Salty Matters

The Blog is written by me, John Warren. Once every three or four weeks or so I will post an article or two on an evaporite topic that has piqued my interest. On the Saltwork Publications webpage (under "the Works") there is a growing library of pdfs and epubs based on these blogs. These articles on the website have much higher resolution extractable graphics in than in the blog. There is also a link to this set of pdfs and epubs on the home page (www.saltworkconsultants.com).

What is an evaporite? Solar versus cryogenic (freeze-dried) salts

John Warren - Tuesday, February 24, 2015

The term evaporite is usually used to describe sediment precipitated during the solar-driven desiccation of a standing water body in a saltern or salina, or a near-surface pore brine in an evaporitic mudflat or sabkha. Almost all the modern and ancient examples of bedded salts that we work with in the rock record are thought to have crystallised via this process of solar evaporation. The chemical dynamics of solar evaporation are simple; on average, water molecules within a standing at-surface brine lake or in near-surface pore spaces, near a water-table and its associated capillary zone, do not have enough kinetic energy to escape the liquid phase and so cross the surface tension barrier (figure 1). Otherwise, liquid water would turn to vapour spontaneously and any at-surface liquid phase would spontaneously disappear, while recharge to an underlying water-table would be an impossibility.

 

Every so often in this situation, the level of solar energy transfer (heat absorption) at the molecular collision site is sufficient to give a water molecule (near the water-air interface) the heat energy necessary to pass into the vapour phase and so exit the liquid water mass (figure 1). That is, for a water molecule to escape into the vapour phase it must absorb heat energy, be located near the liquid surface, be moving in the proper direction and have sufficient energy to overcome liquid-phase intermolecular forces and then pass through the surface tension interface. As the concentration of the residual brine increases, the specific heat capacity decreases, and the density increases (the effects of specific heat and density increases on evaporite mineralogy and distribution in the depositional setting will be the topic of a future blog).

But salts, some with the same mineralogy as solar evaporation salts, can also form as a water or brine body freezes to leave behind cryogenic salt layers (aka the "freeze-dried" salts). This is the process that forms significant volumes of the sodium sulphate salts in various cold-zone brine lakes and saline ice-sheets around the world. Unlike solar evaporites, cryogenic brines and associated salts require temperatures at or below the freezing point of the liquid phase. Cryogenic salts, such as mirabilite (Na2SO4.10H2O), hydrohalite (NaCl.2H2O), antarcticite (CaCl2.6H2O) and epsomite (MgSO4.7H2O), can then accumulate. These cryogenic salts crystallise in cold, near-freezing, residual brines as they concentrate via the loss of the liquid water phase as it converts/solidifies to ice. As the volume of ice grows, the various anions and cations are excluded from the expanding ice lattice. Hence, concentration of the residual brine increases until it reaches saturation with a salt phase that then precipitates (figure 2). There are a number of well-documented cryogenic salt beds in various Quaternary-age cold-continental lacustrine settings. Probably the best known are the sodium sulphate salts in Karabogazgol, Turkmenistan, where strand-zone stacks of cryogenic mirabilite form each winter. Beneath the lake centre there are subsurface beds (meters thick) of Quaternary-age cryogenic glauberite-halite.

 

In the Turkmen language, Karabogazgol means “lake of the black throat,” so named because the gulf is continually gulping down the waters of the Caspian Sea, via a narrow connecting natural channel (figure 3). Ongoing evaporation in Karabogazgol keeps the water surface in the perennial brine lake depression around a metre below that of the Caspian. It is one of our few natural examples of evaporative drawdown occurring via a hydrographic (surface) connection to the mother water body. Groundwater seepage connections with the mother water mass are more typical, especially in hot arid basins.

 

Only since the end of the Soviet era and the re-opening of the lake’s natural connection to the Caspian Sea in 1992, by a newly independent Turkmen government, did Karabogazgol re-fill with perennial brines. Since then, a natural cryogenic mirabilite winter cycle has returned the Karabogaz hydrology to its longterm natural state. Today, the main open water body in the centre of Karabogaz is a Na-Mg-Cl brine, sourced via gravitationally-driven inflow of Caspian Sea waters. Perennial Karabogaz brines today have a density of 1.2 g/cm3, and pH values that range between 7.2 and 9. Surface water temperatures in the lake centre range from around 4°C in December (winter) to 25°C in July (summer). Temperature fluctuations and the cool arid steppe climate (Koeppen BSk) of Karabogazgol combine to drive the precipitation of different mineral phases during the year. Calcite, aragonite and perhaps hydromagnesite usually precipitate from saturated lake surface waters in spring, gypsum and glauberite in summer (via solar evaporation), while rafts of cryogenic mirabilite form at the air brine interface in the winter. These winter rafts are then blown shoreward, to form stacked strand-zone-parallel accumulations of cryogenic mirabilite and halite. By the following summer much of the strand-zone mirabilite has deliquesced or converted to glauberite. In the 1920s and 30’s, prior to the damming of the connecting channel between Karabogaz and the Caspian Sea, the strand-zone salts were harvested by the local peasantry. From the 1950s to 1980s there was a significant Soviet chemical industry operational in the basin, focused on older buried salt bed targets.


Beneath Karabogaz bay there are 4 beds dominated by various NaSO4 salts (figure 4). These cryogenic beds are likely the result of cooler climatic periods over the last 10,000-20,000 years. Back then, under a glacial climate, large amounts of mirabilite formed each winter, much like today. But, unlike today, a cooler more-humid glacial climate meant that the bay was not as subject to as an intense summer desiccation as it is today. Dense residual bottom brines were perennially ponded and so preserved a summer-halite sealing bed atop the winter NaSO4 layer. This allowed the underlying mirabilite/epsomite    precipitates to be preserved across the lake floor. During the following winter the process was repeated as mirabilite/epsomite/halite beds stacked one atop the other to create a future NaSO4 bedded-ore horizon. In time, a combination of groundwater and exposure, especially nearer the Gulf’s strand-zone, converted most of the mirabilite, along with epsomite, to astrakanite, and then both phases to glauberite in the upper three beds. This explains the association of the richer glauberite zones with the lake edges (figure 4). Whenever water of crystallisation is released by a mirabilite to thenardite conversion, it then slightly dilutes any strong residual brine; in Korabogazgol this facilitated the high sodium-sulphate mineral and brine compositions seen in modern and ancient waters across the bay.

There are similar cryogenic salt beds preserved in perennial saline lakes across the cold arid portions of the Great Plains of Canada and there is also a mirabilite bed preserved beneath Holocene sediments in Great Salt Lake, Utah. Last century, some of the richer subaqueous salt beds in the Canadian lakes were sources of commercial NaSO4 salts (figure 5). However, extraction of brine and solid salts and an increasingly expensive product meant this area no longer competes with cheaper product from the solar evaporite NaSO4 lakes of Mexico and Turkey. Only one (Big Quill Lake) of the Canadian sites remains operational.


Hydrohalite is another common cryogenic salt, it quickly redissolves as brine temperatures rise above 0 degrees centigrade and so is said to indicate halite cryogenesis (figure 6). Hydrohalite crystals have distinctive pseudo-hexagonal cross sections (c.f. typical cubic forms of halite) and crystals or NaCl-filled pseudomorphs have been recognised in a number of modern cold saline lake settings. For example, hydrohalite has been extracted from the lake bottom sediments in saline Lake Bonney in Antarctica, where the bottom water temperatures vary between +2.0 and -2.0°C. It also can precipitate in winter in the Baskunchak salt lake, located some 300 km northwest of the Caspian Sea (48°N latitude). There hydrohalite was directly observed on two occasions when formative brine temperatures were between-3° and -23°C. In summer, halite precipitates via solar evaporation in the same saline lake. Hydrohalite also occurs in bottom sediments in salt-saturated cryogenic lakes in Saskatchewan, at about 51°N latitude, and has been observed in nearby saline springs sediments of the Northern Great Plains. Hydrohalite pseudomorphs occur as halite crystals with hexagonal cross sections in cores some 100-140m deep, in Death Valley, California, indicating NaCl cryogenesis occurred in the Pleistocene Death Valley Lake at a time when brine temperatures were less that 0°C.


When polar seawaters freeze on Earth, hydrohalite and mirabilite precipitate from the residual marine brines and accumulate in ice sheet fissures, or in load-induced fractures in the ice understory wherever an increasingly saline brine sinks into rock fractures beneath the growing ice sheets. For example, there are mirabilite layers on the ice floes of the Ross Ice Shelf near Black Island. Likewise, there are dense residual saline brines in interstitial waters extracted from deep cores in sediments of McMurdo Sound. It seems that when ice sheets retreat, the at-surface cryogenic salts dissolve in the freshened at-surface hydrology, but dense hypersaline brines can remain behind in deep fissures, held and preserved in the rock fractures. In the extreme setting of at-surface brine freezing in some of the small saline depressions in the Dry Valleys of Antarctica, a solid form of calcium chloride, antarcticite, grows cryogenically. Antarcticite precipitates today in Don Juan Pond, Antarctica, in what is probably the most saline perennial natural water mass on Earth (47% salinity). Although the Don Juan pond is often cited in the saline literature as a most impressive example of an extremely-hypersaline modern closed-basin cryogenic hydrology, it should be pointed out that this cryogenic salt pond measures some 100 by 300 metres across and is tens of centimetres deep (figure 7). 

 

On Earth, the volume of salt beds formed by cryogenesis is much less than the volumes that result from solar evaporation. Extraterrestially, in planets and moons of our solar system with liquid water and located further out than the earth’s orbit, there are likely, at least locally, volumes of cryogenic salts that are significant. Cryogenesis explains sulphate salt (epsomite-dominant) phases that typify ice crack fissures crisscrossing the surface of Europa (a moon of Jupiter). Sulphate salts also grow seasonally in soils of Mars where, for example, widespread gypsum forms via ice ablation in the circumpolar Martian dune-field. But, for now, I will leave the discussion of the significance of these extraterrestial cryogenic salts, it will be the topic of a future blog dealing with liquid water indications in and on a variety of planets and moons located beyond the earth’s orbit.

On Earth, as ground temperatures increase, cryogenic salts tend to deliquesce or convert to their higher temperature daughter salts (thenardite, glauberite and halite). But worldwide, in appropriate cold climatic settings, there are numerous examples of cryogenic salt beds; the volumes grow even larger if we include sediments containing cryogenic hydrated calcite (ikaite-glendonite; CaCO3.6H2O). Across deep time, the volume of cryogenic salts increases during glacial episodes, their susceptibility to deliquescence and conversion as temperatures increase means a low propensity for significant preservation other than as pseudomorphs. If such pseudomorphs are to be found across the rock record, then there will be a greater likelihood of their retention and recognition in sediments of the late Tertiary, the Permo-Carboniferous, the Ordovician and the late Neoproterozoic, which are all times of an icehouse climate.

Solikamsk sinkhole and potash ore

John Warren - Thursday, February 19, 2015

The Solikamsk-2 mine output currently accounts for a fifth of the Uralkali's potash capacity. The mine is one of Uralkali’s potash mines in the Kama district (western Urals) of Russia. The possible loss of the Solikamsk-2 mine in the near future may put upward pressure on the currently low world price of potash. Even if loss of production from the mine doesn't drive an increase in price, Uralkali as a company will continue to be profitable. All mines in Solikamsk basin benefit from low production costs, related to shallow ore depth. The collapse sinkhole is a classic example of what can happen if any salt or potash mine operates at a depth that is shallow enough to intersect the overlying  zone of active phreatic water crossflow.


In November 2014 the most recent example of an evaporite-related ground collapse or sinkhole, daylighted to the east of the Solikamsk-2 potash production site. It seems likely that halite-undersaturated waters, sourced from above, now flow into an area of the Solikamsk-2 workings that were no longer mined, but were still connected to the active extraction areas of the Solikamsk mine. Worldwide experience shows that flooding is difficult to control once a salt mass is breached. Increasing volumes of inflow waters into the mine workings will likely lead to the ultimate loss of the Solikamsk 2 mine, as it has in what are other now abandoned salt mines and solution brinefields across the world.

Recently the head of the Ural region's Mining Institute, Alexander Baryakh, was quoted as saying (Moscow Times Dec. 11 2014): ....."Based on our analysis and the world's experience in developing potassium mines, the risk of a negative scenario — the complete flooding on the mine — remains high. We are ready for this contingency, but we are doing everything possible to minimize related risks,"  adding that, "fortunately, the accident poses no danger to the residents of [the local town of] Solikamsk....”

When, in mid November, a stoping solution cavity above the abandoned section of the mine workings reached the surface, the resulting sinkhole diameter measured 30m by 40m. As of 6 February 2015, the at-surface sinkhole diameter had increased in size and measured 58 by 87 metres wide and was some 75 metres deep. Uralkali’s ongoing measurements show levels of brine inflow into the Solikamsk-2 mine continuously varied over this time frame. Between 11 December 2014 and 21 January 2015, the average brine inflow was around 200 cubic metres per hour. Between 22 January and 06 February 2015, the average brine inflow increased substantially, reaching approximately 820 cubic metres per hour. 

Accordingly, where underground equipment at Solikamsk 2 is not being used to mitigate the consequences of the collapse and water inflow, Uralkali has started to remove plant via the mine shaft. Three "Ural" continuous miners have already been dismantled and taken out. In line with their accident mitigation plan, Uralkali in a recent press release states: that the company continues to comprehensively monitor the situation both underground and at the surface; water inflows are monitored through brine level checks; groundwater levels are monitored by water monitoring wells and via the drilling of additional water monitoring wells currently in progress; gas levels are monitored around the sinkhole and in the mine; while the sinkhole is continuously monitored from a distance, using stationary cameras and air drones; and a seismologic network has been set up over the sinkhole area.

This latest collapse is one of a series of evaporite collapse dolines or sinkholes that have daylighted atop the mined regions in this part of Russia. Collapse cavities typically reach the surface some years after extraction operations below the collapse have ceased. For example, in 1995, a collapse sinkhole formed atop the Solikamsk-2 potash mine’s Verkhnekamsky deposit. The collapse on January 5th, 1995 resulted in a 4.7 magnitude seismic event on the Richter scale, with an associated initial 4.5 m of surface subsidence. Underground, the mine roof collapsed over an area measuring 600 m by 600 m. Across the period 1993 to 2005, several hundred earthquakes were recorded in the Berezniki-Solikamsk region with magnitudes varying from 2 to 5. These earthquakes were caused by collapsing underground tunnels of potash mines, mined out over the 70 continuous years of production. In October 2006, in order to prevent catastrophic outcomes of a sudden brine influx into the underground workings, Berezniki potash mine #1 was flooded by Uralkali. After that, three major sinkholes occurred in the region above the flooded workings.

On July 28th, 2007, a huge sinkhole appeared on the surface above the closed Berezniki mine #1, its creation likely aided by infiltration of undersaturated floodwaters water into the abandoned underground workings. At the surface this sinkhole had an initial size of 50 by 70 meters and was 15 meters deep. By November, 2008, the sinkhole had expanded into a crater measuring 437m by 323m and some 100 m deep.  The July 28th collapse released an estimated 900,000 cubic metres of gas (a mix of methane, hydrogen, carbon dioxide, carbon monoxide and other gases), which in turn led to gas explosions on the following day. Timely placement by the mine operators of a “significant volume” of backfill, prior to flooding, is credited with preventing further catastrophic collapses.

The mined potash ore level at both collapse sites (Solikamsk and Berezniki) is Middle Permian (Kungurian) in ag. The potash is halite-hosted and occurs in one of six evaporitic foreland sub-basins, extending from the Urals foreland to the Caspian basin. Sylvinite (potash) beneath the 1995 Verkhnekamsky collapse area was extracted from two to three halite-potash beds, with 10 to 16 metres of total extraction height. At that time the mine used a panel system of rooms and pillars under 200 to 400 m of overburden. Rooms were 13-16 m wide and pillars 11-14 m wide by 200 m long. Due to the relatively shallow nature of the Solikamsk and Berezniki potash ore levels, compared to other potash mines in the world, a “rule of thumb” used across the Upper Kama mining district is that surface subsidence typically reaches 50% of the subsurface excavation height around 48 months after excavation. 

The 1995 collapse event occurred 15 years after mining began, and 7 years after mining was completed in the area beneath the sinkhole. The delay before the main collapse doline surfaced implies there was a rigid bridging of overburden as a roof to the mine level. This is consistent with the uncommonly high release of seismic energy associated with the1995 collapse. The next largest collapses associated with published seismic measurements occurred in 1993 and 1997 with seismic magnitudes of 2.6 and 2.8, respectively.

An even earlier surface collapse occurred on July 25, 1986 atop a portion of the nearby 3rd Bereznki potash mine and is yet another case of a sinkhole forming atop a mine that was operating at relatively shallow depths. Potash extraction at Bereznki was active at depths of 235 and 425 m below surface. There, the targeted ore zone was overlain by a 100 m thick “salt complex” made up of halite and carnallite beds, overlain in turn by clays, carbonates, aquifers and sediments. Mining created “yield pillars,” with 5.3 m wide rooms, 3.8 m wide pillars and a 5.5 m mining height. After mining, conditions in mined-out areas were described as, “pillars crushed and roofs sagged.”

Observations of significant brine leakage into the 3rd Bereznki potash mine workings at a depth of 400m indicated a loss of hydraulic control as early as January of 1986. This was a prelude to the massive dissolution cavitation that was occurring in the 90 m interval of disturbed salt and clastics that overlay the potash level. Some 7 months later a large cavity formed in the sandstone/limestone overburden, which was nearly 200 m thick. In the mine it appeared the water inflow situation remained relatively stable, at least from January until July 1986. Failure of the mine head then occurred, the result of a cavity that had migrated vertically through more than 300m of limestones, mudstones and sandstones. 

Final cavity stoping was indicated by the near instantaneous appearance of a caprock sinkhole, which was 150 m deep and 40-80 m across and located at the top of a stoping breccia pipe or chimney of the same dimensions. Failure of this sequence began at 18:30 hours on July 25 with “clearly felt underground shocks” culminating with a final collapse at midnight, which was accompanied by an explosion with “flashes of light.” In the final stages of stoping by the rising solution pipe, before the sinkhole daylighted, it took only 12 days to migrate through the last 100 metres of mudstone. This very high rate of stoping was likely aided by structural weakness in a fracture zone along a local fold axis.

In all these cases of rapid sinkhole creation, the collapse occurred above what was formerly an active area of the mine  and took place some years after mining had ceased. In all cases, the ultimate cause of the size of the collapse was likely a combination of a significant cavity growth below what was a mechanically strong rock rock, likely a dolomite or a limestone bed. This unit had significant structural integrity and so allowed a solution cavity to expand prior to the ultimate brittle collapse of roof rock. Once collapse did occur, undersaturated groundwaters, sourced in the overburden, then reached the salt level in large volumes and further expanded the region of collapse. Likewise, once the upward stoping cavity reached the shallower unconsolidated sediment levels, the cavity's passage to the surface sped up so that it daylighted and expanded in a rapid fashion.  

Dissolving evaporites and solution dolines occur naturally in all parts of the world, wherever salt is within a few hundred metres of the landsurface, but mining of both salt and potash at depths shallower than 250-350 metres can exacerbate the speed and and intensity of what is an ongoing natural process of evaporite solution, surface collapse and sinkhole growth. While Uralkali's operations in this region continue to exploit a relatively shallow potash ore source, it will continue to supply the Company a relatively inexpensive product, but the company will have live with sinkholes breaking out above some areas of the mined region. That is, as long as Uralkali can continue to be a low cost supplier of potash, there will be likely be ongoing landsurface-stability problems. Some of the problems may not daylight until years after the extraction operation has ceased.

Intro

John Warren - Wednesday, February 18, 2015

The aim of the blog is to discuss issues relevant to geological topics that are centred on all matters evaporitic.

Once every couple of weeks or so I will post a paragraph or two, and a few images, on a topic that has piqued my interest. It may be something as simple as an idea or a discussion coming out of a paper I have read. It may be an issue related to a salt-related problem that has occurred recently, like the Solikamsk 2 collapse doline that first daylighted last November, or it may be my preliminary ramblings on a topic I am working on for the next book, paper or a review piece.

The arguments and bias in these blogs will my own, so feel free to comment, or disagree.

Here’s hoping that once in a while you find it worth the time to check in. 


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