various iron impurities impart a brownish pink to dark violet colour to the coarse translucent crystals and, when ground into a powder, transform into a light purple to pink color.

Traditionally, mined salt was transformed from the raw natural form of salt into commercially-sold kala namak through a reductive chemical process. This heating transforms some of the naturally occurring iron oxidew and sodium sulfates in the raw salt into pungent hydrogen sulfide and sodium sulfide daughter products (along with greigite.[ The various sulphate salt impurities in the halite typify the partially recrystallised meteoric overprints that typify textures and structures in nearsurface salt residues in the Himalayan thrust belt (see Richards et al., 2015 for documentation of the geological and structural characteristics of this salt – this article can be downloaded from the publications page on this website).

Historically, the transformation of Himalayan thrust belt salt into kala namak involved firing the raw salt in a furnace for 24 hours, while sealed in a ceramic jar containing charcoal along with small quantities of harad seeds, amla, bahera, babul bark, or natron. The fired salt was then cooled, stored, and aged prior to sale. Kala namak is still prepared in this manner in northern India with production concentrated in Hisar district, Haryana. Although the kala namak can still be produced from natural salts with the required compounds, it is now common to now manufacture it synthetically using halite from non-Himalayan sources. This is done through combining sodium chloride with smaller quantities of sodium sulfate, sodium bisulfate and ferric sulfate, which are then chemically reduced with charcoal in a furnace. Reportedly, it is also possible to create similar products through reductive heat treatment of sodium chloride, 5–10% of sodium carbonate, sodium sulfate, and some sugar.


 

 

 


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