Stable Isotope Evidence for the Petrogenesis of Carnallite in the Middle Devonian Prairie Evaporite Formation, Saskatchewan1 G.D. Koehler2-, T.K. Kyser2- and T. Danyluk3 Koehler, G.D., Kyser, T.K. and Danyluk, T. (1990): Stable Isotope evidence for the petrogenesis of carnallite in the Middle Devonian Prairie Evaporite Formation, SaSkatchewan; in Summary of Investigations 1990, Saskatchewan Geological Survey; Saskatchewan Energy and Mines, Miscellaneous Report 90-4. The potash-bearing members of the Prairie Evaporite Formation in Saskatchewan are mainly composed of three chloride salts: halite (NaCl), sylvite (KCI), and carnallite (KM9C'3.6H20). Other constituents, termed insolubles, typically make up less than 1O percent of the rock and consist of iron-oxides (haematite and goethite), dolomite, quartz, and clay. Sylvite is mined to produce potash whereas halite and carnallite are considered to be undesirable by-products. layered halite and anhydrite into massive halite. This succession is capped by four potash-bearing members in the upper These are, in ascending stratigraphic order: the Esterhazy, White Bear, Belle Plaine, and Patience Lake Members (Holter, 1969). Carnallite occurs along the northern and northeastern rim of the Prairie Evaporite Formation (Figure 1), and is generally more abundant in the lower potash members (ibid.). The Prairie Evaporite Formation consists of a thick s&quence of evaporites that extend from northern Alberta, through central and southeastern Saskatchewan, and into Manitoba and the northern USA (Figure 1). The formation reaches a thickness of 200 m near Saskatoon and thins toward a dissolution edge at the eastern margin. The Prairie Evaporite grades upward from basal 1. Thermodynamics of Carnallite-Sylvite Relationships eom. The occurrence of sylvite in evaporite sequences is problematic for the interpretation of ancient evaporite deposits because unlike carnallite, precipitation of sylvite directly from evaporating seawater is not predicted from chemical models (Holser, 1979; Harvie et al., 1980). Carnallite, however, may undergo incongruent dissolution to sylvite by reaction with underPCS Lonigcin Mine saturated fluids, a process (D Alwinsol Wifowbrook which has been invoked to explain the occurrence of sylG) IMC K-2 Miie vite in several other evaporite deposits (see Lowenstein and PCS Roconville Mine Spencer 1990, for review). There is considerable petrographic evidence that 200 sylvite and carnallite in the Prairie Evaporite Formation are genetically related, but commonly younger than coexisting halite (Wardlaw, 1968; Fuzesy, 1983; Baadsgaard, 1987) and may have been reversibly transformed from one to the other (Wardlaw, 1968). Further, \ stratigraphic relationships b&.)~M'\~- tween carnallite- and sylviterich zones as described by N.OAI< , \ ._ Wardlaw (1968) indicate that \ sylvite generally overlies carnallite where both are present, the reverse of an exFigure 1 - lsopach map ofth6 Prairie Evaporite Formation. Tht1 shadfld area indicates the occur· pected sequence from simple rence of camallite (Holter, 1969) (modified from Baadsgaard, 1987). evaporating seawater. This 0 © (1) Protect funded by the Saskatchewan Potash Producers Association and NSERC Operating Grant (2) Department Of Geologleal Sciences. University of Saskatchewan, Saskatoon, 5askatcheWan, S7N owo (3) Potash Corporation ol Sllsl<atchewan, Sune 500, 122 1st Ave. s .. Saskatoon, Saskatchewllf'I, S7K 763 218 Summary of Investigations 1990 3.8 evidence argues against a syndepositional origin for most of the syfvite and carnallite, and favours a sub-surface diagenetic process. The behaviour of carnallite and syfvite in response to burial and diagenesis can be modelled with chemical thermodynamics. The reaction between carnallite and syfvite can be represented by: 2 KMgCl3.6H20 = KCI + Mg + + carnallite = sylvite + solution 3.6 ~ bl) 0 2cr + 6H20 Carnallite precipitating from evaporating seawater forms from a solution that has an ion activity product (IAP) within the camallite stability field at 1 bar pressure and approximately 30°C, shown as point A in Figure 2. Increasing the pressure as the carnallite is buried stabilizes the sylvite + solution field and moves the carnallitesylvite boundary to higher values of K, so that at a pressure of 1 kilobar, which corresponds to a lithostatic load equivalent to 2-3 km depth, the IAP of the solution that precipitated the carnallite at 1 bar may now lie in the sylvite + solution field. If equilibrium is maintained, the carnallite will react to form further syfvite + solution. Thus, provi~ed the temperature does not rise substantially, increasing pressure as a result of burial will favour the breakdown of carnallite to sytvite. As burial proceeds and the. geotherm recovers, the temperature may become high enough to favour the formation of carnallite from sylvite + solution. 2. Isotopic Properties of Carnallite Carnallites may record, in their hydration waters, the stable isotopic compositions of fluids that were responsible for the diagenesis and recrystallization of the Prairie Evaporite Formation. To this end, measurement of the fractionation of hydrogen and oxygen isotopes between the hydration water of carnallite and the brine from which it formed is fundamental. 18 Carnallite 3.7 O and 0 fractionations were measured between the hydration water of carnallite and brine for both carnallite ~rown in the laboratory, and for natural samples growing over a number of years in brine pools at PCS Lanig~n and _P ~ Rocanville mines. At 2s°C, laboratory experiments indicate that hydration water in carnallite is 4 depleted in D by about 40 permil and enriched in 180 by about 2 permil relative to the brine from which it forms. Preliminary results from laboratory experiments, where carnallite was precipitated at higher temperature ~41 °C), suggest that the fractionation of hydrogen isotopes between the hydration water of carnallite and brine may be slightly temperature dependant. Natural carnallites from brine pools at PCS Lanigan show similar depletions in D, and enrichment in 180 relative to the w~ter in the brine pools. However, carnallite growing in bnne pools at PCS Rocanville show depletions of O by ~b? ut 20 permil and depletions rather than enrichments 8 in O by about 2 permil (Figure 3a, b, c). Both the brine pools are at similar temperatures so the difference in the apparent carnallite-water D and 180 fractionations ...J 3.5 I kbar 3.4 Sylvite + solution 3.3 1 bar 3.2 20 25 30 35 40 so 45 Temperature 0 c Figum 2 • Phase relationship between the equilibrium constant (K) and temperatu,e for the ,eaction KMgC'3°6H2D c KCI + Mg2 + + 2cr + 6H2D, at various pressures. The Ion activity product (/AP) is related to the product of the concentration of er and Mg2+ in the solution and is equal to K along the boundary between cama/lite and syfvite. Thermodynamic data from Pabalan and Pitzer (1987). must be due to differences in the chfmical compositions of the brines, most notably, Ca +. The concentra2 tion of Ca • in brine at Rocanville is 4 times that at Lanigan. These fractionation factors are applicable for systems in which the amount of water in the fluid is substantially greater than the amount in the carnallite. In addition to equilibrium fractionation of hydrogen and oxygen isotopes between fluid and carnallite, the isotopic composition of carnallite also can be affected by the rate of exchange of isotopes with any later postdepositional fluid. Fast isotopic exchange between carnallite and brine will result in measured stable isotopic compositions that are influenced by the last fluid in conta~ with the carnallite. On the other hand, if carnallite is resistant to isotope exchange with fluids, the stable isotopic compositions of the brine from which the carnallite was originally crystallized may be retained in its hydration water. Because the rate of isotope exchange is unknown, isotope exchange experiments were conducted in the laboratory under conditions of high fluid/carnallite ratios. After 67 days of contact at 25°C, hydration water in carnallite was about 10 percent exchanged with brine saturated with respect to carnallite (Figure 4). This rate of isotope exchange is extremely rapid; carnallite in the potash deposits will be in isotopic equilibrium with any diagenetic fluid after contact for about one year. Theref~:>re, carnallite will record the stable isotopic composition of the most recent diagenetic fluid with which it interacted and isotopic composition will be the most sensitive indicator of recent hydrologic activity affecting the potash deposit. o (4) Sta~ l~top~ compositions are reported In the O notation whlcn Is defined as: ('loo ) z ({Rsample/ Rocean ....Ce<} -1) x 1000 Where R Is the 0 / or 0/ 0 ratio. Toe units Of dlttereoce are referenced to as permll (>/ oo). equivalent to differences In the ratios of parts per tllousand. Saskatchewan Geological Survey 219 b) a) Q -100 Q -100 6 !:,. -9 --------, -8 -6 -7 C-0 ~ 6 -5 •• 0 -100 C-0 C-0 -150 -50 ,-.--- -4 - l 50_9 -8 -7 -6 -5 -4 -8 -6 -7 -5 -4 1 0b 1 bb lfb -150 -9 • F/guf9 3 • Relationship between the isotopic compositions of hydration water in camallite (open symbols) and brine from which carnallite precipitates (closed symbols). a) Camallite grown in the laboratory at 25"C. b} Brine pool at PCS Lanigan. c) Brine pool at 408-00-07, PCS Rocanville. Errors for the r3o measurements are ±5 and for '3 180 values an, ±3 per mil. mations above the Prairie Evaporite and do not represent primary precipitation from ancient seawater. 3. Stable Isotopes in Natural Carnallite Samples of carnallite were collected from the Esterhazy Member of the Prairie Evaporite Formation, from the Alwinsal Willowbrook well drill core (Baadsgaard, 1987), ore at PCS Rocanville, carnallite pods at PCS Rocanville, and from carnallite pods at IMC K-2. The hydration water in the carnallite was analyzed for hydrogen and oxygen isotopic compositions to constrain the origin of fluids responsible for the formation of carnallite in different locations within the basin. The Alwinsal Willowbrook samples and ore samples from Rocanville have stable isotopic compositions that, with a few exceptions, fall below the line formed by the stable isotopic compositions of waters from formations above the Prairie Evaporite Formation (Elk Point Basin Trend) (Wittrup et al., 1987), but are roughly parallel to it (Figure 5a). The stable isotopic compositions of the parent brine from which these carnallites form can be estimated using the hydrogen and oxygen isotopic fractionations measured in the laboratory and in brine pools. The estimated stable isotopic compositions of the fluids in equilibrium with these carnallites tend to follow the Elk Point Basin Trend, suggesting that these carnallites formed from waters that have their origins in for- 20 O N == O II • • • • I-, ~ • -20 • ~ A A C-0 Equilibrium fractionation <::! -40 ~- -• · ••• · • -· - - - -· -- • · · -- - - • - -· - - -· 0 Estimated fluid compositions that lie above the Elk Point Basin Trend, such as those which formed the carnallite pods at PCS RocanvHle and IMC K-2 and some of the Alwinsal Willowbrook samples, most likely indicate that these carnallites formed by incorporating most of the water in the brine as the brine interacted with sylvite to form carnallite (Figure 5b). This mechanism is different from the direct precipitation of carnallite from a brine because most of the water responsible for carnallite precipitation is incorporated into the hydration water of the mineral. In this process, the fractionation of the stable isotopes of hydrogen and oxygen between the hydration water of carnallite and brine will be dependant on the amount of water incorP.orated into the mineral and, as a result, the do and d 180 values of the carnallite will more closely resemble those of the brine responsible for the formation of the carnallite. 4. Conclusions The above thermodynamic and stable isotope constraints indicate that primary carnallite, formed from evaporated seawater during Late Devonian time, dehydrated much later to form sylvite under the influence of increasing lithostatic pressure during burial (Figure 6). Maximum burial of the Prairie Evaporite probably occurred during the Cretaceous, as reflected by the temperatures determined from fluid inclusions in halite (Chipley and Kyser, 1989) and by the preponderance of Rb• A Brine ages on sylvite which correspond to - Sr • B Brine the Cretaceous (Baadsgaard, 1987). • - AC Brine Reversion of sylvite to secondary carnallite may be a result of uplift during the 0 20 40 60 80 Tertiary. From thermodynamic considerations, sylvite + solution may react (days) to form carnallite as lithostatic pressure decreases, or as a result of interaction Flflure -4 - Rate of hydrogen isotope exchange between hydration water in camallite and brine at 2S"C. Cama//ite was allowed to exchange wHh 3 brines having diffe19nt of sylvite with Mg-rich brines (Figure 6). stable Isotopic compositions. Exchange Is evidenced by initial values approaching Rt>Sr ages obtained from Alwinsal Wilthe equilibrium value of -37. L\dDeam-H20 is equal to the difference r3DeamaJJtt• lowbrook carnallites suggest that they -60 Time r3o-.... 220 Summary of Investigations 1990 a) 0 -20 -40 oD 0 Al wins&! Willowbrook /),, PCS Rocanville °"' D PCS Rocanvillt pod• v IMC K-2pod b) 0 O -20 -40 O -60 -60 -80 -80 oD - 100 -120 -140 -140 -160 -160 -12 -16 -8 -4 0 ouo + Pods - Rocanville Pods IMC K-2 -100 - 120 -20 Alwinsal Willowbroolc !:::,. Ore zone - Rocanville - 180 -24 0 -20 -16 - 12 -8 -4 0 o18O Figure 5 • (a) Stable isotope compositions of hydration water in camal/ite from th& Alwinsa/ Willowbrook well, ore at PCS Rocanville, pods at PCS Rocanvl//e, and pods from IMC K-2 (open symbols), and the calculated isotopic composition of the water from which th&y formed (closed symbols) assuming the isotopic fractionations measured from laboratory experiments and an infinite reservoir of water. Natural variation in the isotopic composition of recent global precipitation produces th& Meteoric Water Line (MWL). (b). Calculated isotopic compositions of brines that could have precipitated the camal/lte from the Elk Point Basin under conditions wh&re variable percentages of water in the brine enters the carnal/it&. Unes paral/el to the Elk Point Basin Trend denote the possible percentage of the total water in the brine incorporated into the camallite, assuming the water is from basinal brines that follow the Elk Point Basin Trend. Those samp/es of camalfite that have incorporated a high percentage of the available water in the brine into their stJtJcture (eg. >50%) most likely formed from the conversion of sylvite to carnallite. were formed during the last 30 Ma (Baadsgaard, 1987). The hydrogen and oxygen isotopic composition of the carnallites indicate that they have been precipitated by waters that had their origin in formations above the Prairie Evaporite. r-x/,t .¥n.9.11llJ3YY\ Halite ~ Carnallite contains an isotopic record of fluid events in its hydration water, the age of which can be determined using a variety of radiogenic methods. Thus, detailed study of carnallite will provide a history of fluid flow in the Prairie Evaporite Formation and afford a greater understanding of the fluid events and diagenesis related to the present structure and geology of the potash deposits. Dominantly Hante-carnaflite rock (about 3 70 Ma) BurialIncreasing pressure release of Mg-rich brines ~ Halite Conversion of carnallite to sylvite during burial ( about 100-60 Ma) Mg-r ich b asina! brines ~ Uplift and reaction of existing sy lvite with Mg- rich basinal brines to form secondary carnalfite 5. References Baadsgaard, H. (1987): Rb-Sr and K-Ca isotope systematics from potassium horizons in the Prairie Evaporite Formation, Saskatchewan, Canada; Chem. Geol., v66, p1-15. Chipley, D.L. and Kyser, T.K (1989): Fluid inclusion evidence for the diagenesis of the Patience Lake Member of the Prairie Evaporite Formation; Sed. Geol., v64, p287295. Fuzesy, L.M. (1983) : Petrology of the potash ore in the Middle Devonian Prairie Evaporite Formation of Saskatchewan; in McKercher, R.M. (ed.), Potash Technology, Pergamon Press, p47-57. Harvie, C.E., Weare, J .H., Hardie, LA. and Eugster, L.P. (1980): Evaporation of seawater: calculated mineral sequences; Figure 6 • Simple model of cama/lite - sylvite relationships In the Prairie Evaporit9 Scl., v208, p498·500. Formation. (< 30 Ma) 221 Summary of Investigations 1990 Holser, W.T. (1979): Mineralogy of evaporltes; In Burns, R.G. (ed.), Maline Minerals, Reviews in Mineralogy, Mineral. Soc. NO., Washington D.C., v6, p211-294. Holter, M.E. (1969): The Middle Devonian Prairie Evaporlte Formation of Saskatchewan; Sask. Oep. Miner. Resour., Rep. 123, 134p. Lowenstein, T.K. and Spencer, R.J. (1990): Syndepositional origin of potash evaporltes: petrographic and fluid Inclusion evidence; NO. J. Sci., v290, pt-42. Saskatchewan Geological Sul\18y Pabalan, R.T. and Pitzer, K.S. (1987): Thermodynamics of concentrated electrolyte mlxturff and the prediction of mineral solubilities to high temperatures for mixtures in the system Na-K-Mg-Cl·S04-QH-H20; Geochim. Cosmochim. Acta, v51 , p2429-2443. Wardlaw, N.C. (1968): Carnallite-sylvite relationships in the Middle Devonian Prairie Evaporite Formation, Saskatchewan; Geol. Soc. NO. Bull., v79, p1273-1294. Wittrup, M.B .• Danyluk, T. and Kyser, T.K. (1987): The use of stable isotopes to determine the source of brines in Saskatchewan potash mines; in Gilboy, C.F. and Vigrass, LW. (eds.), Economic Minerals of Saskatchewan, Sask. Geol. Soc., Spec. Publ. No. 8, p159-165. 222
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