Salty Matters

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Brine evolution and origins of potash ore salts: Primary or secondary? Part 1 of 3

John Warren - Wednesday, October 31, 2018

Introduction

There is a dichotomy in mineralogical associations and precipitation series in both modern and ancient potash ore deposits. Interpretations of ancient potash ore mineralogies across time are generally tied to the evolution of the hydrochemical proportions in modern and ancient oceans. We have already discussed this in previous Salty Matters articles and will not repeat the details here (see August 10, 2015; July 31, 2018).

At times in the past, such as in the Devonian and the Cretaceous, the world ocean was depleted in the Mg and SO4 relative to the present-day ocean (Figure 1a). In the relevant literature, this has led to the application of the term MgSO4-depleted versus MgSO4-enriched oceans. In terms of brine evolution, this is related to the gypsum divide, with the term MgSO4-enriched used to describe the ocean chemistry of today and other times in the past, such as in the Permian, when MgSO4 bittern salts typify co-precipitates with sylvite/carnallite (Figure 1b).


The validity of the ocean chemistry argument is primarily based on determinations of inclusion chemistries as measured in chevron halites (Figure 1a; Lowenstein et al., 2014). Inclusions in growth-aligned primary halite chevrons are assumed to preserve the chemical proportions of the ambient oceanic brine precipitating the halite. That is, the working assumption is that pristine aligned-halite chevrons have not been subject to significant diagenetic alteration once the salt was deposited and permeability was lost due to ongoing halite cementation in the shallow (eogenetic) subsurface realm.

The same assumption as to the pristine nature of chevron halite is applied to outcomes of biological experiments where Permian archaeal/halobacterial life has been re-animated using ancient salt samples (Vreeland et al., 2000).

Primary potash ore?

But does the same assumption of pristine texturing across time also apply to the halite layers associated with the world’s potash ores? In my experience of subsurface potash ores and their textures, I have rarely seen primary-chevron halite interlayered with potash ore layers of either sylvite or carnallite. An obvious exception is the pristine interlayering of chevron halite and sylvite in the now-depleted Eocene potash ores of the Mulhouse Basin, France (Lowenstein and Spencer, 1990). There, the sylvite layers intercalate at the cm-scale with chevron halite, and the alternating layering is thought to be related to precipitation driven by temperature fluctuations in a series of shallow density-stratified meromictic brine lakes (documented in the third Salty Matters article).

More typically, ancient potash ore textures are diagenetic and indicate responses to varying degrees of dissolution, brine infiltration and alteration. The simpler styles of brine infiltration consist of a background matrix dominated by cm-dm scale chevron halite layers that have been subject to dissolution and karstification during shallow burial. Resultant cm-dm scale voids typically retain a mm-thick selvedge of CaSO4 lathes and needles, followed by fill of the remaining void by varying amounts of sparry halite, carnallite and sylvite. This type of texture dominates in Quaternary stratoid potash layers in the southern Qaidam Basin in China and the Cretaceous carnallite-rich layers of the Maha Sarakham Fm in NE Thailand and southern China (Warren, 2016). Then there are the even more altered and recrystallised, but still bedded, textures in the potash ore zones of Devonian Prairie Evaporite of western Canada (Wardlaw, 1968) and potash layers in the Permian Basin in west Texas and New Mexico (Lowenstein, 1988; Holt and Powers, 2011). Beyond this level of diagenetic texturing are the flow-orientated and foliated structural textures of the Permian potash ores in potash mines in the diapiric Zechstein evaporites of Germany and Poland, the Kungurian diapirs of the Cis-Urals of Russia and the Devonian diapirs of the Pripyat Basin.

And so, herein lies the main point of discussion for this and the next two Salty Matters articles, namely, what, where and when is(are) the mechanism(s) or association(s) of hydrochemical mechanisms that sufficiently concentrate or alter a brine’s chemistry to where it precipitates economic levels of a variety of potash salts, as either muriate of potash or sulphate of potash. Notably, there are no Quaternary-age solid-state ore systems that are mined for potash.

In this article, we look at the main modern brine systems where muriate of potash (MOP) is produced economically by solar evaporation (Salar de Atacama, Chile; Qarhan sump, China; and the southern Basin of the Dead Sea). In the second article we will focus on sulphate of potash (SOP) production in Quaternary saline sumps (Great Salt Lake, USA and Lop Nur, China). In the third article we shall discuss depositional and diagenetic characteristics of solid-state potash ores some of the world’s more substantial deposits (e.g. Devonian of western Canada) and relate the observations of ancient potash texture to time-based evolution of potash precipitating brines, and subsequent alteration or the ore textures, which are typically driven by later cross-flushing by one or more pulses of diagenetically-evolved brines.


Potash from brine in Salar de Atacama (MOP in a simple near-uniserial set of brine concentration pans)

Potash production in Salar de Atacama is a byproduct of the output of lithium carbonate from shallow lake brines pumped into a series of solar concentration pans (Figure 2). The inflow feed to the concentrator pans comes from fields of brine wells extracting pore waters from the salt nucleus facies in the central and southern part of the Atacama saltflats (Figure 3a,b). However, Atacama pore brines are not chemically homogeneous across the salar (Alonso and Risacher, 1996; Risacher and Alonso, 1996; Carmona et al., 2000; Pueyo et al. 2017). The most common primary inflow brines to the Atacama sump are sulphate-rich (SO4/Ca > 1), but there are areas in the salt flat at the southern end of the playa, such as those near the Península de Chépica, where pore brines are richer in calcium (SO4/Ca < 1- Figure 4). These brines also contain elevated levels of lithium (Figure 3c; Risacher et al., 2003).


Ion proportions in the natural salar inflow and pore waters are dominated by sodium and chloride, followed by potassium, then magnesium then sulphate in the more saline regions of the salar sump (Figure 4; Lowenstein and Risacher, 2009). In addition, owing to the progressive reduction of porosity in depth, driven mainly by diagenetic halite cementation, the pore brine in the upper 40 meters of the salar sediment column accumulates by advection in the area of greatest porosity, i.e., in this top 40 m of sediments of the salt flat at the southern end of Atacama (Pueyo et al., 2017). When pumped from the hosting salar sediments into the concentrator pans the final brines contain elevated levels of lithium chloride (≈ 6000 ppm). These lithium-enriched acidic waters are then pumped to a nearby industrial plant and processed to obtain lithium carbonate as the main commercial product.

In a benchmark paper, Pueyo et al. (2017) document the brine evolution and products recovered in the solar pans of Rockwood Lithium GmbH (Figure 2b; formerly Sociedad Chilena del Litio) in the Península de Chépica. There, a bittern paragenesis of salts precipitates that is mostly devoid of magnesium sulphate salt due to the low levels of sulphate attained in the various concentator pans via widespread precipitation of gypsum in the early concentrator pans (Figures 4, 5).


The depletion of sulphate levels in the early concentrators is done via artificial manipulation of ionic proportions in the feeders. Without alteration of the ionic proportion in halite-stage brines, the evaporation of the saltflat brine feeds, which are rich in sulfate, would result in assemblages that, in addition to potassic chlorides, would contain contain problematic magnesium sulfates (such as schoenite, kainite, glaserite as in Great Salt Lake). The presence of such sulphate salts and ions in the liquor feeding the lithium carbonate plant would complicate the lithium carbonate extraction process. So the aim in the Atacama pans is to remove most of the sulphate via constructing a suitably balanced chemistry in the early concentrator brine stage (to illustrate this compare ionic proportions in sulphate between Figure 4 and Figure 5).


Such a sylvite/carnallite brine paragenesis, sans sulphate (as seen in Figure 5), is similar to that envisaged as the feed chemistry for ancient Mg-sulphate-free marine potash deposits (Braitsch, 1971). That is, as the brines pass through the concentrators, with successive pans transitioning to higher salinities, the potash salts carnallite and sylvite precipitate, without the complication of the widespread magnesium sulphate salts that complicate the processing of marine-derived bitterns. Such MgSO4 double-salts typify SOP production in the Ogden Salt flats, with their primary feed of sulphate-rich Great Salt Lake waters. Relative proportions of sulphate are much higher in the Great Salt Lake brine feed (see article 2 in this series).


Once the balance is accomplished by mixing a Ca-rich brine from further up the concentration series, with the natural SO4-brine in an appropriate ratio, the modified brines are then pumped and discharged into the halite ponds of the saltwork circuit (ponds number 17 and 16, as seen in Figures 5 and 6). In these ponds, halite precipitates from the very beginning with small amounts of accessory gypsum as brines are saturated with both minerals. Subsequently, the brines are transferred to increasingly smaller ponds where halite (ponds 15 and 14), halite and sylvite (pond 13), sylvite (ponds 12, 11 and 10), sylvite and carnallite (pond 9), carnallite (pond 8), carnallite and bischofite (pond 7), bischofite (ponds 6, 5 and 4), bischofite with some lithium-carnallite [LiClMgCl26H2O] (pond 3), and lithium-carnallite (ponds 2 and 1) precipitate. The brines of the last ponds (R-1 to R-3), whose volumes undergo a reduction to 1/50th of the starting volume, are treated at the processing factory to obtain lithium carbonate as the main commercial product.

As documented in Pueyo et al. (2017), the average daily temperature in the Salar de Atacama ranges between 22 °C in February and 8 °C in July, with a maximum oscillation of approximately 14 °C. Wind speed ranges daily from< 2 ms−1 in the morning to 15 ms−1 in the afternoon. Rainfall in the area of the salt flat corresponds to that of a hyperarid desert climate with an annual average, for the period 1988–2011, of 28 mm at San Pedro de Atacama, 15.1 mm at Peine and 11.6 mm at the lithium saltworks, in the last case ranging between 0 and 86 mm for individual years. The adjoining Altiplano to the east has an arid climate with an average annual rainfall of approximately 100 mm. The average relative humidity in the saltpan area, for the period 2006–2011, is 19.8% with a maximum around February (27%) and a minimum in October (15%) and with a peak in the morning when it may reach 50%. The low relative humidity and the high insolation (direct radiation of 3000 kWh m−2 yr−1) in the salt flat increase the efficiency of solar evaporation, giving rise to the precipitation and stability of very deliquescent minerals such as carnallite and bischofite. The average annual evaporation value measured in the period 1998–2011, using the salt flat interstitial brine, is approximately 2250 mm with a peak in December–January and a minimum in June–July. This cool high-altitude hyperarid climatic setting, where widespread sylvite and carnallite accumulates on the pan floor, is tectonically and climatically distinct from the hot-arid subsealevel basinwide desert seep settings envisaged for ancient marine-fed potash basins (as discussed in the upcoming third article in this series).

MOP from brine Dabuxum/Qarhan region, Qaidam Basin, China

The Qarhan saltflat/playa is now the largest hypersaline sump within the disaggregated lacustrine system that makes up the hydrology of Qaidam Basin, China (Figure 7a). The Qaidam basin sump has an area of some 6,000 km2, is mostly underlain by bedded Late Quaternary halite. Regionally, the depression is endorheic, fed by the Golmud, Qarhan and Urtom (Wutumeiren) rivers in the south and the Sugan River in the north, and today is mostly covered by a layered halite pan crust. Below, some 0 to 1.3m beneath the playa surface, is the watertable atop a permanent hypersaline groundwater brine lens (Figure 7b).


The southern Qaidam sump entrains nine perennial salt lakes: Seni, Dabiele, Xiaobiele, Daxi, Dabuxum (Dabsan Hu), Tuanjie, Xiezuo and Fubuxum north and south lakeshore (Figure 7). Dabuxum Lake, which occupies the central part of the Qarhan sump region, is the largest of the perennial lakes (184 km2; Figures 7b, 8a). Lake water depths vary seasonally from 20cm to 1m and never deeper than a metre, even when flooded. Salt contents in the various lakes range from 165 to 360 g/l, with pH ranging between 5.4 and 7.85. Today the salt plain and pans of the Qarhan playa are fed mostly by runoff from the Kunlun Mountains (Kunlun Shan), along with input from a number of saline groundwater springs concentrated along a fault trend defining an area of salt karst along the northern edge of the Dabuxum sump, especially north of Xiezuo Lake (Figure 8a).


The present climate across the Qaidam Basin is cool, arid to hyperarid (BWk), with an average yearly rainfall of 26 mm, mean annual evaporation is 3000–3200 mm, and a yearly mean temperature 2-4° C in the central basin (An et al., 2012). The various salt lakes and playas spread across the basin and contain alternating climate-dependent evaporitic sedimentary sequences. Across the basin the playa sumps are surrounded by aeolian deposits and wind-eroded landforms (yardangs). In terms of potash occurrence, the most significant region in the Qaidam Basin is the Qarhan sump or playa (aka Chaerhan Salt Lake), which occupies a landscape low in front of the outlets of the Golmud and Qarhan rivers (Figure 7a, b). Overall the Qaidam Basin displays a typical exposed lacustrine geomorphology and desert landscape, related to increasing aridification in a cool desert setting. In contrast, the surrounding elevated highlands are mostly typified by a high-alpine tundra (ET) Köppen climate.


Bedded and displacive salts began to accumulate in the Qarhan depression some 50,000 years ago (Figure 9). Today, outcropping areas of surface salt crust consist of a chaotic mixture of fine-grained halite crystals and mud, with a rugged, pitted upper surface (Schubel and Lowenstein, 1997; Duan and Hu, 2001). Vadose diagenetic features, such as dissolution pits, cavities and pendant cements, form wherever the salt crust lies above the watertable. Interbedded salts and siliciclastic sediments underlying the crust reach thicknesses of upwards of 70m (Kezao and Bowler, 1986).

Bedded potash, as carnallite, precipitates naturally in transient volumetrically-minor lake strandzone (stratoid) beds about the northeastern margin of Lake Dabuxum (Figure 8a) and as cements in Late Pleistocene bedded deposits exposed in and below nearby Lake Tuanje in what is known as the sediments of the Dadong ancient lake (Figure 8b). Ongoing freshened sheetflow from the up-dip bajada fans means the proportion of carnallite versus halite in the evaporite unit increases with distance from the Golmud Fan across, both the layered (bedded) and stratoid (cement) modes of occurrence.

At times in the past, when the watertable was lower, occasional meteoric inflow was also the driver for the brine cycling that created the karst cavities hosting the halite and carnallite cements that formed as prograde cements during cooling of the sinking brine (Figure 9). Solid bedded potash salts are not present in sufficient amounts to be quarried, and most of the exploited potash resource resides in interstitial brines that are pumped and processed using solar ponds.

Modern halite crusts in Qarhan playa contain the most concentrated brine inclusions of the sampled Quaternary halites, suggesting that today may be the most desiccated period in the Qarhan-Tuanje sump recorded over the last 50,000 years (values in the inset in figure 9 were measured on clear halite-spar void-fill crystals between chevrons). Inclusion measurements from these very early diagenetic halite show they formed syndepositionally from shallow groundwater brines and confirm the climatic record derived from adjacent primary (chevron) halite. The occurrence of carnallite-saturated brines in fluid inclusions in the diagenetic halite in the top 13 m of Qarhan playa sediments also imply a prograde diagenetic, not depositional, origin of carnallite, which locally accumulated in the same voids as the more widespread microkarst halite-spar cements.

Today, transient surficial primary carnallite rafts can accumulate along the northern strandline of Lake Dabuxum (Figure 9; Casas, 1992; Casas et al., 1992). Compositions of fluid inclusions in the older primary (chevron) halite beds hosting carnallite cements in the various Qarhan salt crusts represent preserved lake brines and indicate relatively wetter conditions throughout most of the Late Pleistocene (Yang et al., 1995). Oxygen isotope signatures of the inclusions record episodic freshening and concentration during the formation of the various salt units interlayered with lacustrine muds. Desiccation events, sufficient to allow halite beds to accumulate, occurred a number of times in the Late Quaternary: 1) in a short-lived event ≈ 50,000 ka, 2) from about 17 - 8,000 ka, and 3) from about 2,000 ka till now (Figure 9).

The greatest volume of water entering Dabuxum Lake comes from the Golmud River (Figure 7b). Cold springs, emerging from a narrow karst zone some 10 km to the north of the Dabuxum strandline and extending hundreds of km across the basin, also supply solutes to the lake. The spring water discharging along this fault-defined karst zone is chemically similar to hydrothermal CaCl2 basin-sourced waters as defined by Hardie (1990), and are interpreted as subsurface brines that have risen to the surface along deep faults to the north of the Dabuxum sump (Figure 9, 10; Spencer et al., 1990; Lowenstein and Risacher, 2009). Depths from where the Ca–Cl spring waters rise is not known. Subsurface lithologies of the Qaidam Basin in this region contains Jurassic and younger sediments and sedimentary rock columns, up to 15 km thick, which overlie Proterozoic metamorphic rocks (Wang and Coward, 1990).


Several lakes located near the northern karst zone (Donglin, North Huobusun, Xiezhuo, and Huobusun) receive sufficient Ca–Cl inflow, more than 1 part spring inflow to 40 parts river inflow, to form mixtures with chemistries of Ca equivalents > equivalents HCO3 + SO4 to create a simple potash evaporation series (this is indicated by the Ca-Cl trend line in Figure 10a). With evaporation such waters, after precipitation of calcite and gypsum, evolve into Ca–Cl-rich, HCO3–SO4-poor brines (brines numbered 5, 7-12 in figure 11a).


Dabuxum is the largest lake in the Qarhan region, with brines that are Na–Mg–K–Cl dominant, with minor Ca and SO4 (Figure 10d, 11a). These brines are interpreted by Lowenstein and Risacher (2009) to have formed from a mix of ≈40 parts river water to 1 part spring inflow, so that the equivalents of Ca ≈ equivalents HCO3 + SO4 (Figure 10b). Brines with this ratio of river to spring inflow lose most of their Ca, SO4, and HCO3 after precipitation of CaCO3 and CaSO4, and so form Na–K–Mg–Cl brines capable of precipitating carnallite and sylvite (Figure 11a). This chemistry is similar to that of ancient MgSO4-depleted marine bitterns (Figure 1)

The chemical composition of surface brines in the various lakes on the Qarhan Salt plain vary and appear to be controlled by the particular blend of river and spring inflows into the local lake/playa sump. In turn, this mix is controlled geographically by proximity to river mouths and the northern karst zone. Formation of marine-like ionic proportions in some lakes, such as Tuanje, Dabuxum and ancient Dadong Lake, engender bitterns suitable for the primary and secondary precipitation of sylvite/carnallite (Figures 10b-d; 11a). The variation in the relative proportion of sulphate to chloride in the feeder brines is a fundamental control on the suitability of the brine as a potash producer.

Figure 11b clearly illustrates sulphate to chloride variation in pore waters in the region to the immediate north and east of Dabuxum Lake. Brine wells in the low-sulphate area are drawn upon to supply feeder brines to the carnallite precipitating ponds. The hydrochemistry of this region is a clear indication of the regional variation in the sump hydrochemistry (Duan and Hu, 2001), but also underlines why it is so important to understand pore chemistry, and variations in aquifer porosity and permeability, when designing a potash plant in a Quaternary saline setting.

Compared to the MOP plant in Atacama, there as yet no lithium carbonate extraction stream to help ameliorate costs associated with carnallite processing. Lithium levels in the Qaidam brines, whilee levated, are much lower than in the Atacama brine feeds. Regionally, away from the Tuanje-Dadong area, most salt-lake and pore brines in the Qaidam flats are of the magnesium sulphate subtype and the ratio of Mg/Li can be as high as 500. With such brine compositions, the chemical precipitation approach, which is successfully applied to lithium extraction using low calcium and magnesium brines (such as those from Zabuye and Jezecaka Lake on the Tibetan Plateau and in the Andean Altiplano), would consume a large quantity of chemicals and generate a huge amount of solid waste. Accordingly, brine operations in the Qarhan region are focused on MOP production from a carnallitite slurry using extraction techniques similar to those utilised in the Southern Dead Sea. But owing to its cooler climate compared to the Dead Sea sump, the pond chemistry is subject to lower evaporation rates, higher moisture levels in the product, and a longer curing time.

Potash in the Qarhan region is produced by the Qinghai Salt Lake Potash Company, which owns the 120-square-kilometer salt lake area near Golmud (Figure 7). The company was established and listed on the Shenzhen Stock Exchange in 1997. Currently, it specialises in the manufacture of MOP from pore brines pumped from appropriate low-sulphate regions in the lake sediments (Figure 12). The MOP factory processes a carnallite slurry pumped from pans using a slurry processing stream very similar to the dual process stream utilized in the pans of the Southern Basin in the Dead Sea and discussed in the next section.

The final potash product in the Qaidam sump runs 60-62% K2O with >2% moisture and is distributed under the brand name of “Yanqiao.” With annual production ≈3.5 million tonnes and a projected reserve ≈ 540 million tonnes, the company currently generates 97% of Chinese domestic MOP production. However, China’s annual agricultural need for potash far outpaces this level of production. The company is jointly owned by Qinghai Salt Lake Industry Group and Sinochem Corporation and is the only domestic producer of a natural MOP product.

Dead Sea Potash (MOP operation in the Southern Basin)

The Dead Sea water surface defines what is the deepest continental position (-417 m asl) on the earth’s current terrestrial surface. In the Northen Basin is our only modern example of bedded evaporitic sediments (halite and gypsum) accumulating on the subaqueous floor of a deep brine body, where water depths are hundreds of metres (Warren, 2016). This salt-encrusted depression is 80 km long and 20 km wide, has an area of 810 km2, is covered by a brine volume of 147 km3 and occupies the lowest part of a drainage basin with a catchment area of 40,650 km2 (Figure 13a). However, falling water levels in the past few decades mean the permanent water mass now only occupies the northern part of the lake, while saline anthropogenic potash pans occupy the Southern Basin, so that the current perennial “Sea” resides in the Northern Basin is now only some 50 km long (Figure 13b).


Rainfall in the region is 45 to 90 mm, evaporation around 1500 mm, and air temperatures between 11 and 21°C in winter and 18 to 40°C in summer, with a recorded maximum of 51°C. The subsiding basin is surrounded by mountain ranges to the east and west, producing an orographic rain shadow that further emphasises the aridity of the adjacent desert sump. The primary source of solutes in the perennial lake is ongoing dissolution of the halokinetic salts of the Miocene Sedom Fm (aka Usdum Fm) a marine evaporite unit that underlies the Dead Sea and approaches the surface in diapiric structures beneath the Lisan Straits and at Mt. Sedom (Garfunkel and Ben-Avraham, 1996).

A series of linked fractionation ponds have been built in the Southern Basin of the Dead Sea to further concentrate pumped Dead Sea brine to the carnallite stage (Figure 13). On the Israeli side this is done by the Dead Sea Works Ltd. (owned by ICL Fertilisers), near Mt. Sedom, and by the Arab Potash Company (APC) at Ghor al Safi on the Jordanian side. ICL is 52.3% owned by Israel Corporation Ltd.(considered as under Government control), 13.6% shares held by Potash Corporation of Saskatchewan and 33.6% shares held by various institutional investors and the general public (33.64%). In contrast, PotashCorp owns 28% of APC shares, the Government of Jordan 27%, Arab Mining Company 20%, with the remainder held by several small Middle Eastern governments and a public float that trades on the Amman Stock Exchange. This gives PotashCorp control on how APC product is marketed, but it does not control how DSW product is sold.

In both the DSW and APC brine fields, muriate of potash is extracted by processing carnallitite slurries, created by sequential evaporation in a series of linked, gravity-fed fractionation ponds. The inflow brine currently pumped from the Dead Sea has a density of ≈1.24 gm/cc, while after slurry extraction the residual brine, with a density of ≈1.34 gm/cc, is pumped back into the northern Dead Sea basin water mass. The total area of the concentration pans is more than 250 km2, within the total area of 1,000 km2, which is the southern Dead Sea floor. The first stage in the evaporation process is pumping of Dead Sea water into header ponds and into the gravity-fed series of artificial fractionation pans that now cover the Southern Basin floor. With the ongoing fall of the Dead Sea water level over the past 60 years, brines from the Northern Basin must be pumped higher and over further lateral distances. This results in an ongoing need for more powerful brine pumps and an increasing problem with karst dolines related to lowered Dead Sea water levels. Saturation stages of the evolving pan brines are monitored and waters are moved from pan to pan as they are subject to the ongoing and intense levels of natural solar evaporation (Figure 13b, c; Karcz and Zak, 1987).

The artificial salt ponds of the Dead Sea are unusual in that they are designed to trap and discard most of the halite precipitate rather than harvest it. Most other artificial salt ponds around the world are shallow pans purpose-designed as ephemeral water-holding depressions that periodically dry out so that salts can be scrapped and harvested. In contrast, the Dead Sea halite ponds are purpose-designed to be permanently subaqueous and relatively deep (≈4m). Brine levels in the ponds vary by a few decimetres during the year, and lowstand levels generally increase each winter when waste brine is pumped back into the northern basin.

As the Dead Sea brine thickens, minor gypsum, then voluminous halite precipitates on the pan floor in the upstream section of the concentration series, where the halite-precipitating-brines have densities > 1.2 gm/cc (Figure 13c). As the concentrating brines approach carnallite-precipitating densities (around 1.3 gm/cc), they are allowed to flow into the carnallite precipitating ponds (Figure 13c). Individual pans have areas around 6-8 km2 and brine depths up to 2 metres. During the early halite concentration stages, a series of problematic halite reefs or mushroom polygons can build to the brine surface and so compartmentalise and entrap brines within isolated pockets enclosed by the reefs. This hinders the orderly downstream progression of increasingly saline brines into the carnallite ponds, with the associated loss of potash product.


When the plant was first designed, the expectation was that halite would accumulate on the floor of the early fractionation ponds as flat beds and crusts, beneath permanent holomictic brine layers. The expected volume of salt was deposited in the pans each year (Talbot et al., 1996), but instead of accumulating on a flat floor aggrading 15-20 cm each year, halite in some areas aggraded into a series of polygonally-linked at-surface salt reefs (aka salt mushrooms). Then, instead of each brine lake/pan being homogenized by wind shear across a single large subaqueous ponds, the salt reefs separated the larger early ponds into thousands of smaller polygonally-defined inaccessible compartments, where the isolated brines developed different compositions (Figure 14). Carnallitite slurries crystallised in inter-reef compartments from where it could not be easily harvested, so large volumes of potential potash product were locked up in the early fractionation ponds (Figure 14a, b). Attempts to drown the reefs by maintaining freshened waters in the ponds during the winters of 1984 and 1985 were only partly successful. The current approach to the salt reef problem in the early fractionation ponds is to periodically breakup and remove the halite reefs and mushrooms by a combination of dredging and occasional blasting (Figure 14c).


Unlike seawater feeds to conventional marine coastal saltworks producing halite with marine inflow salinities ≈35‰, the inflow brine pumped into the header ponds from the Dead Sea already has a salinity of more than 300‰ (Figure 15). Massive halite precipitation occurs quickly, once the brine attains a density of 1.235 (≈340‰) and reaches a maximum at a density of 1.24 (Figure 13c). Evaporation is allowed to continue in the initial halite concentrator ponds until the original water volume pumped into the pond has been halved. Concentrated halite-depleted brine is then pumped through a conveyance canal into a series of smaller evaporation ponds where carnallite, along with minor halite and gypsum precipitates (Figure 13c). Around 300–400 mm of carnallite salt slurry is allowed to accumulate in the carnallite ponds, with 84% pure carnallite and 16% sodium chloride as the average chemical composition (Figure 6a; Abu-Hamatteh and Al-Amr, 2008). The carnallite bed is harvested (pumped) from beneath the brine in slurry form and is delivered through corrosion-resistant steel pipes to the process refineries via a series of powerful pumps.

This carnallitite slurry is harvested using purpose-specific dredges floating across the crystalliser ponds. These dredges not only pump the slurry to the processing plant but also undertake the early part of the processing stream. On the dredge, the harvested slurry is crushed and size sorted, with the coarser purer crystals separated for cold crystallisation. The remainder is slurried with the residual pan brine and then further filtered aboard the floating dredges. At this stage in the processing stream the dredges pipe the treated slurries from the pans to the refining plant.


On arrival at the processing plant, raw product is then used to manufacture muriate of potash, salt, magnesium chloride, magnesium oxide, hydrochloric acid, bath salts, chlorine, caustic soda and magnesium metal (Figure 16a). Residual brine after carnallitite precipitation contain about 11-12 g/l bromide and is used for the production of bromine, before the waste brine (with a density around 1.34 gm/cc) is returned to the northern Dead Sea water mass. The entire cycle from the slurry harvesting to MOP production takes as little as five hours.

In the initial years of both DSW and APC operations, MOP was refined from the carnallite slurry via hot leaching and flotation. In the coarser-crystalline carnallitite feed, significant volumes of sylvite are now produced more economically in a cold crystallisation plant (Figure 16b). The cold crystallisation process takes place at ambient temperature and is less energy-intensive than the hot crystallisation unit. The method also consumes less water but requires a higher and more consistent grade of carnallite feed (Mansour and Takrouri, 2007; Abu-Hamatteh and Al-Amr, 2008). Both hot (thermal) and cold production methods can be utilized in either plant, depending on the quality of the slurry feed.

Sylvite is produced via cold crystallisation using the addition of water to incongruently dissolve the magnesium chloride from the crystal structure. If the carnallite slurry contains only a small amount of halite, the solid residue that remains after water flushing is mostly sylvite. As is shown in Figure 16b, if the MgCl2 concentration is at or near the triple-saturation point (the point at which the solution is saturated with carnallite, NaCl, and KCl), the KCl solubility is suppressed to the point where most of it will precipitate as sylvite. For maximum recovery, the crystallising mixture must be saturated with carnallite at its triple-saturation point. If the mixture is not saturated, for example, it contains higher levels of NaCl, then more KCl will dissolve during the water flushing of the slurry. Industrially, the cold crystallizers are usually fed with both coarse and fine carnallite streams, such that 10% carnallite remains in the slurry, this can be achieved by adjusting addition of process water (Mansour and Takrouri, 2007).

Successful cold crystallisation depends largely on a consistent high-quality carnallite feed. If a large amount of halite is present in the feed slurry, the resulting solid residue from cold crystallisation is sylvinite, not sylvite. This needs to be further refined by hot crystallisation, a more expensive extraction method based on the fact that the solubility of sylvite varies significantly with increasing temperature, while that of salt remains relatively constant (Figure 16c). As potash brine is hot leached from the sylvinite, the remaining halite is filtered off, and the brine is cooled under controlled conditions to yield sylvite.

Residual brine from the crystallisation processes then undergoes electrolysis to yield chlorine, caustic soda (sodium hydroxide) and hydrogen. Chlorine is then reacted with brine filtered from the pans to produce bromine. The caustic soda is sold, and the hydrogen is used to make bromine compounds, with the excess being burnt as fuel. Bromine distilled from the brine is sold partly as elemental bromine, and partly in the form of bromine compounds produced in the bromine plant at Ramat Hovav (near Beer Sheva). This is the largest bromine plant in the world, and Israel is the main exporter of bromine to Europe. About 200,000 tons of bromine are produced each year.

Residual magnesium chloride-rich solutions created by cold crystallisation are concentrated and sold as flakes for use in the chemical industry and for de-icing (about 100,000 tons per year) and dirt road de-dusting. Part of the MgCl2 solution produced is sold to the nearby Dead Sea Periclase plant (a subsidiary of Israel Chemicals Ltd.). At this plant, the brine is decomposed thermally to give an extremely pure magnesium oxide (periclase) and hydrochloric acid. In Israel, Dead Sea Salt Work’s (DSW) production has risen to more than 2.9 Mt KCl since 2005, continuing a series of increments and reflecting an investment in expanded capacity, the streamlining of product throughput in the mill facilities, and the amelioration of the effects salt mushrooms, and increased salinity of the Dead Sea due to extended drought conditions (Figure 17).

On the other side of the truce line in Jordan, the Arab Potash Co. Ltd. (APC) output rose to 1.94 Mt KCl in 2010 The APC plant now has the capacity to produce 2.35 Mt KCl and like the DSW produces bromine from bittern end brines. Early in the pond concentration stream, APC also has to remove salt mushrooms from its ponds, a process which when completed can increase carnallite output by over 50,000 t/yr. Currently, APC is continuing with an expansion program aimed at increasing potash capacity to 2.5 Mt/yr.


MOP brines and Quaternary climate

As mentioned in the introduction, exploited Quaternary potash deposits encompass both MOP and SOP mineral associations across a range of climatic and elevation settings. This article focuses on the three main MOP producing examples, the next deals with SOP Quaternary producers (Great Salt Lake, USA and Lop Nur, China). Interestingly, both sets of Quaternary examples are nonmarine brine-fed depositional hydrologies. All currently-active economic potash plants hosted in Quaternary systems do not mine a solid product but derive their potash solar evaporation of pumped hypersaline lake brines. For MOP processing to be economic the sulphate levels in the brines held in bittern-stage concentrator pans must be low and Mg levels are typically high, so favoring the precipitation of carnallite over sylvite in all three systems.

In Salar de Atacama the low sulphate levels in the bittern stage is accomplished by artificially mixing a CaCl2 brine from further up the evaporation stream with a less saline more sulphate-enriched brine. The mixing proportions of the two brine streams aims to maximise the level of extraction/removal of CaSO4 in the halite pans prior to the precipitation of sylvite and carnallite. In the case of the pans in the Qarhan sump there is a similar but largely natural mixing of river waters with fault-fed salt-karst spring waters in a ratio of 40:1 that creates a hybrid pore brine with a low sulphate chemistry suitable for the precipitation of both natural and pan carnallite. In the case of the Dead Sea brine feed, the inflowing Dead Sea waters are naturally low in sulphate and high in magnesium. The large size of this natural brine feed systems and its homogeneous nature allows for a moderate cost of MOP manufacture estimated in Warren 2016, chapter 11 to be US$ 170/tonne. The Qarhan production cost is less ≈ US$ 110/tonne but the total reserve is less than in the brine system of the Dead Sea. In Salar de Atacama region the MOP cost is likely around US$ 250-270/tonne, but this is offset by the production of a bischofite stage brine suitable for lithium carbonate extraction.

Outside of these three main Quaternary-feed MOP producers there are a number of potash mineral occurrences in intermontane depressions in the high Andes in what is a high altitude polar tundra setting (Koeppen ET), none of which are commercial (Figure 18a). Similarly, there a number of non-commercial potash (SOP) mineral and brine occurrences in various hot arid desert regions in Australia, northern Africa and the Middle East (Koeppen BWh) that we shall look at in the next article. In the Danakhil depression there is the possibility of a future combined MOP/SOP plant (see Salty Matters April 19, 2015; April 29, 2015; May 1, 2015; May12, 2015 and Bastow et al., 2018). In the Danakhil it is important to distinguish between the current non-potash climate (BWh - Koeppen climate) over the Dallol saltflat in Ethiopia, with its nonmarine brine feed and the former now-buried marine fed potash (SOP)/halite evaporite system. The latter is the target of current exploration efforts in the basin, focused on sediments now buried 60-120m below the Dallol saltflat surface. Nowhere in the Quaternary are such dry arid desert climates (BWh) associated with commercial accumulations of potash minerals.


Climatically most commercial potash brine systems in Quaternary-age sediments are located in cooler endorheic intermontane depressions (BWk, BSk) or in the case of the Dead Sea an intermontane position in the sump of the Dead Sea, the deepest position of any continental landscape on the earth’s surface (-417 msl). The association with somewhat cooler and or less arid steppe climates implies a need for greater volumes of brine to reside in a landscape in order to facilitate the precipitation of significant volumes of potash bitterns (Figure 18a,b).

In summary, all three currently economic Quaternary MOP operations are producing by pumping nonmarine pore or saline lake brines into a series of concentrator pans. The final bittern chemistry in all three is a low-sulphate liquour, but with inherently high levels of magnesium that favors the solar pan production of carnallite over sylvite that is then processed to produce the final KCl product. The brine chemistry in all three examples imitates the ionic proportions obtained when evaporating a ancient sulphate-depleted seawater (Figure 1). The next article will discuss the complexities (the double salt problem at the potash bittern stage when concentrating a more sulphate-enriched mother brine.

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