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John Warren - Friday, Dec 31, 2018 BrineSalty evolution Matters & origins of pot- ash: primary or secondary? Ancient potash ores: Part 3 of 3 Introduction Cross ow of In the previous two articles in this undersaturated water series on potash exploitation, we Congruent dissolution looked at the production of either Mouldic MOP or SOP from anthropo- or Porosity genic pans in modern saline lake settings. of interest formed in solar evaporation pans Dissolved solute shows stoichiometric match to precursor, and dropped out of solution as: dissolving goes 1) Rafts at the air-brine interface, A. completely into solution 2) Bottom nucleates or, 3) Syn- depositional cements precipitated MgCl in solution B. 2 within a few centimetres of the Cross ow of depositional surface. In most cases, undersaturated water periods of more intense precipita- Incongruent dissolution tion tended to occur during times of brine cooling, either diurnally Sylvite or seasonally (sylvite, carnallite and halite are prograde ). All Dissolved solute does not anthropogenic saline pan deposits stoichiometrically match its precursor, examples can be considered as pri- while the dissolving salt goes partially into solution and a mary precipitates with chemistries new daughter remains tied to surface or very nearsurface Figure 1. Congruent (A) versus incongruent (B) dissolution. brine chemistry. In contrast, this article discusses the and the Qaidam sump most closely resemble ancient potash deposits where the post-deposition chem- those of ancient MgSO4-depleted oceans, while SOP fac- istries and ore textures are responding to ongoing alter- tories in Great Salt Lake and Lop Nur have chemistries ation processes in the diagenetic realm. Unlike the mod- more enriched in MgSO4. ern brine pans where chemistries and harvested are controllable, at least in part, these ancient Incongruent dissolution in burial deposits show ore purities and distributions related to on- Many primary salts dissolve congruently in the going natural-process overprints. diagenetic realm; i.e., the composition of the solid and the dissolved solute stoichiometrically match, while the dis- Table 1 lists some modern and ancient potash deposits and solving salt goes entirely into solution (Figure 1a). This prospects by dividing them into Neogene and Pre-Neogene situation describes the typical subsurface dissolution of deposits (listing is extracted and compiled from SaltWork® anhydrous evaporite salts such as halite or sylvite. How- database Version 1.7). The Neogene deposits are associated ever, some evaporite salts, typically hydrated salts, such as with a time of MgSO4-enriched seawaters while a majority or carnallite, dissolve incongruently in the dia- of the Pre-Neogene deposits straddle times of MgSO4 en- genetic realm, whereby the composition of the solute in richment and depletion in the ocean waters. Ionic propor- solution does not match that of the solid (Figure 1b). This tions in the feed brines to modern MOP brine factories in solubilisation or mineralogical alteration is defined by the

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transformation of the "primary solid" into a secondary sol- gypsum to via dehydration (reaction 1) id phase, typically an anhydrous salt, along with the loss of CaSO .2H O --> CaSO + 2 H O ... (1) water formerly held in the lattice structure. The resulting 4 2 4 2 solution generally also carries some ions away in solution. or the in-situ conversion of carnallite to sylvite via the loss of magnesium in aqueous solution (reaction 2) More than a century ago, van't Hoff (1912) suggested that ++ - much subsurface sylvite is the result of incongruent solu- KMgCl3.6H2O --> KCl + Mg + 2Cl + 6H2O ...(2) tion of carnallite yielding sylvite and a Mg-rich solution. Typically, with incongruent dissolution a new solid miner- According to Braitsch (1971, p. 120), the incongruent al- al remains and the related complex equilibrium teration (dissolution) of carnallite is perhaps the most cru- creates a saline pore water that may, in turn, drive further cial process in the alteration of subsurface potash salts and alteration or dissolution as it leaves the reaction site (War- the formation of diagenetic (secondary) sylvite. ren, Chapters 2 and 8). Specifically for ancient potash, Widespread burial-driven incongruent evaporite reactions reaction 2 generates magnesium and chloride in solution in the diagenetic realm include the burial transition of and has been used to explain why diagenetic and

Location, country, main Age Köppen Brine Target unit Comments/key reference product source

Quill Lake, Quat. Dfb Nonmarine Lake brine Saline depression in Quaternary glacial outwash. Supratill, sulphate salts in SOP lake floor beds, lake brine pumping and winter processing brine then combined with MOP (trucked in) to produce SOP (Eatok, 1987). Salar de Atacama brine, Quat. BWk Nonmarine Lake brine Brine Processing. Sylvinite, MOP and SOP is recovered as byproducts of lithium car- Chile bonate production (830,000 metric tons potash in 2016). Situated in Andean Altiplano at SOP/MOP 2250m above sealevel. Lop Nur, China Quat. BWk Non Marine Lake brine Natural lake are a nonmarine assemblages of --polyhal- SOP ite-bloedite-gypsum-halite. Recent evaporitic stages of the lake fill in Lop Nur contain massive amounts of glauberite and , compared to the other salts present. Their predominance, is indicative of pervasive back-reactions, as is the presence of very minor amounts of carnallite and sylvite. Lake waters are processed to produce SOP (Ma et al., 2010; Dong et al., 2012). Annual capacity 1.7 million tonnes SOP. Largest set of salt ponds in world. Dabuxum Lake, Qahran Quat. BWk Nonmarine Lake brine Carnallite (via solar processing of lake brine along with bishofite).Transtensional basin Playa, Qaidam Basin, China at 2675m elev. The Qahran playa region is main local supplier of potash to Chinese

SOP/MOP market (annual production of 1.2 Mt K2O). Other Quaternary K-rich lakes in Qaidam Basin include Seni Lake and Tuanje Playa (Duan and Hu, 2001) Dead Sea brines, Israel and Quat. BSh Nonmarine Holocene Brine Processing (carnallite ppt. and converted to KCl) of lake brine pumped into a se- Jordan anthrop. ries of processing pans at southern end of Dead Sea. The Dead Sea brine contains an

MOP (due to inflow brine estimate 2 Gt of dissolved KCl, 1 Gt of MgBr2 and 20 Gt of MgCl2. Annual production of

mostly dissolving older KCl ≈ 3.4 Mt (MgCl2 is coproduct) Subsealevel transtensional basin with brine surface marine evaporites) some 415 m below sealevel. (Recent) (Zak, 1997, Garrett, 2004) Great Salt Lake region, Quat. Csa Nonmarine Lake brine Processing of lake brines in North Arm of lake and of shallow brines in Great Salt Lake Neogene , USA desert (Bonneville Basin) at Wendover (MgCl is coproduct). Lake surface is 1270 m SOP above msl. (Bingham, 1980; Garrett, 2004) Paradox Potash Basin, brine BSk Nonmarine Lake brine Solution mining of Paradox Fm. in converted conventional mine on Cane Creek Utah, USA source from Para- anticline at a depth of 850 m. Middle Pennsylvanian collision basin related to Mara- MOP (due to inflow dissolv- Penn. dox Fm. thon-Ouchita orogeny, 18 of 29 halite cycles contain potash, mostly sylvite. (Moscovian) ing older marine evaporites) Mid. Tachyhydrite present (Desmoinian). (Hite, 1961; Williams-Stroud, 1994) Dallol Saline pan, Ethiopia Quat. BWh Marine Lake brine Three members; uppermost is sylvinite member up to 10 thick; intermediate is 3-24 SOP in m thick with carnallite throughout, (sylvite at its top and at its base) and lower member is kainite that is 4-13 m thick. It is a Pleistocene marine-fed unit that now Fm. lies beneath continental halite in a subsealevel (-115 msl) hydrographically-isolated marine-fed rift valley, region of active volcanism and hydrothermal overprints. (Garrett, 2004; Bastow et al., 2018) Sicilian Basin, Italy Mioc., - Marine Solfifera Inactive since mid 1990s. Kainite was dominant ore mineral (manufactured SOP Late Series sulphate). Other in ore were sylvite, , and bischofite in 2-30m thick beds dipping to 60°. Piggy-back basin in thrust belt. (Messinian) (Adamo, 1992). Carpathian foredeep, Mioc. - Marine Tyras Suite Stebnik mine and Kalush-Golyn region. Four evaporite cycles upper three with potash; Ukraine Middle exploited potash units composed of kainite, , kainite–langbeinite, sylvinite MOP/SOP and carnallite rocks with layers of rock salt or interbedded clays and carbonates. Fourth bed is polyhalite. (Burdigalian-Helvetian). (Hryniv et al., 2007) Table 1. Potash occurrences, listed by age, reserves listed in thousand metric tons (kt), million tons (mt), or billion (Gt) metric tons of K2O equivalent. SOP = Sulphate of Potash, MOP = Muriate of Potash (Listing is extracted from SaltWork® Database Version 1.7; for overviews of the of the deposits see Garrett, 2004; Prud’homme and Krukowski, 2006; Warren, 2010, 2016 and references therein). Page 2 www.saltworkconsultants.com

Location, country, Age Köppen Brine Target unit Comments/key reference main product source

Mulhouse Potash Eoc.- - Marine Upper Salt Main potash target is primary sylvite bed in Salt IV in Oligocene Rupelian succession at depths Basin, Rhine rift, Olig. Group between 420 and 1100m. Basin was a consequence of Paleogene collision between European and African plates. Periodically mined for carnallite/sylvite ore. Subsealevel rift graben was MOP active along western sidewall of the Alpine orogen during collision of the Apulian indentor with the European passive margin. (Sannoisan) (Cendon et al., 2008) Catalonia and Eoc. - Marine to Transitional from marine evaporite to continental, deposited in two depocentres in Southern Pyr- Navarra Potash Upper continental enean foreland. Sylvite+halite at base of unit, carnallite + halite toward top (Bartonian). Lower

Basins, sylvite member is ore bed. MgSO4-free. (Rosell and Orti, 1981; Cendon at al., 2003) MOP Khorat & Sakhon Cret. - Marine Maha Possible sylvinite target on basin margin. Widespread massive halite, carnallite (with local Nakhon Potash Upp. Sarakham zones of sylvinite), tachyhydrite and bischofite traces of priceite/. Unconformable base, Basins, Thailand, Fm. interbedded with three continental redbed successions and overlain by continental deposits. Laos (prospect, Variably halokinetic toward basin centre. (Albian-Cenomanian?) (Hite and Japakasetr, 1979; El likely MOP) Tabakh et al., 1999; Warren, 2000c) Congo and Gabon Cret. - Marine Kouilou Carnallite, sylvinite in halite host, variable tachyhydrite (Aptian). Previously mined at Holle Mine

basins, Africa (Con- Low. horizons (Republic of Congo) in 2 variable layers of 1.9 m and 3 m thickness with K2O contents of 18% go, Zaire, Angola) and 38% respectively with mineable reserves of 17 mt and 26 mt K2O respectively. Mine lost to (prospect, likely flooding (breccia zone) in 1977. Future projected solution mine targeting of K and Mg brines in MOP) Kouilou evaporite horizons. (De Ruiter, 1979) Neuquén and Cret. - Marine Potash Possible future solution mine. Sylvinite ore divided into 2 zones, upper zone about 3 m thick

Mendoza Basins, interval and lower about 11 m thick, average grade 20-25% K2O. A 1000m depth and high formation Andes, Argentina temperature (>50°C) precludes conventional mine (Prud’homme and Krukowski, 2006). (prospect) Salado Potash Perm.- - Marine Salado Fm. Resource now largely depleted, 12 potash horizons in part of known as McNutt Basin, NM, USA Upp. Zone (sylvite ore), few mines still active. Ore zones contain sylvite, carnallite, lesser amounts of historically MOP/ Lower sulphate minerals such as polyhalite and langbeinite (Tatarian - Olenekian). (Lowenstein,1988) increasingly SOP Trias. English Zechstein Perm. - Marine Zechstein 3 Boulby Mine in UK extracts sylvinite ore from two 6-8 m beds at depths between 1000 and

Potash Basin, UK Upp. 2700m, essentially no MgSO4 phases. Water inflow and instability problems (Tatarian). (Smith, MOP, to polyhalite 1996; Woods, 1979) Zechstein Potash Perm. - Marine Zechstein Actively mined at depths between 300-800m, Zechstein comprises four evaporite cycles, with Basin, Upp. Group potash as five ore horizons in lower three (Thuringen, Hessen, Stassfurt, Ronnenberg and (MOP, minor SOP) Riedel) (Tatarian). Tachyhydrite present in Stassfurt. (Smith and Crosby, 1979; Richter-Bern-

Pre-Neogene berg, 1986) Solikamsk depres- Perm. - Marine Iren horizon Bezeneski and Solimgansk mines. potash interval lies at depths of 200-500m and is divided into

sion, Russia Upp. lower sylvinite and upper sylvinite-carnallite, little to no MgSO4 salts. Av. lower interval thickness MOP 21 m, upper interval 60m. (Kungurian) (Zharkov, 1984) Pricaspian depres- Perm. - Marine Potash Not mined. Potash interval contains polyhalite-halite, bishofite-carnallite, carnallite-halite, inter- sion, Kazakhstan Low. interval val is strongly halokinetic in central part of basin. Oil wells intersected several potash horizons in MOP this region. (Kungurian). (Volozh et al., 2003; Garrett, 2004) Amazonas Basin, Upp. - Marine Nova Olin- Two potential sylvinite deposits (sylvite cap to uppermost of 7 evaporite cycles) near Manaus

Brazil (prospect, Carb.- da Fm. ≈ 1000m depth, with average thickness of 2.7 m and grade 16.5% K2O. (Ufimian - Olenekian) MOP) Perm, (Szatmari et al., 1979) Low. Pripyat Depression, Dev., - Marine Liven Livet (Frasnian) interval made up of four potash horizons with areas between 130 to 1500 sq. Belarus Upp. and Elets km. Sylvite ore with minor carnallite in beds 4cm to 1.5 m thick interbedded with muddy halite. MOP horizons Elets (Fammenian) interval > 60 potash beds over 5,000 sq. km at depth of 200 to 3,000m.

Major potash production from Elets at average depth 480m, grade 18% K2O. (Zharkov, 1984) Alberta Potash Dev., - Marine Prairie Fm Actively mined, some ten mines (2 solution mines) at depths between 800-1000m, region is Basin, Canada Middle world’s major supplier of potash ore. Three potash horizons (sylvite, carnallite, halite) 20-25m MOP thick in upper part of Prairie Fm. (Esterhazy, Belle Plain and Patience Lake members). Dips gently to south at 1-8m/km with potash level some 600-2500m below surface. Prairie Evaporite basin is a marine-fed foreland basin situated behind foreland bulge created by Antlerian orogen. (Givetian) (see text) , Sil. - Marine Salina A-1 Sylvinite and carnallite ore within central part of an intracratonic sag basin. Potash zone > MI, USA Low.- Evap. 30m thick in central part of basin but ore concentration is erratic locally up to 40% K2O and as MOP Upp. deep as 2,550m but only solution mining is possible at these depths. (Wenlockian-Ludlovian). Tachyhydrite present. (Matthews and Egleson, 1974)

Eastern Siberia Camb. - Marine Chara Potash lies at depths of 600-900m and contains some ore-grade sylvite intervals (>30% K2O) in Potash Basin, Rus- Lower horizon Usolye and Angara Fm. Not currently exploited. (Botoman - Amgan) (Zharkov, 1984) sia (MOPprospect) Table 1 continued

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0.22 and Cl- by Br- and I-. These sub- stitutions change the lattice sym- 0.20 y=0.2148x-0.0128 metry from orthorhombic in the (r2=0.9804) 0.18 original carnallite to monoclinic.

0.16 When interpreting the genesis of ancient potash deposits and 0.14 solutions, the elemental segre- 0.12 Secondary sylvite modelled (Wardlaw, 1968) gation in the lattice means trace Primary sylvite modelled (Braitch 1962, 1966) element contents of bromide, ru- Secondary sylvite Khorat Plateau (Hite an Japakasetr, 1979) Rb (‰) 0.10 Secondary sylvite Khorat Plateau (Hite an Japakasetr, 1979) bidium and in primary

Vientiene, Laos (Cheng et al., 2016) L carnallite versus sylvite daughter 0.08 Secondary sylvite, Sergipe (Wardlaw, 1972) Secondary sylvite, Prairie Evaporites (Wardlaw, 1970) crystals from incongruent disso- Secondary sylvite, Prairie Evaporites (Wardlaw, 1968) 0.06 Primary sylvite, Prairie Evaporites (Wardlaw, 1968) lution can provide valuable infor- mation. For example, in a study by 0.04 Wardlaw, (1968), a trace element 0.02 model was developed for sylvite derived from carnallite that gave 0.00 Br and Rb concentration ranges 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 of 0.10–0.90 mg/g and 0.01–0.18 Br (‰) mg/g, respectively. In a later study Figure 2. Primary sylvite (red squares and white triangles has higher Br than incongruent sylvite. That of sylvite derived by fresh-water is, sylvite formed by incongruent conversion creates low Br and high Rb concentrations in sylvite as leaching of magnesium chloride secondary sylvite from the carnallite precursor (after Cheng et al., 2016). under isothermal conditions at 25 °C. Cheng et al. (2016), defined a dolomite can be found in proximity to newly formed sub- model whereby primary sylvites surface sylvite. Bischofite 2MgCl( 2.12H2O) is a highly sol- precipitated from MgSO4-deficient sea water, gave Br and uble salt and so is metastable in many subsurface settings Rb concentration ranges of 2.89–3.54 mg/g and 0.017– where incongruent dissolution is deemed to have occurred, 0.02 mg/g, respectively (no evaporation occurred at satura- including bischofite thermal pool deposits in the Dallol tion with KCl). In general, they concluded sylvite derived sump in the Danakhil of Ethiopia (Salty Matters, May 1, incongruently from carnallite will contain less Br and more 2015). In many hydrologically active systems, solid-state Rb than primary sylvite (Figure 2; Cheng et al., 2016). bischofite is flushed by ongoing brine crossflow and so, via Mg enrichment of the flushing brine, helps drive the for- Subsurface examples mation of various burial dolomites. Only at high concen- The burial-driven mechanism widely cited to explain the trations of MgCl2 can carnallite dissolve without incon- incongruent formation of sylvite from carnallite is illus- gruent decomposition. trated in Figure 3 (Koehler et al., 1990). Carnallite pre- cipitating from evaporating seawater at time 1 forms from Laboratory determinations a solution at 30°C and atmospheric (1 bar) pressure, and In the lab, the decomposition of carnallite in an undersat- so plots as point A, which lies within the carnallite sta- urated aqueous solution is a well-documented example of bility field (that is, it sits above the dashed light brown incongruent dissolution (Emons and Voigt, 1981; Xia et line). With subsequent burial, the pressure increases so al., 1993; Hong et al., 1994; Liu et al., 2007; Cheng et al., that the line defining carnallite-sylvite boundary (solid 2015, 2016). When undersaturated water comes into con- dark brown line) moves to higher values of K. By time 2, tact with carnallite, the rhombic carnallite crystals dissolve when the pressure is at 1 Kbar (corresponds to a lithostatic and, because of the common ion effect, small cubic KCl load equivalent to 2-3 km depth), the buried carnallite is crystals form in the vicinity of the dissolving carnallite. As thermodynamically unstable and so is converting to syl- time passes, the KCl crystals grow into larger sparry sub- vite + solution (as the plot field now lies in the sylvite + hedral forms and the carnallite disappears. solution field (Figure 3). If equilibrium is maintained the

Carnallite’s structure is built of Mg(H2O)6 octahe- carnallite reacts incongruently to form further sylvite and + dra, with the K ions are situated in the holes of chloride MgCl2-solution. Thus, provided the temperature does not ion packing meshworks, with a structural configuration rise substantially, increasing pressure as a result of burial similar to perovskite lattice types (Voigt, 2015). Potassium will favour the breakdown of carnallite to sylvite. Howev- in the carnallite lattice can be substituted by other large sin- er, as burial proceeds, the temperature may become high + + + + + gle-valence ions like NH4 , Rb , Cs or Li(H2O) , (H3O) enough to favour once again the formation of carnallite Page 4 www.saltworkconsultants.com

3.8 stein and Spencer, 1990 for an excellent, if 30-year-old, re- view). We know from numerous evaporation experiments, Carnallite that sylvite does not crystallise during the evaporation of modern seawater at 25°C, except under metastable equilib- 3.6 A rium conditions (Braitsch, 1971; Valyashko, 1972; Hardie, 1984). The sequence of bitterns crystallising from modern Sylvite + MgClburial Time2 log K @1 Kbar seawater bitterns was illustrated in the previous Salty Mat- 3.4 ters article in this series (see Figure 1 in October 31 2018). 2 solution Time 1 Across the literature documenting sylvite-carnallite as- @1 bar sociations in ancient evaporites, the dilemma of primary 3.2 versus secondary sylvite is generally solved in one of three ways. Historically, many workers interpreted widespread 25 35 45 55 sylvite as a diagenetic mineral formed by the incongruent Temperature °C dissolution of carnallite (Explanation 1). Then there is the Figure 3. Increasing the pressure as the carnallite is buried stabilises the interpretation that some sylvite beds, perhaps associated sylvite + solution field and moves the carnallite-sylvite boundary (black line) to higher values of K (frome Time 1 to Time 2), so that at a pressure with tachyhydrite, were precipitated in the evaporite bit- of 1 kilobar, which corresponds to a lithostatic load equivalent to 2-3 km tern part of a basin hydrology that was fed by CaCl2-rich depth, the lAP (indicated by log K) of the solution that precipitated the basinal hydrothermal waters (Explanation 2: see Hardie, carnallite at 1 bar now lies in the sylvite + MgCl2 solution field (after Koehler et al., 1990). 1990 for a good discussion of this mechanism). Then there is the third, and increasingly popular explanation of pri- from sylvite + solution (that is the solution plot point from mary or syndepositional sylvite at particular times in the A moves toward the right-hand side of the figure and back chemical evolution of the world oceans (MgSO4-depleted into the carnallite stability field). oceans). Sylvite, interpreted to have formed from incongruent dis- Changes in the relative proportions of magnesium, sulphur solution of primary carnallite, is reported from the Late and calcium in the world’s oceans are well supported by Permian Zechstein Formation of Germany (Borchert and brine inclusion chemistry of co-associated chevron halite Muir, 1964), Late Permian of New Mex- (Figure 4). Clearly, there are vast swathes of times in the ico (Adams, 1970), Early Mississippian Windsor Group earth’s past when the chemistry of seawater changed so of (Evans, 1970), Early Cretaceous Muribeca that MgSO4 levels were lower than today and it was pos- Formation of Brazil and its equiv- Arag. Calcite Aragonite Calcite Arag. alents in the Gabon Basin, West ? ? ? MgSO4 KCl MgSO4 KCl MgSO4 Africa (Wardlaw, 1972a, b; Ward- 7 Dispersion of Pangean Accretion of law and Nicholls, 1972; Szatmari Pangea supercontinent Pangea et al., 1979; de Ruiter, 1979), Late 6 Cretaceous of the Maha Sara- Fluid inclusions in halite Echinoderms kham Formation, Khorat Pla- 5 Calcite veins teau, Thailand and Laos (Hite 4 and Japakasetr, 1979), Pleistocene MgSO 4 oceans Houston Formation, Danakil De- pression, Ethiopia (Holwerda and Hutchinson, 1968), and Middle 3

Devonian Prairie Formation of + high-Mg calcite Aragonite western Canada (Schwerdtner, 2 Seawater Mg/Ca ratio (molar) 1964; Wardlaw, 1968) (See Table 2 1). 1 Calcite CaCl oceans

This well-documented literature Ng PgPg K J Tr Pm P M D S O C Pre-C 0 base supports a long-held notion 0 100 200 300 400 500 600 that there is a problem with sylvite Time (Ma) as a primary (first precipitate) ma- Figure 4. Secular variation in the Mg/Ca ratio of seawater during the Phanerozoic. Red points are rine bittern salt, especially if the Mg/Ca ratios from inclusions in chevron halite, open circles from marine echinoid skeletons and tri- mother seawater had ionic pro- angles from vein calcites. Horizontal line at Mg/Ca = 2 represents the approximate divide between aragonite + high-Mg calcite (Mg/Ca > 2: indicative of MgSO - enriched oceans) and calcite (Mg/ portions similar to those present 4 Ca < 2; indicative of MgSO4 - depleted of CaCl2 oceans) nucleation fields in seawater at 25°C (after in modern seawater (see Lowen- Holt et al., 2014 and references in text). Page 5 www.saltworkconsultants.com

sible that sylvite was a primary marine bittern precipitate stages during its burial evolution. Alteration can occur syn- (see Lowenstein et al., 2014 for an excellent summary). depositionally, in brine reflux, or later during flushing by compactional or thermobaric subsurface waters or during In my opinion, there is good evidence that all three ex- re-equilibration tied to uplift and telogenesis. Tectonism planations are valid within their relevant geological con- (extensional and compactional) during the various stages texts but, if used exclusively to explain the presence of an- of a basin’s burial evolution acts as a bellows driving fluid cient sylvite, the argument becomes somewhat dogmatic. I flow within a basin, so forcing and speeding up the focused would say that that, owing to its high solubility, the various circulation of potash-altering waters. textures and mineralogical associations of carnallite/sylvite and sulphate bitterns found in ancient potash ore beds re- A similar, but somewhat less intense, textural evolution flect various and evolving origins. Ambient textures and tied to incongruent alteration is seen in the burial histo- mineralogies are dependent on how many times and how ry of other variably hydrated evaporite salts. For example, pervasively in a potash sequence’s geological burial history CaSO4 can flip-flop from gypsum to anhydrite and back an evolving and reactive pore brine chemistry came into again depending on temperature, pore fluid salinity and contact with parts or all of the extent of highly reactive the state of uplift/burial. Likewise, with the more compli- potash beds (Warren, 2000; 2010; 2016). In my experience, cated double salt polyhalite, there are mineralogical chang- very few ancient examples of economic potash show lay- es related to whether it formed in a MgSO4 enriched or ered textures indicating primary precipitation on a brine depleted world ocean and the associated chemistry of the lake floor, instead, most ancient sylvite ores show evidence syndepositional reflux brines across extensive evaporite of at least one episode of alteration. platforms (for a more detailed discussion of polyhalite see Salty Matters, July 31, 2018). Kainite-kieserite-carnallite In other words, various forms and textures of potash may also shows evidence of ongoing incongruent interactions. dissolve, recrystallise and backreact with each other from This means that, as in gypsum/anhydrite/polyhalite or kain the time a potash salt is first precipitated until it is extracted ite/kieserite sequences, there will be primary and second- by coring or mining The observed textural and mineralog- ary forms of both carnallite and sylvite that can alternate ical evolution of a potash ore association depends on how during deposition, during burial and any deep meteoric open was the hydrology of the potash system at various A. B.

Sylvite Halite

Clay 2 cm C. Sylvite drapes chevrons and has a at top (dissolution?) Halite chevrons are bottom -nucleated and growth-aligned

10 mm

Figure 5. Sylvinite ore (Ci in Salt IV) in the Oligocene Mulhouse Basin, Rhine Graben. A) Photograph (metre-scale) of mine wall showing lateral continuity of layering in the sylvinite units. B) Close-up (cm-scale) showing tripartite and vertically-segregated nature of ore body layering (clayey dolomite-halite-sylvite). C) Interpreted photomicrograph of layering (in part after Lowenstein and Spencer, 1990).

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flushing and then again with uplift. In Quaternary brine contact with Triassic, Jurassic and Permian materials. In factories these same incongruent chemical relationships the region of the evaporite basins, the Paleogene fill of the are what facilitate the production of MOP (sylvite) from graben lies directly on the Jurassic basement. The sedimen- a carnallitite feed or SOP from kainite/kieserite/schoenite tary filling of this rift sequence is asymmetrical with the feed (see articles 1 and 2 in this series). deeper parts located at the southwestern and northeastern sides of the Graben (Rouchy, 1997). To document the three end-members of ancient syl- vite-carnallite decomposition/precipitation we will look Palaeogeographical reconstructions place the potential at three examples; 1) Oligocene potash in the Mulhouse marine-seaway or seepage-feed to the north or perhaps Basin where primary sylvite textures are commonplace, 2) also southeast of the Mulhouse Basin, while marginal con- Devonian potash ores in western Canada, where multiple tinental conglomerates tend to preclude any contempora- secondary stages of alteration are seen, and 3) Igneous-dyke neous hydrographic connection with Oligocene ocean wa- associated sylvite in east Germany where thermally-driven ter (Blanc-Valleron, 1991; Hinsken et al., 2007; Cendon et volatisation (incongruent melting) forms sylvite from de- al., 2008). At the time of its hydrographic isolation, some hydrated carnallite. 34 Ma, the basin was located 40° north of the equator. To- tal fill of Oligocene lacustrine/marine-fed sediments in Oligocene Potash, Mulhouse Basin France the graben is some 1,700m thick. The saline stage is dom- Moving back into deep time, this 34 Ma mined potash inated by anhydrite, halite and mudstone. The main saline deposit contains some of the first indications of well pre- sequence is underlain by non-evaporitic Eocene continen- served primary marine-fed sylvinite (MOP) textures, ex- tal mudstones, with lacustrine fossils and local anhydrite emplified by laterally-continuous mm-scale alternations beds. Evaporite bed continuity in the northern part of the of potash, halite layers and clay lamina (Figure 5a-c). In- basin is disturbed by (Permian-salt cored) diapiric and or terestingly, all solid-state potash deposits laid down in the erosional/fault movement. Consequently, these northern post-Oligocene period contain increased proportions of basins are not considered suitable for conventional potash

MgSO4 salts, making them much more difficult to eco- mining (Figure 6a). nomically mine and process (see Table 1 and Salty Matters, The Paleogene fill of the basin is divided into 6 units; a May 12, 2015) pre-evaporitic series, Lower Salt Group (LSG), Middle From 1904 until 2002, potash was conventionally mined Salt Group (MSG), an Upper Salt Group (USG - with in France from the Mulhouse Basin (near Alsace, France). potash), Grey Marls Fm., and the Niederroedern Fm (Fig- With an area of 400 km2, the Mulhouse Basin is the south- ure 7; Cendon et al., 2008). The LSG and lower section of ernmost of a number of Lower

Oligocene evaporite basins that Karlsruhe Diapiric or MULHOUSE BASIN Potassium salts + tectonized zone occupied the upper Rhine Graben, halite+ sulphates which at that time was a narrow Miocene Halite-dominated volcanism adiabatic-arid rift valley (Figure + sulphates Kaiserstuhl Borehole 6a). The graben was a consequence Sulphates of the collision between Europe- Strasbourg Shafts an and African plates during the Paleogene. It is part of a larger intracontinental rift system across Western Europe that extended VOSGES Rhine R. from the North Sea to the Med- Colmar BLACK FOREST iterranean Sea, stretching some Freiburg 300 km from Frankfurt (Germa- ny) in the north, to Basel (Swit- MULHOUSE zerland) in the south, with an BASIN average width of 35 km (Cendon Mulhouse et al., 2008). The southern extent of the graben is limited by a sys- 0 30 tem of faults that place Hercynian JURA Mulhouse Rhine km 10 km massifs and Triassic materials into A. B. Horst River contact with the Paleogene filling. Figure 6. Mulhouse Basin, Rhine Graben. A) Regional distribution of salt basins showing how the potash dominant section is the southernmost of a number of small saline lacustrine deposits in the Across the north, a complex sys- graben. B) Detail of the Mulhouse (Alsace) Basin show how the exploited bedded potash area lay tem of structures (including salt to the southeast of a more disturbed and Permian salt-cored diapiric zone (after Blanc-Valleron and diapirs) put the basin edges in Schuler, 1997). Page 7 www.saltworkconsultants.com

the MSG are interpreted as lacustrine in origin, based on Mi Unit: With a thickness of 6 m, it is mostly halite with the limited palaeontologic and geochemical data. Howev- similar characteristics to the S1 Unit. Sylvite was detected er, based on the presence of Cenozoic marine nannoplank- in one sample, but its presence is probably related to the ton, shallow water benthic foraminifera, and well-diversi- evolution of interstitial brines (Cendon et al., 2008). fied dinocyst assemblages in the fossiliferous zone below Ci Unit (“Couche inférieure”): Is formed by 4 m of alter- Salt IV, Blanc-Valleron (1991) favours a marine influence nating marls/anhydrite, halite, and sylvite beds (Figure 7). near the top of the MSG, while recognising the ambigui- ty of marine proportions with brackish faunas. Many ma- The Ti unit consists of alternating beds of halite, marl and rine-seepage fed brine systems have salinities that allow anhydrite. The top of the interval is the T unit, which is halotolerant species to flourish in marine-fed basins with similar to the S unit and consists of alternating beds of no ongoing marine hydrographic connection (Warren, marl and anhydrite. Above this is the Ms or upper Marl, 2011). According to Blanc-Valleron and Schuler (1997), near identical to the lower marl Mi. The Mi is overlain by the region experienced a Mediterranean climate with long the upper potash bed (Cs), a thinner, but texturally equiv- dry seasons during Salt IV member deposition. alent, bed compared to the sylvinitic Ci unit. In detail, the Salt IV member is made up of some 210 m of evap- Halite-dominant Sylvinite-dominant oritic sequence, with two relatively Quaternary 5-250m Marl- dominant thin potash levels (Ci and Cs). The stratigraphy associated with this 643.1m potash zone is, from base to top O Niederroedern Fm., 550m Ci (Figure 7): L

S2 Unit: 11.5 m thick with dis- CHATTIAN 646.9m tinct layers of organic-rich marls, I Cyrena Marls, 110m often dolomitic, with dispersed Meletta Marls, 110m anhydrite layers. G Fm. Foraminifer Marls + Mi Fish scales, 20m S1 Unit: 19 m thick, evenly-bed- O MarlsGrey ded and made up of alternating Marls without salt, 60m 652.9m metre-scale milky (inclusion-rich) C halite layers, with much thinner E S marls and anhydrite layers (Figure RUPELIAN Salt V, 260m 5a). Marls show a sub-millimet- N 656.6m ric lamination formed by micrit- ic carbonate laminae alternating E with clay, quartz, and organic mat- GROUP UPPER SALT Salt IV, 210m ter-rich laminae. Hofmann et al. Fossiliferrous Zone, 80m (1993a, b) interpreted these cou- plets as reflecting seasonal varia- E 3m tions. Anhydrite occasionally dis- SALT Cs GROUP MIDDLE Ms plays remnant swallowtail ghost O T Salt II, 140m Ti textures, which suggest that at Ci least part of the anhydrite first pre- C Mi S1 Lymnaea Marls II, 170m S cipitated as subaqueous gypsum. Halite shows an abundance of E S1 growth-aligned primary chevron N S2 textures, along with fluid-inclu- Salt I, 390m sion banding suggesting halite was E subaqueous and deposited beneath PRIABONIAN shallow brine sheets (Lowenstein GROUP SALT LOWER and Spencer, 1990). Lymnaea Marls I, 160m 675.5m Pre-Evaporitic Eocene S2 S Unit: Is 3.7 m thick and consists 677.3m of thin marl layers and anhydrite, 0-100m S2 similar to the S2 Unit, with a few Figure 7. Potash stratigraphy in the Mulhouse Basin, Rhine Graben, France (after Cendon et al., 2008) thin millimetric layers of halite. Page 8 www.saltworkconsultants.com

Thus, the Oligocene halite section includes two thin, for- 70 merly 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). 60 Both potash beds are made up of stacked, thin, paral- lel-sided cm-dm-thick beds (averaging 8 cm thickness), 50 KCl which are in turn constructed of couplets composed of grey-coloured halite overlain by red-coloured sylvite (Fig- Wt % Salt ure 5b). Each couplet has a sharp base that separates the 40 NaCl basal halite from the sylvite cap of the underlying bed. In some cases, the separation is also marked by bituminous 30 partings. The bottom-most halite in each dm-thick bed 26 consists of halite aggregates with cumulate textures that 0 100 200 300 400 500 600 pass upward into large, but delicate, primary chevrons and A. Temperature (°C) 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). Rhine Graben, Couche Inferieure 25 Other The sylvite member of a sylvinite couplet consists of granu- Sequence RG D, C, B, A 20 lar aggregates of small transparent halite cubes and rounded Sequence RG 12, 13, 1, 2 grains of red sylvite (with some euhedral sylvite hoppers) 15 infilling the swales in the underlying hummocky halite 10 (Figure 5b, c). The sylvite layer is usually thick enough to bury the highest protuberances of the halite, so that the 5 top of each sylvite layer, and the top of the couplet, is flat. Number of inclusions Dissolution pipes and intercrystalline cavities are notice- ably absent, although some chevrons show rounded coigns, 0 20 40 60 80 100 implying shallow bittern-brine sheets controlled potash B. T (°C) deposition. Intercalated marker beds, formed during times Figure 8. Temperature controls. A) Prograde solubilty curves of sylvite of brine pool freshening, are composed of a finely laminat- and halite (from Warren, 2016). Solubility decreases with cooling ed bituminous shale, with dolomite and anhydrite. temperature. B) Oligocene evaporite temperatures from inclusions in halite chevrons in the Salt IV series in the Mulhouse Basin, France (after The sylvite-halite couplets record combinations of unal- Lowenstein and Spencer, 1990). tered settle-out and bottom-nucleated growth features, in- dicating primary chemical sediment accumulating in shal- burial. Temperature-based inclusion studies in both the low perennial brine pools (Lowenstein and Spencer, 1990). sylvite and the halite average 63°C, suggesting solar heat- Based on the crystal size, the close association of ing of surface brines as precipitation took place (Figure 8b; with sylvite layers, their lateral continuity and the manner Lowenstein and Spencer, 1990). Similar high at-surface in which sylvite mantles overlie chevron halites, the syl- brine temperatures are not unusual in many modern brine vites are interpreted as primary precipitates. Sylvite first pools, especially those subject to periodic density stratifi- formed at the air-brine surface or within the uppermost cation and heliothermometry (Warren 2016; Chapter 2). brine mass and then sank to the bottom to form well-sort- Mineralogically, potash evaporites in the Mulhouse Basin ed accumulations. As sylvite is a prograde salt it, like ha- in the Rhine Graben (also known as the Alsatian (Alsace) lite, probably grew during times of cooling of the brine or Wittelsheim Potash district) contain sylvite with sub- mass (Figure 8a). These times of cooling could have been ordinate carnallite, but lack the abundant MgSO4 salts diurnal (day/night) or weather-front induced changes in characteristic of the evaporation of modern seawater. The the above-brine air temperatures. Similar cumulate sylvite Rhine graben formed during the Oligocene, via crustal deposits form as ephemeral bottom accumulations on the extension, related to mantle upwelling. It was, and is, a floor of modern Lake Dabuxum in China during its more continental graben typified by high geothermal gradients saline phases. along its rift axis. In depositional setting, it is not dissim- The subsequent mosaic spar textural overprint seen in many ilar to the pre-120,000-year potash fill stage in the Qua- of the Mulhouse sylvite layers was probably produced by ternary Danakil Basin or the Dead Sea during deposition postdepositional modification of the crystal boundaries, of potash salts in the Pliocene Sedom Fm. The role of a much in the same way as mosaic halite is formed by re- high-temperature geothermal inflow in defining the CaCl2 crystallisation of raft and cumulate halite during shallow nature of the potash-precipitating brines, versus a deriva- Page 9 www.saltworkconsultants.com

tion from a MgSO -de- 640 4 Ci pleted marine feed, is considered significant Mi 650 in the Rhine Graben deposits, but is poorly S understood and still not 660 resolved (Hardie, 1990;

Cendón et al., 2008). S1 Na World ocean chemis- 670 Mg Cl try in the Oligocene is on a shoulder between 0.04 0.06 0.080 0.4 0.8 1.2 0 2 4 6 8 0 1000 200 300 SO mol/kgH O K mol/kgH O mol/kgH O Br (ppm) the MgSO4-deplet- A. 4 2 2 2 ed CaCl2-rich oceans of the Cretaceous and 640 24 Marine-derived the MgSO4-enriched sources S1 oceans of the Neogene Ci S2 (Figure 4). 650 Mi 20 mixing Cendón et al. (2008) S S2 S

conclude brine reac- S‰ mixing tion processes were the Triassic seawater 34 660 Permian evaporites 16 most important factors Oligocene seawater controlling the ma- Av. thermal Mi mixing Depth (m) S1 S jor-ion (Mg, Ca, Na, water (Vosges & Rhine Graben Ci Ci

Sulphate � Sulphate Ci K, SO4, and Cl) evo- 670 Triassic 12 Ci lution of Mulhouse gypsum Ci brines (Figure 9a-d). Terrestrial-derived A combined analy- S2 sources sis of fluid inclusions 680 8 in primary textures by 0.7080 0.7100 0.7120 0.7140 0.7090 0.7092 0.7094 0.7096 0.7098 Cryo-SEM-EDS with B. 87Sr/86Sr C. 87Sr/86Sr sulphate- d34S, d18O and 87Sr/86Sr isotope ra- tios revealed likely hy- 24 Ci drothermal inputs and 22 recycling of Permian Mi Ambient marine S2 evaporites, particularly 20 S S1 during the more ad- S‰ 18 34 S2 vanced stages of evap- 16  oration that laid down 14 the Salt IV member. 12 Increasing nonmarine Bromine levels imply Ci in uences an increasingly concen- 10 trated brine at that time D. 14 15 16 17 18 19 20 21 22 23 (Figure 9a). The lower 18O‰ part of the Salt IV (S2 and S1) likely evolved Figure 9. Potash chemistry in the Mulhouse basin, Rhine Graben, France (after Cendon et al., 2008). A) Vertical from an initial marine evolution trends of main solutes in primary halite fluid inclusions (mol/kg H2O) and bromine content in halite input (Figure 9b-d). (ppm). B) 87Sr/86Sr range for potential Sr sources at time of evaporite precipitation. The circles plot 87Sr/86Sr in the Salt IV. C) Sulphate 87Sr/86Sr range for potential Sr sources at time of evaporite precipitation. The dotted line Throughout, the basin represents variations in δ34S–87Sr/86Sr as sedimentation progresses. The shaded areas represent the marine and was disconnected from terrestrial end-members. D) Crossplot and interpretation of sulphur and oxygen stable isotope data, replotted direct marine hydro- from Table 2 in Cendon et al. (2008). graphic connection and terconnections and chemical signatures of input waters. was one of a series of sub-basins formed in an active rift 34 Sulphate-d S shows Oligocene marine-like signatures at setting, where tectonic variations influenced sub-basin in- Page 10 www.saltworkconsultants.com

the base of the Salt IV member (Figure 9c, d). However, likely brine interactions occurred both during initial and enriched sulphate-d18O reveals the importance of syn- early post-depositional reflux overprinting of the original chronous re-oxidation processes. potash salt beds. As evaporation progressed, other non-marine or ma- West Canadian potash (Devonian) rine-modified inputs from neighbouring basins became more important. This is demonstrated by increases in K The Middle Devonian (Givetian) Prairie Evaporite For- concentrations in brine inclusions and Br in halite, sulphate mation is a widespread potash-entraining halite sequence isotopes trends, and 87Sr/86Sr ratios (Figure 9b, c). The re- deposited in the Elk Point Basin, an early intracratonic cycling (dissolution) of previously precipitated evaporites phase of the Western Canada Sedimentary Basin (WCSB) of Permian age was increasingly important with ongoing (Figure 10; Chipley and Kyser, 1989). Economic levels of evaporation. In combination, this chemistry supports the bedded potash were first intersected in 1946 by the gas ex- notion of a connection of the Mulhouse Basin with basins poloration well Verbata No. 2 well, near the town of Unity, situated north of Mulhouse. The brine evolution eventually . At a depth around 1050 m the well pen- reached sylvite precipitation. Hence, the chemical signa- etrated 140 metres of salt, and recovered core grade was ture of the resulting brines is not 100% compatible with 21.6 per cent K20 over 3.35 metres. This core was was first global seawater chemistry changes. Instead, the potash indication of potash beds with commercial grade, and with phase is tied to a hybrid inflow, with significant but -de a depth of 1056 metres meant shaft mining (as opposed to creasing marine input. There was likely an initial marine A. source, but this occurred within a series of rift-valley basin depres- sions for which there was no di- rect hydrographic connection to the open ocean, even at the time the Middle Salt Member (pot- ash-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-ba- sin with an initial marine-seep- age stage. This gradually changed to ≈ 40% marine source near the beginning of evaporite precipita- tion, with the rest of hydrological inputs being non-marine. There was a significant contribution of solutes from recycled, in part di- apiric, Permian evaporites, likely remobilised by the tectonics driv- ERA PERIOD EPOCH Sandstone Three Bakken ing the formation of the rift valley Forks Big Valley Evaporite Group Torquay (Hinsken et al., 2007; Cendon et Birdbear Carbonate Upper al., 2008). The general proportion Devonian Duperow

Red bed N

of solutes did not change sub- A

I

N stantially over the time of evap- O Manitoba Souris River

EV 1st Red Bed Group orite precipitation. However, as D 2nd Red Bed Dawson Bay

Devonian Stratigraphy, PALEOZOIC Middle the basin restriction increased, the Elk Prairie Devonian Evaporite Winnipegosis South-central Point formerly marine inputs changed Group Saskatchewan Ashern to continental, diapiric or ma- Lower rine-modified inputs, perhaps fed Devonian B. from neighbouring basins north of Figure 10. Stratigraphy of the Prairie Evaporite, Canada. A) Regional context. B) Local to south-central Mulhouse basin. As in the Ethi- Sakatchewan. opian Danakhil potash-rift, it is Page 11 www.saltworkconsultants.com

East West Saskatchewan Manitoba ALBER TA SASKATCHEWAN MANITOBA Dawson Bay Fm.

Winnipegosis Fm. plm bpm wbm Pr Prairie em ec calcareous shale am Evaporite br ian S hield 30m Potash members plm Patience Lake member 0 100 km bpm Belle Plaine member wbm White Bear member Edmonton B. em Esterhazy member

1. Vanscoy 6. Lanigan 2. Cory 7. Yarbo (K1) Calgary Regina 3. Patience Lake* 8. Gerald (K2) 4. Allan 9. Rocanville CANADA Winnipeg 5. Colonsay 10. Belle Plaine** 11. Legacy** U.S.A. MONTANA Saskatoon Williston 2 3 1 5 Bismarck 4 6 A 7 TH DAKOT 11 NOR 8 9 Basin edge Helena A 10 Regina Billings SOUTH DAKOT bleached Solution edge and collapsed

Anhydrite km Halite, anhydrite 0 300 Prairi e

Evaporit e Potash, halite, anhydrite (darker red areas indicate C. potash-entraining salt beds A. thicker than 150m) Figure 11. Potash in the Elk Point Basin, western Canada. A) Regional geology showing thickest salt and potash intervals in the Prairie Evaporite and its dissolution edge. B) Cross section of basin showing distribution of potash members. C) Map of potash mines in the basin; ** indicates solution mine with brine field, *solution mine utilising flooded mine shafts (compiled and modified from Worsley and Fuzesy, 1979; Fuzesy, 1982; Boys, 1993; SaltWork® Database Version 1.8) solution mining) was feasible (Fuzesy, 1982). However, it Regionally halite constitutes a large portion of the four was the thickness, purity and the availability of water and formations that make up the Devonian natural gas that made solution mining with hot crystallisa- (Figure 10): 1) the Lotsberg (Lower and Upper Lotsberg tion processing of the halite beds an attractive proposition. Salt), 2) the Cold Lake (Cold Lake Salt), 3) the Prairie Plans were made by the Prairie Salt Company, a subsidi- Evaporite (Whitkow and Leofnard Salt), and 4) the Daw- ary of Dominion Tar and Chemical Company, to brine the son Bay (Hubbard Evaporite). Today the remnants of the salt. (Other substances brought to the surface during solu- Middle Devonian Prairie Evaporite Formation constitute tion mining were to remain the property of the Crown.) a bedded unit some 220 metres thick, which lies atop the After further test drilling a salt refinery was erected and irregular topography of the platform carbonates of the production began in 1949. Winnipegosis Fm. Extensive solutioning of the various salts has given rise to an irregular thickness to the forma- Today, the Praire Evaporite is the world’s predominant tion and the local absence of salt within the main salt mass source of MOP fertiliser (Warren, 2016; Chapter 11). The and a periphery of anhydritic solution residues (Figure flexure that formed the WCSB basin and its subsealevel 11a). Interestingly, the positions of the various active pot- accommodation space was a distal downwarp to, and driv- ash mines lie near the the dissolution edge of the current en by, the early stages of the Antler Orogeny (Root, 2001). extent of the evaporite (Figure 11c). This positioning re- Texturally and geochemically the potash layers in the thick lates to shallower zones with depths appropriate for min- bedded halites of the Prairie Evaporite Formation show ing (700-1000m) being nearer the shallow salt edge and to the effects of multiple alterations and replacements of its reworking/alteration of the potash by a varity of subsurface potash minerals, especially interactions between sylvite water crossflows. and carnallite in a variably recrystallised halite host.

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The Elk Point Group was deposited within what is termed halite with clay bands and stratiform sylvite. This is the the Middle Devonian “Elk Point Seaway,” a broad in- targeted ore unit in conventional mines in the Saskatoon tracratonic sag basin extending from North Dakota and and Lanigan areas and is the solution-mined target, along northeastern Montana at its southern extent north through with the underlying Belle Plaine Member, at the Mosa- southwestern Manitoba, southern and central Saskatche- ic Belle Plaine potash facility. The Belle Plaine member is wan, and eastern to northern Alberta (Figure 11a). Its Pa- separated from the Esterhazy by the White Bear Mark- cific coast was near the present Alberta-British Columbia er beds made up of some 15 m of low-grade halite, clay border, and the basin was centred at approximately 10°S seams and sylvinite. The Belle Plaine Member is more latitude. To the north and west the basin was bound by a carnallite-prone than the Patience Lake member (Figure series of tectonic ridges and arches; but, due to subsequent 12). It is the ore unit in the conventional mines at Rocan- erosion, the true eastern extent is unknown (Mossop and ville and Esterhazy (Figure 11b) where its thickness ranges Shetsen, 1994). In northern Alberta, the Prairie Evaporite from 0-18 m and averages around 9 m. In total, the Prai- is correlated with the Muskeg and Presqu’ile formations rie Evaporite Formation does not contain any significant

(Rogers and Pratt, 2017). MgSO4 minerals (kieserite, polyhalite etc.) although some members do contain abundant carnallite. This mineralo- Hydrographic isolation of the intracratonic basin from its gy indicates precipitation from a Devonian seawater/brine marine connection resulted in the deposition of a drawn- chemistry somewhat different from today’s, with inherent- down sequence of basinwide (platform-dominant) evapo- ly lower relative proportions of sulphate and lower Mg/Ca rites with what is a uniquely high volume of preserved pot- ratios (Figure 4). ash salts deposited within a clayey halite host. The potash resource in GAMMA RAY LOG NEUTRON LOG this basin far exceeds that of any other known potash basin in the world.

Potash geology Second Red Bed Potash deposits mined in Sas- Top Prairie Evap. katchewan are all found within the upper 60-70 m of the Prairie Evaporite Formation, at depths 1000 m 33% K2O of more than 400 to 2750 me- Patience Lake tres beneath the surface of the Member Saskatchewan Plains. Within the

32.1% K2O Prairie Evaporite, there are four 24% K2O main potash-bearing members, in ascending stratigraphic order they are: Esterhazy, White Bear, Belle Plaine and Patience Lake mem- 29.7% K O 36.6% K O 1025 m bers (Figure 11b). Each member 2 2 Belle is composed of various combina- 41.26% K O Plaine 2 Carnallitic tions of halite, sylvite, sylvinite, Member and carnallitite, with occurrences of sylvite versus carnallite reliably definable using wireline signatures Halite: Halite with traces (once the wireline is calibrated to of sylvite or carnallite core or mine control - Figure 12; Sylvite and halite Fuzesy, 1982). 1050 m The Patience Lake Member is Carnallite and halite the uppermost Prairie Evaporite Carnallite, sylvite & halite member and is separated from the Belle Plaine by 3-12 m of barren Clay as thin beds, seams, partings and interstitially halite (Holter, 1972). Its thickness ranges from 0-21 m and averages Figure 12. Typical ore grades, thicknesses and wireline characteristics of the potash members in the 12 m, its top 7-14 m is made up Upper Prairie Evaporite (After Fuzesy, 1982).

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The Prairie Evaporite Fm. is nonhalokinetic throughout potash is recovered from greater depths by solution min- the basin, it is more than 200 m thick in the potash mining ing; for example, the Belle Plaine operation leaches potash district in Saskatoon and 140 m thick in the Rocanville from the Belle Plaine member at a depth of 1800m. area to the southeast (Figure 11a; Yang et al., 2009). The The Prairie Evaporite typically thins southwards in the Patience Lake member is the main target for convention- basin; although local thickening occurs where carnallite, al mining near Saskatoon. The Esterhazy potash member not sylvite, is the dominant potash mineral (Worsley and rises close to the surface in the southeastern part of Sas- Fuzesy, 1979). The Patience Lake member is mined at the katchewan near Rocanville and on into Manitoba. This Cory, Allan and Lanigan mines, and the Esterhazy Mem- is a region where the Patience Lake Member is thinner ber is mined in the Rocanville area (Figure 11c). Ore mined or completely dissolved (Figure 11b). Over the area of from the 2.4 m thick Esterhazy Member in eastern Sas- mineable interest in the Patience Lake Member, centred katchewan contain minimal amounts of insolubles (≈1%), on Saskatoon, the ore bed currently slopes downward only but considerable quantities of carnallite (typically 1%, but slightly in a westerly direction, but deepens more strongly up to 10%) and this reduces the average KCl grade value to to the south at a rate of 3-9 m/km. Mines near Saskatoon an average of 25% K O. The converse is true for ore mined are at depths approaching a kilometre and so are nearing 2 from the Patience Lake potash member in western Sas- the limits of currently economic shaft mining. katchewan near Saskatoon, where carnallite is uncommon The main shaft for the Colonsay Mine, which took IMC in the Cory and Allan mines. The mined ore thickness is a Global Inc. more than five years to complete through a 2.74-3.35 metre cut off near the top of the 3.66-4.57metre water-saturated sediment column, finally reached the tar- Prairie Lake potash member. Ore grade is 20-26% K2O get ore body at a depth of 960 metres. Such depths and a and inversely related to thickness (Figure 12). The insolu- southerly dip to the ore means that the conventional shaft ble content is 4-7%, mostly clay and markedly higher than mines near Saskatoon define a narrow WNW-ESE band in the Rocanville mines. of conventional mining activity (Figure 11c). To the south

Sylvinite % Dolomite Amount of Amount of and anhydrite type Sylvite insolubles Clay 25 35 45 55 UNITS Seam Low High Low High 412 R M6 O abrupt contact R 411 M5 O R M4 O

R abrupt contact M3

O R Middle R

M2 R O R 410 top convolute, M1 R abrupt contact

R 410 bottom Halite+ disseminated insolubles

Sylvinite Sylvinite type 60 cm Insoluble (clay) seam O Orange Clay seam with halite 1 metre Disseminated insolubles R Red gradational contact Lenses or blebs Dolomite O R of orange sylvinite in red sylvinite Anhydrite A. B.

Figure 13. and textures in the ore section in the Patience Lake member of the Prairie Evaporite Formation in the PCS Cory potash mine. A) Typical mineralogy in cycles (units). B) Contacts in two ore cycles showing early karst (sub-vertical) outlines (redrawn and modified based on Boys 1990). Page 14 www.saltworkconsultants.com

A typical sylvinite ore zone in the Clay A. B. Patience Lake member can be di- vided into four to six units, based Sylvite on potash rock-types and clay Halite seams (Figures 12, 13a; M1-M6 Halite of Boys, 1990). Units are map- Sylvite Clay pable and have been correlated throughout the PCS Cory Mine with varying degrees of success, Hematite rims dependent on partial or complete loss of section from dissolution. Subhedral to euhedral sylvite and halite crystals with Polygonal mosaic texture where sylvinite contains Potash deposition appears to have equigranular-polygonal mosaic texture larger halite crystals than coexisting sylvite crystals. Assay result indicates 42% of sample is sylvite. been early and related to short- term brine seaway cooling and syndepositional brine reflux. So C. D. the potash layering (M1-M6) is cyclic, expressed in the repetitive Carnallite distribution of hematite and oth- er insoluble minerals (Figure 13). Desiccation polygons, desiccation Halite cracks, subvertical microkarst pits and chevron halite crystals indi- cate that the Patience Lake mem- ber that encompasses the potash Carnallitite consists of isolated centimetre-sized Photomicrograph of bottom nucleated chevron halite crystals of clear halite enclosed by coarser pinkish bed away from potash intervals. Arrows at base of ore was deposited in and just be- orange carnallite crystals (halite distribution implies image indicate top of an anhydrite lamina (after neath a shallow-brine, salt-pan possible microkarst in ll - syndepositional?). Brodlyo and Spencer 1987) environment (Figure 13b; Boys, Figure 14. Representative textures from core samples, see text for detail. 1990; Lowenstein and Spencer, 1990; Brodlyo and Spencer, 1987; the zero-edge of the evaporite basin supports this concept pers. obs). (Figure 9, 10). Clay seams form characteristic thin stratigraphic segre- Potash Textures gations throughout the potash ore zone(s) of the Prairie Texturally, at the cm-scale, potash salt beds in the Prairie Evaporite, as well as disseminated intervals, and constitute Evaporite (both carnallitite and sylvinite) lack the lateral about 6% of the ore as mined. For example, the insolu- continuity seen in primary potash textures in the Oligo- ble minerals found in the PCS Cory samples are, in ap- cene of the Mulhouse Basin (Figure 14). Prairie potash proximate order of decreasing abundance: dolomite, clay probably first formed as syndepositional secondary precip- [illite, chlorite (including swelling-chlorite/chlorite), and itates and alteration products at very shallow depths just septechlorite, quartz, anhydrite, hematite, and goethite. beneath the sediment surface. These early prograde pre- Clay minerals make up about one-third of the total insolu- cipitates were then modified to varying degrees by ongo- bles: other minor components include: potassium feldspar, ing fluid flushing in the shallow burial environment. The hydrocarbons, and sporadic non-diagnostic palynomorphs cyclic depositional distribution of disseminated insolubles (Figure 13; Boys, 1990). as the clay marker beds was possibly due to a combination In all mines, the clays tend to occur as long continuous of source proximity, periodic enrichment during times of seams or marker layers between the potash zones and are brine freshening and the strengthening of the winds blow- mainly composed of detrital chlorite and illite, along with ing detritals out over the brine seaway. Possible intra-pot- authigenic septechlorite, montmorillonite and sepiolite ash disconformities, created by dissolution of overlying (Mossman et al., 1982; Boys, 1990). Of the two chlorite potash-bearing salt beds, are indicated by an abundance of minerals, septechlorite is the more thermally stable. The residual hematite in clay seams with some cutting subver- septechlorite, sepiolite and vermiculite very likely originat- tically into the potash bed. Except in, and near, dissolution ed as direct products of settle-out, syndepositional dissolu- levels and collapse features, the subsequent redistribution tion or early diagenesis under hypersaline conditions from of insolubles, other than iron , is not significant. a precursor that was initially eolian dust settling to the bot- In general, halite-sylvite (sylvinite) rocks in the Prai- tom of a vast brine seaway. The absence of the otherwise rie Evaporite ore zones generally show two end member ubiquitous septechlorite from Second Red Beds west of Page 15 www.saltworkconsultants.com

textures; 1) the most common is 16 PCS Cory a recrystallised polygonal mosa- Clear halite + carnallite daughter crystals ic texture with individual crystals Clear halite + sylvite daughter crystals ranging from millimetres to cen- 12 timetres and sylvite grain bound- Chevron halite ± sylvite aries outlined by concentrations 8 of blood-red halite (Figure 14a). 2) The other end member texture 4 is a framework of euhedral and subhedral halite cubes enclosed by 0 anhedral crystals of sylvite (Figure 20 30 40 50 60 70 80 90 100 110 120 dms 14b). This is very similar to ore Tm °C textures in the Salado Formation of interpreted as ear- ly passive precipitates in karstic PCS Lanigan voids. 16

Petrographically, the halite-car- 12 nallite (carnallitite) rocks display three distinct textures. Most ha- 8 lite-carnallite rocks contain isolat- ed centimetre-sized cube mosaics 4 of halite enclosed by poikilitic carnallite crystals (Figure 14c); 1) 0 Individual halite cubes are typi- 40 50 60 70 80 90 100 110 120 cally clear, with occasional cloudy T dms°C crystal cores that retain patches of m syndepositional growth textures Figure 15. Histograms of fluid Inclusion daughter mineral dissolution temperatures (Tmdms) in halite (Lowenstein and Spencer, 1990). samples from A) the sylvite-rich ore zone of the PCS Cory mine and B) the car­nallite-rich ore zone of the Lanigan mine. Brown squares represent fluid inclusions that produced sylvite in the chevron-tex- 2) The second texture is coarsely tured halites, pink squares represent larger, randomly distributed inclusions that contained sylvite crystalline halite-carnallite with daughter minerals in sparry (clear) halite, and green squares indicate fluid in­clusions in sparry halite equigranular, polygonal mosa- that contained carnallite daughter minerals. Classes are 1.9°C wide (e.g., from 40.0 to 41.9°C). ic textures. In zones where halite Replotted from Chipley et al. (1990) overlies bedded anhydrite, most of supported by observations of intergrowth and overgrowth the halite is clear with only the occasional crystal showing textures (McIntosh and Wardlaw, 1968), collapse and dis- fluid inclusion banding. solution features at various scales and timings (Gendzwill, Bedded halite away from the ore zones generally retains 1978; Warren 2017), radiometric ages (Baadsgaard, 1987) a higher proportion of primary depositional textures typ- and palaeomagnetic orientations of the diagenetic hema- ical of halite precipitation in shallow ephemeral saline pans (Figure 14d; Brodylo and Spencer, 1987). Crystalline Sample Mineral Location K (ppm) Age (Ma) Mag growth fabrics, mainly remnants of vertically-elongate ha- lite chevrons, are found in 50-90% of the halite from many Site 3 sylvite Rocanville 509850 375.2 C intervals in the Prairie Evaporite. Many of the chevrons are Site 6 sylvite Rocanville 618581 150 C truncated by irregular patches of clear halite that formed as Site 11 sylvite IMCK-2 582060 326 C early diagenetic cements in syndepositional karst. Site 35 sylvite Allan 488094 128 B In contrast, the halite hosting the potash ore layers lacks Site 37 sylvite Allan 518478 317 A well-defined primary textures but is dominated by inter- Site 40 sylvite Allan 441457 228 C grown mosaics. From the regional petrology and the lower than expected Br levels in halite in the Prairie Evaporite Site 45 sylvite Lanigan 511628 270 A Formation, Schwerdtner (1964), Wardlaw and Watson Site 46 sylvite Lanigan 504808 177 C (1966) and Wardlaw (1968) postulated a series of recrys- Site 47 sylvite Lanigan 517570 146 C tallisation events forming sylvite after carnallite as a result Table 2. K-Ar ages from sylvite in potash ore from Prairie Evaporite of periodic flushing by hypersaline solutions. This origin various and tied to related magnetic types ABC (see also figure 15 and as a secondary precipitate (via incongruent dissolution) is discussion in text; after Koehler, 1997).

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tite linings associated with the emplacement of the potash 400 (Koehler, 1997; Koehler et al., 1997). Normal ore (C - type) Site 03 Dating of clear halite crystals in void fills within the ore Site 11 levels shows that some of the exceptionally coarse and 300 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-Pleisto- cene (Baadsgard, 1987). Even today, alteration and remo- 200 Site 40 bilisation of the sylvite and carnallite and the local precip- (Ma) Age K-Ar Site 47 itation of bischofite, is an ongoing process, related to the encroachment of the contemporary dissolution edge or the Site 06 ongoing stoping of chimneys fed by deep artesian circula- 100 tion (pers obs.). 60 70 80 90 100 110 120 130 Fluid inclusion studies support the notion of primary tex- Magnetic declination (°N) tures (low formation temperatures in chevron halite in the Figure 16. K-Ar dates from sylvites with haematite, so allowing mea- Prairie evaporite and an associated thermal separation of surement of co-associated magnetic declination (after Koehler 1997). non-sylvite and sylvite associated halite (Figure 15; Chip- Compiled from data in Table 1. ley et al., 1990). Most fluid inclusions found in primary, ash levels. Sylvite daughter crystal dissolution tempera- fluid inclusion-banded halite associated with the Prairie tures from fluid inclusions in the cloudy centres of halite potash salts contain sylvite daughter crystals at room tem- crystals associated with potash salts are generally warm- perature or nucleate them on cooling (e.g. halite at 915 and er (Brodlyo and Spencer, 1987; Lowenstein and Spencer, 945 m depth in the Winsal Osler well; Lowenstein and 1990). Sylvite and carnallite daughter crystal dissolution Spencer, 1990). In contrast, no sylvite daughter crystals temperatures from fluid inclusions in fluid inclusion band- have been observed in fluid inclusions outlining primary ed halite from bedded halite-carnallite are the hottest. This growth textures from chevron halites away from the potash mineralogically-related temperature schism establishes deposits. that potash salts occur in stratigraphic intervals in the ha- The data illustrated as Figure 15 clearly show that inclu- lite where syndepositional surface brines were warmer. In sion temperatures in primary halite chevrons are cooler the 50° - 70°C temperature range there could be overlap than those in halites collected in intervals nearer the pot- with heliothermal brine lake waters. Even so, these warm-

Modern seawater A. PCS Lanigan (chevron, clear) B. Na PCS Bredenbury (chevron, clear) 800 IMC K-1 Mine shaft waters Normalised Brine seeps 700 Mine level waters Janeke

O) 600 Halite + diagram 2 500 solution 400

300 Carnallite K (mmol/kgH 200 + solution 100 Sylvite + solution 0 0 10 20 30 40 50 60 70 K Mg Br (mmol/kgH2O)

Figure 17. Fluid chemistry in Prairie Evaporite. A) Brine inclusion chemistry (K vs Br) from halite samples in mines and waters collected from seeps at mine levels compared to the concentration trend seen during evaporation of modern seawater (after Horita et al., 1996). B) Chemical com- positions of seepage waters collected from mine-shafts and at mine-levels (plotted on a normalized Janecke Na-K-Mg diagram.) The stability fields are shown for halite, sylvite and carnallite in contact with a solution (after Wittrup and Kyser, 1990).

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er potash temperatures imply par- 40 40 ent brines would likely be moving A 20 D C 20 via a shallow reflux drive and are 2σ B SMOW not the result of primary bottom X 1 0 SMOW 0 C X2 Evaporating nucleation (in contrast to prima- X D 3 A E seawater ry sylvite in the Mulhouse Basin). -20 MWL -20 B Whether the initial Prairie reflux Michigan -40 Basin -40 potash precipitate was sylvite or MWL  D carnallite is open to interpretation -60 Elk  D -60 Dawson Bay Fm. (Lowenstein and Hardie, 1990). Point Elk Point -80 Basin -80 Basin Trend Fluid evolution from mineral -100 -100 and isotope chemistry Souris River Fm -120 -120 Mannville Gp. Analysis of subsurface waters from various Canadian potash -140 -140 mines and collapse anomalies in -160 -160 the Prairie Evaporite suggest that, -20 -10 0 10 -20 -10 0 10 18O 18O after initial potash precipitation, a A. B. series of recrystallising fluids ac- Figure 18. Isotopes (after Chipley et al., 1991, and references therein). A) D andd180 values for cessed the evaporite levels at mul- meteoric water (MWL), seawater (SMOW), basin brines, and changes in the isotopic compositions tiple times throughout the burial of seawater during evaporation . A -humid evaporation conditions , B-arid evaporation conditions (Holser , 1979) , C -evaporation studies of waters in experimental and natural systems, D - results history of the Prairie Formation from Ojo de Libre lagoon, Mexico, evaporated to halite precipitation, E - and evaporated seawater

(Chipley, 1995; Koehler, 1997; from salt crystallising ponds , Bonaire Island , X1 = pre-gypsum , X2 = pre-halite , and X3 = post-halite, Koehler et al., 1997). Likewise, the pre-sylvite. B) Isotopic compositions of water from formations overlying the Prairie Evaporite (Elk Point Basin Trend) and fluids extracted from fluid inclusions. Fields A and B represent halite fluid inclusion isotope systematics and K-Ar ages waters from chevron and non-chevron fluid inclusions, respectively , in the Palo Duro Basin, field C of sylvite in both halite and syl- represents water in halite fluid inclusions from the Delaware Basin thought to be derived from dehy- vite layers indicate that the Prairie dration of gypsum which recrystallised the halite and curve D represents evaporation of seawater from Bonaire Island salt crystallization ponds ( trend E in 16a). Squares (PCS Cory) and stars (PCS Evaporite was variably recrystal- Lanigan Mine) represent fluids extracted from halite fluid inclusions from the Patience Lake Member lised during fluid overprint events of the Prairie Evaporite. (Table 2; Figure 16). These event ages are all younger than original ure 17b; Wittrup and Kyser, 1990; Chipley, 1995). What deposition (≈390Ma) and likely correspond to ages of var- is more, the mine waters of today show substantial overlap ious tectonic events that influenced subsurface hydrology with waters collected more than thirty years ago ( Jensen along the western margin of North America. et al., 2006) Chemical compositions of inclusion fluids in the Prairie This notion of ongoing fluid-rock interaction controlling d Evaporite, as determined by their thermometric properties, the chemistry of mine waters is supported by D and d18 reveal at least two distinct waters played a role in potash O values of inclusion fluids in both halite and sylvite, formation: a Na-K-Mg-Ca-Cl brine, variably saturated which range from -146 to 0‰ and from -17.6 to -3.0‰, with respect to sylvite and carnallite; and a Na-K-Cl brine respectively (Figure 18). Most of the various preserved iso- (Horita et al., 1996). That is, contemporary inclusion tope values are different from those of evaporated seawater, d d18 water chemistry is a result in part of ongoing fluid-rock which should have D and O values near 0‰. interaction. The ionic proportions in some halite samples Furthermore, the dD and d18O values of inclusion fluids are not the result of simple evaporation of seawater to the are probably not the result of precipitation of the evapo- sylvite bittern stage (Figure 17a; Horita et al., 1996). There rite minerals from a brine that was a mixture of seawater is a clear separation of values from chevron halites in sam- and meteoric water. The low latitude position of the basin ples from the Lanigan and Bredenbury (K-2 area) mines, during the Middle Devonian (10-15° from the equator), which plot closer to the concentration trend seen in ha- the required lack of meteoric water to precipitate basin- lite from modern seawater and values from clear or sparry wide evaporites, and the expected dD and d18O values of halite. The latter encompass much lower K and higher Br any meteoric water in such a setting, make this an unlikely related to fractionation tied to recrystallisation. Likewise, explanation. Rather, the dD and d18O values of inclu- the influence of ongoing halite and potash salt dissolution sion fluids in the halites reflect ambient and evolving brine is evident in the chemistry of shaft and mine waters with chemistries as the fluids in inclusions in the various growth mine level waters showing elevated Mg and K values, (Fig- layers were intermittently trapped during the subsurface

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A A A 300m 1 Halite 25% K O 2 Sylvinite A1

A 1 A A1 2 Halite

Sylvinite 12.5% K2O

Salt anomaly

Sylvinite K2O Insol. 2.9 0.7 Halite 25.1 3.1 40.1 0.4 Sylvinite 6.4 79.6

B Disseminated clays B B B1 2

Figure 19. Salt anomalies mapped in an ore level in a potash mine near Saskatoon, Canada (after Baar 1974; Warren, 2017). A) Subsurface distribution of small scale salt anomalies mapped during mining. B) Scaled cross sections of salt anomalies and associated K2O values. evolution of the Prairie Formation in the Western Canada mate, which in turn may not be related to tectonism (War- Sedimentary Basin. They also suggest that periodic mi- ren, 2016; Chapters 2 and 8 for details). gration of nonmarine subsurface water was a significant In the potash areas of the Western Canada Sedimenta- component of the crossflowing basinal brines throughout ry Basin, the notion of 10-100 km lateral continuity is a much of the recrystallisation history (Chipley, 1995). commonly stated precept for both sylvinite and carnalli- Prairie carnallite-sylvite alteration over time tite units across the extent of the Prairie Evaporite. But when the actual distribution and scale of units are mapped Ongoing alteration of carnallite to sylvite and the reverse based on mined intercepts, there are numerous 10-100 reaction means a sylvite-carnallite bed must be capable of metre-scale discontinuities (anomalies) present indicating gaining or losing fluid at the time of alteration. That is, fluid ingress or egress (Warren, 2017). any reacting potash beds must be permeable at the time of the alteration. By definition, there must be fluid egress to Sometimes ore beds thin and alteration degrades the ore drive incongruent alteration of carnallite to sylvite or fluid level (Section A-A1-A2), other times these discontinuities ingress to drive the alteration of sylvite to carnallite. There can locally enrich sylvite ore grade (B-B1; Figure 19). Dis- can also be situations in the subsurface where the volume continuities or salt anomalies are much more widespread of undersaturated fluid crossflow was sufficient to remove in the Prairie evaporite than mentioned in much of the (dissolve) significant quantities of the more soluble evap- potash literature (Figure 19). Mining for maintenance of orite salts. Many authors looking at the Prairie evaporite ore grade shows that unexpectedly intersecting an anomaly argue that the fluid access events during the alteration of in a sylvite ore zone can have a range of outcomes ranging carnallite to sylvite or the reverse, or the complete leaching from the inconsequential to the catastrophic, in part be- of the soluble potash salts was driven by various tectonic cause there is more than one type of salt anomaly or “salt events (Figure 16). In the early stages of burial alteration horse" (Warren, 2017). (few tens of metres from the landsurface) the same alter- Figure 20 summarises what are considered the three most ation processes can be driven by varying combinations of common styles of salt anomaly in the sylvite ore beds brine reflux, prograde precipitation and syndepositional of the Prairie Evaporite, namely 1) Washouts, 2) Leach karstification, all driven by changes in brine level and cli- Page 19 www.saltworkconsultants.com

anomalies, 3) Collapse anomalies. a) Washout anomaly (erosional furrow or karst- ll) These ore bed disturbances and their occurrence styles are in part SYLVINITE time-related. Washouts are typi- cally early (eogenetic) and defined Microkarst pits HALITE as... “salt-filled V- or U-shaped structures, which transect the nor- mal bedded sequence and oblit- 4m SYLVINITE erate the stratigraphy” (Figure 20a; Mackintosh and McVittie, b) Leach anomaly (metasomatic - brine evolution) 1983, p. 60). They are typically enriched in, or filled by, insoluble materials in their lower one-third HALITE SYLVINITE and medium-coarse-grained spar- Leached/altered beds ry halite in the upper two thirds. 200m may be thinner SYLVINITE Up to several metres across, when traced laterally they typically pass into halite-cemented paleo-sinks c) Collapse anomaly (point or line-sourced ingress of unsaturated water) and cavern networks (e.g. Fig- HALITE Collapse ure 20b). Most washouts likely Breccia formed penecontemporaneous to KCl leach SYLVINITE the potash beds they transect, that anomaly is, they are preserved examples of synkarst, with infilling of the karst SYLVINITE void by a slightly later halite ce- ment. They indicate watertable HALITE lowering in a potash-rich saline 200m sump. This leaching was followed soon after by a period of higher Figure 20. Three main types of salt anomalies or salt horses (based on Boys 1990 and Mackintosh watertables and brine saturations, and McVittie, 1983, see Warren 2017 for details). when halite cements occluded and McVittie, 1983; McIntosh and Wardlaw, 1968). the washouts and palaeocaverns. Modern examples of this process typify the edges of subcropping and contemporary Of the three types of salt anomaly illustrated, leach zone evaporite beds, as about the recently exposed edges of the processes are the least understood. Historically, when in- modern Dead Sea. As such, “washouts” tend to indicate congruent dissolution was the widely accepted interpreta- relatively early interactions of the potash interval with un- tion for loss of unit thickness in the Prairie Evaporite, many dersaturated waters, they may even be a part of the syn- leach anomalies were considered metasomatic. Much of the depositional remobilisation hydrology that focused, and original metasomatic interpretation was based on decades locally enriched, potash ore levels. of detailed work in the various salt mines of the German Zechstein Basin. There, in an endemic halokinetic terrane, In a leach anomaly zone, the stratabound sylvinite ore evaporite textures were considered more akin to meta- zone has been wholly or partially replaced by barren halite, morphic rocks, and the term metasomatic alteration was without significantly disturbing the normal stratigraphic commonly used when explaining leach anomalies (Bochert sequence (clay marker beds) which tend to continue across and Muir, 1964, Braitsch, 1971). In the past two decades, the anomaly (Figure 20b). Some loss of volume or local general observations of the preservation of primary chev- thinning of the stratigraphy is typical in this type of salt ron halite in most bedded evaporites away from the potash anomaly. Typically saucer-shaped, they have diameters layers in the Prairie Evaporite have led to reduced use of ranging from a few metres up to 400m. Less often, they notions of widespread metamorphic-like metasomatic or can be linear features that are up to 20 m wide and 1600m solid-state alteration processes in bedded evaporites. There long. Leach zones can form penecontemporaneously due to is just too much preserved primary texture in the bedded depressions and back-reactions in the ore beds, or by later salt units adjacent to potash beds to invoke pervasive burial low-energy infiltration of Na-saturated, K-undersaturated metasomatism of the Prairie Evaporite. brines. The latter method of formation is also likely on the margins of collapse zones, creating a hybrid situation typ- So how do leach anomalies, as illustrated in Figure 20b, ically classified as a leach-collapse anomaly (Mackintosh occur in nonhalokinetic settings? One possible explanation

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metres 80 . M r

pper alite Sylvite 60 Mr.

40 .

Carnallite Mr. M r Sylvite Mr. Loer alite 20 Carnallite Halite + clays (≈1cm thick cycles) Loer alite Mr. Sylvite Halite + clays (≈5cm thick cycles) 0.5 m 0 Basal Anhydrite Slmp level Figure 21. Stratigraphy of Upper Eocene potash section based on sequence cored in Biurrun borehole and tied to a mine wall sketch from Subiza Mine, showing barren body made up of two superimposed slump structures in halite with corresponding upper sections, where the onlapping sylvite beds evolve from absent to continuous above the anomaliy (after Cendon et al., 1998). is given by the depositional textures documented in anom- lized material, with the breccia blocks typically made of alies in the Navarra Potash Province (Figure 21). There, the the intrasalt or roof lithologies (Figure 20c), so angular underlying and overlying salt stratigraphy is contiguous, fragments of the Second Red beds and dolostones of the while the intervening sylvite passed laterally into a syn- Dawson Bay Formation are the most conspicuous compo- depositional anomaly or “salt horse” created by an irregular nents of the collapse features in the Western Canada Sed- topography on the salt pan floor prior to the deposition of imentary Basin. When ore dissolution is well developed, onlapping primary sylvinite layers (see Warren 2016, 2017 all the halite can dissolve, along with the potash salts, and for detailed discussion) the overlying strata collapse into the cavity (these are clas- sic solution collapse features). Transitional leached zones On the other hand, in halokinetic situations (which typically separate the collapsed core from normal bedded characterises much Zechstein salt) solid-state alteration potash. Such collapse structures indicate a breach of the via inclusion related migration in flowing salt beds is a ore layers by unsaturated waters, fed either from below or well-documented set of texture-altering processes (dif- above. For example, in the Western Canada Sedimenta- fusion metasomatism). Most workers in such halokinetic ry Basin, well-developed collapse structures tend to occur systems would agree that there must have been an original over the edges and top Devonian mud mounds, while in stratiform potassium segregation present during or soon the New Mexico potash zone the collapse zones are re- after deposition related to initial precipitation, fractional lated to highs in the underlying Capitan reef trend (War- dissolution and karst-cooling precipitation. But what is ren, 2017). Leaching fluids may have come from below or controlling potassium distribution now in the Zechstein above to form collapse structures at any time after initial salts is a recrystallised and remobilised set of textures, deposition. When connected to a water source, these are which preserve little or no crystal-scale evidence of pri- the subsurface features that when intersected can quickly mary conditions (Warren, 2016; Chapter 6). The complex move the mining operation out of the salt into an adjacent layering in such deposits may preserve a broad depositional aquifer system, a transition that led to flooding in most of stratigraphy, but the decimetre to metre scale mineral dis- the mine-lost operations listed earlier. tributions are indications of complex interactions of folds, overfolds, and disaggregation with local flow thickening. Identifying at the mine scale the set of processes that cre- We shall return to this discussion of Zechstein potash ated a salt anomaly in a sylvite bed also has implications in textures in the next section dealing with devolatisation of terms of its likely influence on mine stability and whatever hydrated salts such as carnallite. in zones of local heating decision is made on how to deal with it as part of the ongo- ing mine operation (Warren, 2016, 2017). Syndepositional Collapse zones in the Prairie Evaporite are characterized karst fills and leach anomalies are least likely to be prob- by a loss of recognizable sylvinite ore strata, which is re- lematic if penetrated during mining, as the aquifer system placed by less saline brecciated, recemented and recrystal- Page 21 www.saltworkconsultants.com

12 textures. At times, relatively rapid 200° magma emplacement can lead to 10 linear breakout trends outlined by phreatomagmatic explosion cra- 8 ters, as imaged in portions of the 250° North Sea (Wall et al., 2010) and 6 300° the Danakhil/Dallol potash beds in Ethiopia (Salty Matters, May 1, Time (months) Time 4 350° 400° 2015). 2 150° Based on studies of inclusion chemistry and homogenization 0 1 2 3 4 5 Distance (m) into salt from edge of a 1.8m-wide basalt dyke temperatures in fluid inclusions in bedded halite near intrusives, Figure 22. Temperature effects in salt across time (1 year) and distance (m) from the edge of a 1.8m-wide basalt intrusion into halite (after Knipping, 1989). it seems that the extent of the in- fluence of a dolerite sill or dyke that formed them is likely no longer active. In contrast, in bedded salt is marked by flu- penetration or removal of the region around a salt-deplet- id-inclusion migration, evidenced by the disappearance of ed collapse breccia may lead to uncontrollable water in- chevron structures and consequent formation of clear ha- flows and ultimately to the loss of the mine. lite with a different set of higher-temperature inclusions. Such a migration envelope is well documented in bedded Unfortunately, in terms of production planning, the fea- Cambrian halites intruded by end-Permian dolerite dykes tures of the periphery of a leach anomaly can be similar in the Tunguska region of Siberia (Grishina et al., 1992). if not identical to those in the alteration halo that typi- cally forms about the leached edge a collapse zone. The Defining h as the thickness of the dolerite intrusion in processes of sylvite recrystallisation that define the edge these salt beds, and d as the distance of the halite from the of collapse anomaly can lead to local enrichment in sylvite edge of the intrusion, then the disappearance of chevrons levels, making these zones surrounding the collapse core occurs at greater distances above than below the intrusive attractive extraction targets (Boys 1990, 1993). Boundaries sill. For d/h < 0.9 below the intrusion, CaCl2, CaCl2, KCl of any alteration halo about a collapse centre are not con- and nCaCl2, mMgCl2 solids occur in association with wa- centric, but irregular, making the prediction of a feature’s ter-free and liquid-CO2 inclusions, with H2S, SCO and geometry challenging, if not impossible. The safest course orthorhombic or glassy S8. For a d/h of 0.2-2 above the of action is to avoid mining salt anomalies, but longwall intrusion, H2S-bearing liquid-CO2 inclusions are typical, techniques make this difficult and so they must be identi- fied and dealt with (see Warren 2017). Salt Formula Decomposition/Melt point (°C) Halite NaCl 804°C anhydrous melt Cooking sylvite: Dykes & sills in potash Gypsum CaSO4.2H2O 100-150°C loss of water salts Anhydrite CaSO4 1460°C anhydrous melt

In addition to; 1) primary sylvite and 2) sylvite/carnallite Carnallite KMgCl3.6H2O 150-180°C loss of water alteration via incongruent transformation in burial, there Sylvite KCl 750-790°C anhydrous melt is a third mode of sylvite formation related to 3) igne- Bischofite MgCl2.6H2O >118°C loss of water ous heating driving devolatisation of carnallitite, which 712°C anhydrous melt can perhaps be considered a form of incongruent melt- Epsomite MgSO4.7H2O >70-80°C loss of water ing (Warren, 2016; Chapter 16). And so, at a local scale Kieserite MgSO4.H2O 150-200°C loss of water (measured in metres to tens of metres) in potash beds 1120-1150°C anhydrous melt cut by igneous intrusions, there are a number of docu- Trona Na3H(CO3)2.2H2O >70°C loss of water mented thermally-driven alteration styles and thermal NaHCO3 270°C anhydrous melt haloes. Most are created by the intrusion of hot doleritic or basaltic dykes and sills into cooler salt masses, or the TYPICAL MAGMA/ERUPTION TEMPERATURES outflow of extrusive igneous flows over cooler salt beds Picritic 1400 -1500°C (Knipping, 1989; Grishina et al, 1992, 1998; Gutsche, Basaltic 1100-1200°C 1988; Steinmann et al., 1999; Wall et al., 2010). Hot ig- neous material interacts with somewhat cooler anhydrous Rhyolitic 800-900°C salt masses to create narrow, but distinct, heat and mobile Natrocarbonatite 500-600°C fluid-release envelopes, also reflected in the resulting salt Table 3. Decomposition and melting points of selected salts and typical ranges of magma temperatures (after Warren 2016). Page 22 www.saltworkconsultants.com

In the later Tertiary, basaltic melts intruded these Zech- MPa Una ected stein evaporites as numerous sub-vertical dykes, but only a 140 Partial melting few dykes attained the Miocene landsurface. Basaltic melt production was related to regional volcanic activity some Melted 10 to 25 Ma. Basalts exposed in the mine walls, where it cuts non-hydrous units of halite or anhydrite, are typically 120 subvertical dykes, rather than subhorizontal sills. The ba- salts are phonolitic tephrites, limburgites, basanites and olivine nephelinites. Dyke margins are usually vitrified, 100 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 80 cm-wide carapace of high-temperature salts (mostly an- hydrite and ferroan carbonates). Further out, the effect of the high-temperature envelope is denoted by transitions 60 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 40 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 20 inclusion-free halite typically filling vesicles in the basalt. Heating of hydrated (carnallitic) salt layers, adjacent to a 0.1MPa dyke or sill, tends to drive off the water of crystallisation (Atmospheric) 166 170 170 180°C (chemical or hydration thixotropy) at much lower tem- 167.5 peratures than that at which anhydrous salts, such as ha- Figure 23. Results of incongruent carnallite melting during autoclavation lite or anhydrite, thermally melt (Figure 24c; Table 3). For experiments using rock salt with disseminated carnallite (replotted form example, in the Fulda region, the thermally-driven release Fabricius and Rose-Hampton, 1988). Carnallite melts at 167.5°C at of water of crystallisation within carnallitic beds creates atmospheric pressure. thixotropic or subsurface “peperite” textures as carnallitite with various amounts of water. Thus, as a rule of thumb, alters to sylvinite layers. These are layers where heated wa- an alteration halo extends up to twice the thickness of the ter of crystallisation escaped from the hydrated-salt lattice. dolerite sill above the sill and almost the thickness of the Dehydration-driven loss of mechanical strength focuses sill below (Figure 22). zones of magma entry into particular subhorizontal hori- zons in the salt mass, wherever hydrated salt layers were In a series of autoclavation laboratory experiments, Fabri- present. In contrast, dyke and sill margins are much sharp- cius and Rose-Hampton (1988) found that; 1) at at mo- er and narrower in zones of contact with anhydrous salt spheiric pressure carnallite melts incongruently to sylvite intervals and the intrusive is sub-vertical to steeply dipping and hydrated MgCl2 at a temperature of 167.5°C. 2) the (Figure 24b versus 24c). melting/transformation temperature increase to values in excess of 180°C as the pressure increases (Figure 23). Accordingly, away from the immediate vicinity of the direct thermal aureole, heated and overpressured dehy- A similar situation occurs in the dyke-intruded halite lev- dration waters can enter carnallite halite bed, and drive els exposed in the mines of the Werra-Fulda district of the creation of extensive soft sediment deformation and Germany (Steinmann et al., 1999; Schofield, et al., 2014). peperite textures in hydrated layer (Figure 24c). Miner- There the Herfa-Neurode potash mine is located in the alogically, sylvite and coarse recrystallised halite dominate Werra-Fulda Basin in the Hessian district of central Ger- the salt fraction in the peperite intervals of the Herfa-Neu- many (Figure 24a). The targeted ore levels consist of the rode mine. Sylvite in the altered zone is a form of dehy- carnallite-rich Kaliflöz Hessen (K1H) and Kaliflöz Thürin- drated carnallite, not a primary-textured salt. Across the gen (K1Th) intervals, which form part of the Zechstein 1 Fulda region, such altered zones and deformed units can (Z1) bedded Werra salt succession (Warren, 2016). In the extend along former carnallite layer to tens or even a hun- mine the K1H and K1Th units range in thickness from 2 m dred or more metres from the dyke feeder. Ultimately, the to 10 m, are generally subhorizontal and occur at a depth deformed potash bed passes back out into the unaltered of 650–710 m below the present-day surface. Page 23 www.saltworkconsultants.com

South Basalt dykes North A. Shaft Herrigen Neuhof Shaft Hattorf Shaft Wintershall Fulda Graben Werra 200 Approx. 100m clay Bunter sandstone 30m dolomite K H 0 1 Salt subrosion Z1 Upper Werra rocksalt -200

-400 Depth (m) -600 K Th Rotliegend 1 Basal Zechstein Z Lower Werra rocksalt 1 5 km -800

Dyke bulges opposite former carnallite- sylvite ore zone Halite

1 m Linear knife-sharp contact of basalt dyke with minor alteration halo Dyke expands into sill ( <5cm wide) carrying volatiles and creating B. C. peperite textures

Figure 24. Influence of Tertiary basalt dyke intrusions on volatile distribution in Zechstein evaporites in the Fulda region, Germany. A) Geological cross section. B) steeply inclined dyke in laminated halite showing knife-sharp contacts. C) Near vertical dyke showing knife-sharp contacts opposite layered halite and alteration bulges extending tens ot hundreds of metres as peperite sill into level of former carnallitic (now sylvitic) layer (see Schofield et al, 2014 and Salty Matters, November 30. 2016 for detail). bed, which retains abundant inclusion-rich halite and car- tersecting salt beds tend to widen to become sills in two nallite (Schofield et al., 2014). zones: 1) along evaporite units within the halite mass that contain hydrated salts, such as carnallite or gypsum (Fig- That is, nearer the basalt dyke, the carnallite is largely ure 24c) and, 2) where rising magma has ponded and so transformed into inclusion-poor halite and sylvite, the created laccoliths at the upper or lower halite contact with result of incongruent flushing of warm saline fluids mo- the adjacent nonsalt strata or against a salt wall (Figure 22 bilised from the hydrated carnallite crystal lattice as it vs 24). The first is a response to a pulse of released water was heated by dyke emplacement. During Miocene salt as dyke-driven heating forces the dehydration of hydrat- alteration/thermal metamorphism in the Fulda region, ed salt layers. The second is a response to the mechanical NaCl-fluids were mixed with fluids and gases originating strength contrast at the salt-nonsalt contact. from thermally-mobilised crystallisation water in the car- nallite, as it converted to sylvite. This brine/gas mixture In summary, sylvite formed from a carnallite precursor altered the basalts during post-intrusive cooling, an event during Miocene salt alteration/thermal metamorphism in which numerical models suggest was quite rapid (Knip- the Fulda region, NaCl-fluids were mixed with fluids orig- ping, 1989): a dyke of less than 0.5 m thickness probably inating from thermally-mobilised crystallisation water in cooled to temperatures less than 200°C within 14 days of the carnallite, as it converted to sylvite. This brine mixture dyke emplacement. altered the basalts during post-intrusive cooling, an event which numerical models suggest was quite rapid (Knip- The contrast in alteration extent between anhydrous and ping, 1989): a dyke of less than 0.5 m thickness probably hydrous salt layers shows alteration effects are minimal cooled to temperatures less than 200°C within 14 days of wherever the emplacement temperature of the magma is dyke emplacement. below that of the anhydrous salt body as it is next to a basalt dyke. If this is the mechanism driving entry of ig- How to produce economic potash salts neous-related volatiles (gases and liquids) into a salt body, Over this series of three articles focused on current ex- then the distribution of products (including CO2) will be highly inhomogeneous and related to the minerally of the amples of potash production, we have seen there are two salt unit adjacent to the intrusive. Worldwide, dykes in- main groups of potash minerals currently utilised to make fertiliser, namely, muriate of potash (MOP) and sulphate Page 24 www.saltworkconsultants.com

of potash (SOP). MOP is both mined (generally from a All the Quaternary saline lake factories supply less than Pre-Neogene sylvinite ore) or produced from brine pans 20% of the world's potash; the majority comes from the (usually via processing of a carnallitite slurry). In contrast, conventional mining of sylvinite ores. The world's larg- large volumes of SOP are today produced from brine pans est reserves are held in Devonian evaporites of the Prai- in China and the USA but with only minor production rie Evaporite in the Western Canada Sedimentary Basin. for solid-state ore targets. Historically, SOP was produced Textures and mineral chemistry show that the greater vol- from solid-state ores in , the Ukraine, and Germany ume of bedded potash salts in this region is not a primary but today there are no conventional mines with SOP as the sylvite precipitate. Rather the ore distribution, although prime output in commercial operation (See Salty Matters, stratiform and defined by a series of clay marker beds, ac- May 12, 2015). tually preserves the effects of multiple modifications and alterations tied to periodic egress and ingress of basinal The MgSO -enriched chemistry of modern seawater 4 waters. Driving mechanisms for episodes of fluid crossflow makes the economic production of potash bitterns from range from syndepositional leaching and reflux through to a seawater-feed highly challenging. Today, there is no ma- tectonic pumping and uplift (telogenesis). Ore distribu- rine-fed plant anywhere in the world producing primary tion and texturing reflect local-scale (10-100 metres) dis- sylvite precipitates. However, sylvite is precipitating from continuities and anomalies created by this evolving fluid a continental brine feed in salt pans on the Bonneville salt chemistry. Some alteration episodes are relatively benign flat, Utah. There, a brine field, drawing shallow pore waters in terms of mineralogical modification and bed continui- from saltflat sediments, supplies suitably low-MgSO in- 4 ty. Others, generally tied to younger incidents (post early flow chemistry to the concentrator pans. Sylvite also pre- Cretaceous) of undersaturated crossflow and karstification, cipitates in solar evaporator pans in Utah that are fed brine can have substantial effects on ore continuity and suscep- circulated through the abandoned workings of the Cane tibility to unwanted fluid entry. In contrast, ore textures Creek potash mine (Table 1). and bed continuity in the smaller-scale sylvinite ores in the Large-scale production of MOP fertiliser from potash pre- Oligocene Mulhouse Basin, France, indicate a primary ore cipitates created in solar evaporation pans is taking place in genesis. perennially subaqueous saline pans of the southern Dead Sea and the Qaidam Basin. In the Dead Sea, the feed brine What makes it economic? is pumped from the waters of the northern Dead Sea ba- Across the Quaternary, we need a saline lake brine sys- sin, while in the Qaidam sump the feed is from a brine tems with the appropriate brine proportions, volumes and field drawing pore brines with an appropriate mix of river climate to precipitate the right association of processable and basinal brine inputs. In both cases, the resulting feed potash salts. So far, the price of potash, either MOP or brine to the final concentrators is relatively depleted in SOP, and the co-associated MgSO4 bitterns, precludes in- magnesium and sulphate. These source bitterns have ionic dustrial marine-fed brine factories. proportions not unlike seawater in times of ancient Mg- In contrast, to the markedly nonmarine locations of potash SO4-depleted oceans. Carnallitite slurries, not sylvinite, are the MOP precipitates in pans in both regions. When recovery from the Quaternary sources, almost all pre-Qua- feed chemistry of the slurry is low in halite, then the pro- ternary potash operations extract product from marine-fed cess to recover sylvite is a cold crystallisation technique. basinwide ore hosts during times of MgSO4-depleted and When halite impurity levels in the slurry are higher, sylvite MgSO4-enriched oceans (Warren, 2016; Chapter 11). This is manufactures using a more energy intensive, and hence time-based dichotomy in potash ore sources with nonma- more expensive, hot crystallisation technique. Similar sul- rine hosts in the Quaternary deposits and marine evaporite phate-depleted brine chemistry is used in Salar Atacama, hosted ore zones in Miocene deposits and older, reflects a where MOP and SOP are recovered as byproducts of the simple lack of basinwide marine deposits and appropriate production of brines. marine chemistry across the Neogene (Warren, 2010). As for all ancient marine evaporites, the depositional system Significant volumes of SOP are recovered from a combi- that deposited ancient marine-fed potash deposits was one nation of evaporation and cryogenic modification of sul- to two orders of magnitude larger and the resultant depos- fate-enriched continental brines in pans on the edge of its were typically thicker stacks than any Quaternary pot- the Great Salt Lake, Utah, and Lop Nur, China. When ash settings. The last such “saline giant” potash system was concentrated and processed, SOP is recovered from the the Solfifera series in the Sicilian basin, deposited as part processing of a complex series of Mg-K-SO4 double salts of the Mediterranean “salinity crisis,” but these potential (schoenitic) in the Odgden pans fed brines from the Great ore beds are of the less economically attractive MgSO4- Salt Lake. The Lop Nur plant draws and concentrates enriched marine potash series. pore waters from a brine field drawing waters from glau- berite-polyhalite-entraining saline lake sediments. So, what are the factors that favour the formation of, and hence exploration for, additional deposits of exploitable Page 25 www.saltworkconsultants.com

ancient potash? First, large MOP solid-state ore sources Bastow, I. D., A. D. Booth, G. Corti, D. Keir, C. Magee, C. are all basinwide, not lacustrine deposits. Within the basin- A.-L. Jackson, J. Warren, J. Wilkinson, and M. Lascialfari, wide association, it seems that intracratonic basins host 2018, The development of late-stage continental breakup: significantly larger reserves of ore, compared to systems Seismic reflection and borehole evidence from the Danakil that formed in the more tectonically-active plate-edge rift Depression, Ethiopia: Tectonics, v. 37. and suture association. This is a reflection of: 1) accessibil- Bingham, C. P., 1980, Solar production of potash from ity – near the shallow current edge of a salt basin, 2) a lack brines of the Bonneville Salt Flats, in J. W. Gwynn, ed., of a halokinetic overprint and, 3) the setup of longterm, Great Salt Lake; a scientific, history and economic over- stable, edge-dissolution brine hydrologies that typify many view. , v. 116, Bulletin Utah Geological and Mineral Sur- intracratonic basins. Known reserves of potash in the De- vey, p. 229-242. vonian Prairie evaporite in West Canadian Sedimentary Basin (WCSB) are of the order of 50 times that of next Blanc-Valleron, M.-M., and M. Schuler, 1997, The Salt largest known deposit, the Permian of the Upper Kama Basins of Alsace (Southern Rhine Graben), in G. Busson, basin, and more than two orders of magnitude larger than and B. C. Schreiber, eds., Sedimentary Deposition in Rift any other of the other known exploited deposits (Table 1). and Foreland Basins in France and Spain (Paleogene and Lower Neogene): , Columbia University Press, Part of this difference in the volume of recoverable reserves p. 95–135. lies in the fact that the various Canadian potash members in the WCSB are still bedded and flat-lying. Beds have not Blanc-Valleron, M. M., 1991, Les formations paléogènes been broken up or steepened, by any subsequent halokine- évaporitiques du bassin potassique de Mulhouse et des sis. The only set of processes overprinting and remobilising bassins plus septentrion aux d'Alsace (Document BRGM, the various potash salts in the WCSB are related to multiple 204), Université Louis Pasteur, Paris, 350 p. styles and timings of aquifer encroachment on the potash Borchert, H., and R. O. Muir, 1964, Salt deposits-The or- units, and this probably took place at various times since igin, metamorphism and deformation of evaporites: Lon- the potash was first deposited, driven mainly by a combi- don, D. Van Nostrand Co., Ltd., 338 p. nation of hinterland uplift and subrosion. In contrast, most of the other significant potash basins listed in Table 1 have Boys, C., 1990, The geology of potash deposits at PCS been subjected to ongoing combinations of halokinesis and Cory Mine, Saskatchewan: Master's thesis, University of groundwater encroachments, making these beds much less Saskatchewan; Saskatoon, SK; Canada, 225 p. laterally predictable. In their formative stages, the WCSB Boys, C., 1993, A geological approach to potash mining potash beds were located a substantial distance from the problems in Saskatchewan, Canada: Exploration & Min- orogenic belt that drove flexural downwarp and creation ing Geology, v. 2, p. 129-138. of the subsealevel sag depression. Like many other intra- cratonic basins, the WCSB did not experience significant Braitsch, O., 1971, Salt Deposits: Their Origin and Com- syndepositional compression or rift-related loading. positions: New York, Springer-Verlag, 297 p. Brodylo, L. A., and R. J. Spencer, 1987, Depositional envi- References ronment of the Middle Devonian Telegraph Salts, Alberta, Adamo, S., 1992, The Sicilian rock salt and potash mines: Canada: Bulletin Canadian Geology, v. 35, p. Mining Magazine, v. 166, p. 277-283. 186-196. Adams, S. S., 1970, Ore controls, Carlsbad potash district, Cendon, D. I., C. Ayora, J. J. Pueyo, and C. Taberner, 2003, southeast New Mexico, in J. L. Rau, and L. F. Dellwig, eds., The geochemical evolution of the Catalan potash subbasin, Third Symposium on Salt, v. 1: Cleveland, , Northern South Pyrenean foreland basin (Spain): Chemical Geolo- Ohio Geological Society, p. 246-257. gy, v. 200, p. 339-357. Baadsgaard, H., 1987, Rb-Sr and K-Ca isotope systemat- Cendon, D. I., C. Ayora, J. J. Pueyo, C. Taberner, and M. ics in minerals from potassium horizons in the Prairie M. Blanc-Valleron, 2008, The chemical and hydrological Evaporite Formation, Saskatchewan, Canada: Chemical evolution of the Mulhouse potash basin (France): Are Geology, v. 66, p. 1-15. "marine" ancient evaporites always representative of syn- Baar, C. A., 1974, Geological problems in Saskatchewan chronous seawater chemistry?: Chemical Geology, v. 252, potash mining due to peculiar conditions during deposi- p. 109-124. tion of Potash Beds, in A. H. Coogan, ed., Fourth Sympo- Cendon, D. I., C. Ayora, and J. P. Pueyo, 1998, The ori- sium on Salt, v. 1: Cleveland, Ohio, North Ohio Geologi- gin of barren bodies in the Subiza potash deposit, Navar- cal Society, p. 101-118. ra, Spain - Implications for sylvite formation: Journal of

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Sedimentary Research Section A-Sedimentary Petrology Emons, H., and H. Voigt, 1981, Untersvchungen zur & Processes, v. 68, p. 43-52. kalten zersetzunung von Carnallit.: Freiberg Forschungsh- er, v. A628, p. 69-78. 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, Implica- Evans, R., 1970, Genesis of sylvite- and carnallite-bear- tions for the origin of secondary sylvite from a simulation ing rocks from Wallace, Nova Scotia: Third Symposium on of carnallite dissolution: Journal of Geochemical Explora- Salt, v. 1, p. 239-245. tion, v. 165, p. 189-198. Fabricius, J., and Rose-Hansen, J., 1988, Pressure-depen-

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