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).

Evaporite interactions with magma Part 2 of 3: Nature of volatile exhalations from saline giants?

John Warren - Saturday, March 16, 2019

 

Introduction

This article discusses general mechanisms of earth-scale volatile entry into the ancient atmosphere during events that involved rapid and widespread heating of saline giants. It develops this notion by looking at whether volumes of volatiles escaping to the atmosphere are enhanced by either the introduction of vast quantities of molten material to a saline giant or the thermal disturbance of that salt basin by bolide impacts. This begins a discussion of the contribution of heated evaporites in two (or three if the Captitanian is counted as a separate event) of the world's five most significant extinction events. It also looks at possible evaporite associations with a substantial bolide impact that marks the end of the Cretaceous. The next article presents the geological details and implications of the various magma-evaporite-volatile associations tied to major extinction events.

As we have seen for evaporite interactions with giant and supergiant volumes of commodities in particular deposits, such as hydrocarbons, base metals (Cu, Pb-Zn and IOCG deposits) evaporites do not form a commodity accumulation. But if evaporites are involved in the accumulation and enrichment processes, the size and strength of the accumulation are much improved. Because of their high reactivity compared to the kinetic stability at and near  thelithosphere's surface across most other lithologies, evaporite act not as creators of enrichment but as facilitators of enrichment (Warren, 2016 Chapters 9, 10, 14, 15 and Salty Matters, March 31, 2017).


End-Permian event

The end-Permian extinction event, colloquially known as the Great Dying, occurred around 252 Ma (million years) ago, and defines the boundary between the Permian and Triassic geologic periods, as well as between the Palaeozoic and Mesozoic eras. It is the Earth's most severe extinction event, when up to 96% of all marine species, 70% of terrestrial vertebrate species disappeared (Table 1, Figure 1). It also involves the only known mass extinction of a number of insect species (≈25%). Some 57% of all biological families and 83% of all genera became extinct. The end-Cretaceous extinction, which marks the demise of dinosaurs, is less severe, although it probably has a stronger hold on the western zeitgeist, while on land, the end-Triassic event marks the ascendancy of the dinosaurs.


Suggested mechanisms driving the end-Permian extinction event include; massive volcanism centred on the Emeishan and Siberian Traps and the ensuing coal or gas fires and explosions, along with a runaway greenhouse effect that was triggered by temperature increases in marine waters (Figure 2). It also may have involved one or more large meteor impact events and a rise in oceanic water temperatures that drove a sudden release of methane from the sea floor due to methane-clathrate dissociation.

The end-Permian event follows on closely from the Capitanian (Emeishan) extinction event when in south China fusulinacean foraminifers and brachiopods lost 82% and 87% of species, respectively (Bond et al., 2015). Proximity in time of the two events may explain why the breadth of the end-Permian extinction event was so severe. The Earth's biota was still recovering from the Emeishan event when the vicissitudes of the End-Permian calamity further decimated the world's biota.

Both the Emeishan and end-Permian extinction events tie to elevated mercury levels in sediments that encompass their respective boundaries (Grasby et al., 2016). Astride both boundaries, the mercury stratigraphy shows relatively constant background values of 0.005–0.010 μg g–1. However, there are notable spikes in Hg concentration over an order of magnitude above background associated with the two extinction events. The Hg/total organic carbon (TOC) ratio shows similar large spikes, indicating that they represent a real increase in Hg loading to the environment. These Hg loading events are associated with enhanced Hg emissions created by the outflows of the Emeishan and end-Permian large igneous province (LIP) magmas.

Interestingly, there is indirect evidence for a synchronous antipodeal impact crater that some argue may have instigated the Siberian volcanism, in much the same way that the end-Cretaceous bolide impact on the Yucatan Peninsula is considered by some to be the antipodeal driver of the Deccan Trap volcanism (von Frese et al., 2009). Other contributing, but likely more gradual tiebacks to the Great Dying, include sea-level variations, increasing oceanic anoxia, increasing aridity tied to the accretion of the Pangean supercontinent, and shifts in ocean circulation driven by climate change (Figure 2).

End-Triassic event

The end-Triassic extinction event, some 201.3 Ma, defines the Triassic-Jurassic boundary. In the oceans, a whole class (conodonts) and 23-34% of marine genera disappeared. On land, all archosaurs other than crocodylomorphs (Sphenosuchia and Crocodyliformes) and Avemetatarsalia (pterosaurs and dinosaurs), some remaining therapsids, and many of the large amphibians became extinct. About 42% of all terrestrial tetrapods went extinct (Figure 3). This event vacated terrestrial ecological niches, allowing the dinosaurs to assume the dominant roles in the Jurassic period. It happened in less than 10,000 years and occurred just before the Pangaean supercontinent started to break apart (Tanner, 2018).


The extinction event marks a floral turnover as well. About 60% of the diverse monosaccate and bisaccate pollen assemblages disappear at the T-J boundary, indicating a significant extinction of plant genera. Early Jurassic pollen assemblages are dominated by Corollina, a new genus that took advantage of the empty niches left by the extinction.

Worldwide the end-Triassic extinction horizon is marked by perturbations in ocean and atmosphere geochemistry, including the global carbon cycle, as expressed by significant fluctuations in carbon isotope ratios (Korte et al., 2019). At this time the Central Atlantic Magmatic Province (CAMP) volcanism triggered environmental changes and likely played a crucial role in this biotic crisis (Schoene et al., 2010). Biostratigraphic and chronostratigraphic studies link the end-Triassic mass extinction with the early phases of CAMP volcanism, and notable mercury enrichments in geographically distributed marine and continental strata are shown to be coeval with the onset of the extrusive emplacement of CAMP (Percival et al. 2017; Marzoli et al., 2018). Sulphuric acid induced atmospheric aerosol clouds from subaerial CAMP volcanism can explain a brief, relatively cool seawater temperature pulse in the mid-paleolatitude Pan-European seaway across the T–J transition. The occurrence of CAMP-induced carbon degassing may explain the overall longterm shift toward much warmer conditions.

End-Cretaceous event

The end-Cretaceous extinction event defines Cretaceous-Tertiary (K–T) boundary, and was a sudden mass extinction event some 66 million years ago. Except for some ectothermic species, such as the leatherback sea turtle and crocodiles, no tetrapods weighing more than 25 kilograms survived. The K-T event marked the end of the Cretaceous period and with it, the entire Mesozoic Era, opening the Cenozoic Era.

A wide range of species perished in the K–T extinction, the best-known being the non-avian dinosaurs. It also destroyed a plethora of other terrestrial organisms, including certain mammals, all pterosaurs, some birds, lizards, insects, and plants. In the oceans, the extinction event killed off plesiosaurs and the giant marine lizards (Mosasauridae) as well as devastating fish, sharks, molluscs (especially ammonites, which became extinct) populations, and many species of plankton. It is estimated that 75% or more of all species on Earth vanished in the end-Cretaceous event.

In its wake, the same extinction event also provided evolutionary opportunities as many groups underwent remarkable adaptive radiation—sudden and prolific divergence into new forms and species within the disrupted and emptied ecological niches. Mammals in particular diversified in the Paleogene, evolving new forms such as horses, whales, bats, and primates. Birds, fish, and perhaps lizards also radiated in newly vacant niches.


In the geologic record, the K–T event is marked by a thin layer of sediment called the K–Pg (Cretaceous - Paleogene) boundary, that is found throughout the world in both marine and terrestrial rocks. The boundary clay shows high levels of the metal iridium and is widely interpreted as indicating the impact of a massive comet or asteroid 10 to 15 km (6 to 9 mi) wide some 66 million years ago (Figure 4a,b). The impact devastated the global environment, mainly through a lingering impact winter, which halted photosynthesis in plants and plankton.

The impact hypothesis, also known as the Alvarez hypothesis (Alvarez et al., 1980), was bolstered by the discovery of the 180-kilometer-wide (112 mi) Chicxulub crater in the Gulf of Mexico in the early 1990s, which provided conclusive evidence that the K–Pg boundary clay represented debris from an asteroid impact. In a 2013 paper, Paul Renne dated the impact at 66.043±0.011 million years ago, based on argon-argon dating (Renne, 2013). He went on to conclude that the main end-Cretaceous mass extinction event occurred within 32,000 years of this date. A 2016 drilling project into the Chicxulub peak ring, confirmed that the peak ring was comprised of granite, likely ejected within minutes from deep in the earth, but the well contained hardly any anhydrite/gypsum, the usual sulphate-containing seafloor rock across the region (Figure 4a, b). As we shall see in part 3, the missing CaSO4 was vaporised in the impact and dispersed as sulphurous aerosols into the atmosphere, causing longer-term deleterious effects on the climate and food chain. Another causal or contributing factors to the end-Cretaceous extinction event may have been the synchronous outflows of the Deccan Traps and other volcanic eruptions, so driving climate change, and possibly sea level change (von Frese et al., 2009).

Volatiles released when cooking saline giants and associated organic-rich sediments

Particular sets of assimilations and metamorphic alterations of evaporites occur within the explosive milieu associated with both igneous interactions and pressurised heating of salts tied to a bolide impact. Any carbonate and organic matter layers present in the saline sequence or adjacent strata generates additional volatiles that will quickly enter the earth's atmosphere. Figure 5 is a schematic of the estimated amount of volatiles released during contact metamorphism of different types of sedimentary rocks in contact with an igneous sill or magma body (after Ganino et al., 2009; Pang et al., 2013). More catastrophic volumes of similar volatile suites enter the atmosphere if a large bolide impacts a region underlain by a saline giant.


Hence, salty interactions must be considered and quantified when attempting to understand earth-scale environmental changes whenever large evaporite masses are caught up in regions of LIP emplacement or bolide impact. In such areas:

  • Basalt and granitoids do not release large volumes of volatiles, as compared to the amounts of volatiles that are released by the heating or assimilation of saliniferous country rock (heat transfer and hydrothermal circulation).
  • Most porous sandstones and organic-lean shales caught up in a contact aureole or consumed in a magma, release water vapour; a release that has little effect on global climate.
  • During desulphation of a magma, gypsum or anhydrite masses are assimilated into a rising magma chamber or the emplacement of a thick sill. If anhydrite beds are consumed (melted and absorbed) by a magma batholith, the reaction releases abundant SO2 constituting up to 47 wt% of the bedded sulphate (Gorman et al., 1984). Direct melting requires high temperatures (≈ 1300- 1400 °C). Such widespread desulphation of thick Devonian anhydrite beds occurred during the emplacement of the supergiant Noril'sk nickel deposit in Siberia (Black et al., 2014; Warren, 2016, Chapter 16).
  • But such elevated temperatures (≈1400°C) are not typical of most contact aureoles where a sill or dyke intrudes anhydritic country rock. However, similar high-volume SO2 releases can proceed at temperatures as low as 615°C if the anhydrite is impure and contains interlayers rich in organics and hydrocarbons (e.g., West and Sutton, 1954; Pang et al., 2013). This is especially so if the interacting calcium sulphate is gypsum (hydrated salt) rather than anhydrite. Experiments by Newton and Manning (2005) demonstrated that the solubility of anhydrite increases enormously with NaCl activity (salinity) in hydrothermal solutions at ≈600 to 800°C (Figure 6).


  • Pure limestone contains large amounts of CO2, but like anhydrite the thermal decomposition of limestone or dolomite into CaO, MgO and CO2 takes place at high temperatures (>950 °C) that are typical when blocks of sedimentary carbonate are assimilated into a magma chamber, but less typical of contact aureoles tied to dykes and sills. Impure limestones can release large amounts of CO2 (up to 29 wt%) during the formation of calc-silicates in the contact aureole at moderate temperatures of 450–500 °C. As early as 1940, Bowen documented the release of CO2 by decarbonisation reactions during progressive metamorphism of siliceous dolomites (Bowen, 1940)
  • Likewise, devolatilization of fine-grained calcareous and saline sedimentary rocks during contact metamorphism directly generates fluids rich in CO2 (i.e., decarbonisation) and SO2 (i.e., desulphatation), which in theory can enter the magmatic system.
  • When heated at a relatively low temperature (<300-400 °C), contact metamorphism and hydrothermal leaching of bituminous halite and organic-carbon-rich saline mudstones releases large volumes of chlorohalogens and methane (Visscher et al., 2004; Beerling et al., 2007). Halocarbon compounds (aka halogenated hydrocarbons) are chemicals in which one or more carbon atoms are linked by covalent bonds with one or more halogen atoms (fluorine, chlorine, bromine or iodine). Methyl chloride (CH3Cl) and methyl bromide (CH3Br) are commonplace halocarbons when a halite-dominant saline giant interacts with igneous sill emplacement. When thermally-derived chlorohalogens enter the upper atmosphere, they tend to be reactive and will degrade ozone.
  • Buring coal and coal gas release abundant CO2. Depending on its grade, coal can ignite at temperatures between 400-530°C. Methane will auto-ignite at temperatures around 550-600°C and in an oxygenated setting produces large volumes of carbon dioxide and water vapour. Flashpoints are much lower than these ignition temperatures.
  • Sulphidic (pyritic) sediments release abundant SO2 when heated at lower temperatures (<400°C).
  • Heating of hydrated salts at moderate temperatures (90-250°C) can release pressurised pulses of hypersaline chloride or sulphate brine, with the dominant ionic proportions dependent on predominant hydrated salt; e.g., carnallite incongruently alters as it releases an MgCl2 brine, gypsum incongruently alters as it releases a Ca-SO4 brine (see part 1). Such pressurised pulses are essential in the generation of explosive breccia pipes sourced at the sill penetration level in the hydrated evaporite interval (discussed in detail for the Siberian Traps in part 3).
  • Getting volatiles into the atmosphere

    When a saline giant is heated during emplacement of a large igneous province (LIP) or during the impact of a large bolide, it and adjacent carbonates and organic-rich mudstones release large volumes of volatiles that can have short and long term harmful effects on the Earth's biosystems (Black et al., 2012, 2014; Jones et al., 2016; Part 3 this series). The volume of volatiles released to the atmosphere by these interactions, especially sulphurous products (SO2, H2S), thermogenic CH4, organohalogens and CO2, are considered primary contributors to three or four of the major extinction events outlined in Figure 1, and perhaps others, as discussed in part 3.

    Height and volume of various volatile injections into the layers of Earth's atmosphere controls the longevity and intensity of climatic effects and are tied to the chemistry of particular volatiles (Figure 7; Textor et al., 2003; Robock, 2000). The low concentration of water in typical modern volcanic plumes results in the formation of relatively dry aggregates entering the atmosphere. More than 99% of these aggregates are frozen because of their fast ascent to low-temperature regions of the atmosphere. With increased salinities, the salinity effect increases the amount of liquid water attaining the stratosphere by one order of magnitude, but the ice phase is still highly dominant. Consequently, the scavenging efficiency for HCl is very low, and only 1% is dissolved in liquid water.


    Scavenging by ice particles via direct gas incorporation during diffusional growth is a significant process for volatile transport. The salinity effect increases the total scavenging efficiency for HCl from about 50% to about 90%. The sulfur-containing gases SO2 and H2S are only slightly soluble in liquid water; however, these gases are incorporated into ice particles in the atmosphere with an efficiency of 10 to 30%. Despite scavenging, more than 25% of the HCl and 80% of the sulphur gases reach the stratosphere during a more intense modern explosive eruption because most of the particles containing these species are typically lifted there by the force of the eruption (Figure 7b).

    Sedimentation of the particles tends to remove the volcanic gases from the stratosphere. Hence, the final quantity of volcanic gases injected in a particular eruption depends on the fate of the particles containing them, which is in turn dependent on the volcanic eruption intensity and environmental conditions at the site of the eruption.

    Today, volcanically-derived SO2 and H2S are the dominant sources for sulphur species in the atmosphere (Jones et al., 2016; Robock, 2000). Conversion of SO2 to aerosols is one of the critical drivers of climatic cooling during recent eruptions (Figure 7a; Robock, 2000). For SO2 to be effective in causing cooling in the atmosphere, escaping hydrogen sulphide quickly oxidises to SO2. Over hours to weeks following its eruptive escape the ongoing reaction of SO2 with atmospheric H2O forms a H2SO4 (sulphuric acid) aerosol, and this is a major cause of the acid rains tied to volcanism (Figure 7a, b).

    Tropospheric sulphate aerosols have an atmospheric lifetime of a couple of weeks due to the rapid incorporation as precipitation into the hydrological cycle (Figure 7b; Robock, 2000). However, if the intensity of the escaping volatile plume is capable of injecting sulphurous material above the tropopause into the stratosphere, then due to the lack of removal by precipitation, the lifetimes of sulphurous aerosols and the associated cooling effects are considerably extended (years rather than weeks: Figure 7a versus 7b).

    Modern eruptions

    World-scale cooling has been observed following a number of modest (by large igneous province standards) volcanic eruptions over the past few centuries (Figure 8; Bond and Wignall, 2014; Sigurdsson, 1990; and references therein). A recent example is provided by the Mount Pinatubo eruption of 1991, which injected 20 megatons of SO2 more than 30 km into the stratosphere. The result was a global temperature decrease approaching 0.5 °C for three years (although this cooling was probably exacerbated contemporaneous Mount Hudson eruption in Chile). One of the largest historical eruptions occurred in 1783-1784 from the Laki fissure in Iceland when a ≈15 km3 volume of basaltic magma was extruded, releasing ≈122 Mt of SO2, 15 Mt of HF, and 7 Mt of HCl. Laki’s eruption columns extended vertically up to 13 km, injecting sulfate aerosols into the upper troposphere and lower stratosphere, where they reacted with atmospheric moisture to produce ≈200 Mt of H2SO4. This aerosol-rich fog hung over the Northern Hemisphere for five months, leading to short-term cooling, and harmful acid rain in both Europe and North America. Additionally, HCl and HF emissions damaged terrestrial life in Iceland and mainland Europe, as this low-level fluorine-rich haze stunted plant growth and acidified soils.

    By causing or aiding in the collapse of food chains during the more intense sulphurous releases involved in the heating of large volumes of anhydrite held in ancient saline giants, vast quantities of acid rain may have killed much of the vegetation on land and photosynthetic organisms in the oceans during the three extinction events discussed in part 3.


    Halocarbons

    For halocarbons to form in a volcanic eruption requires the combination halogens with organic matter/methane or other hydrocarbons. We shall consider the levels and origins of two of the more common halocarbons in today's atmosphere; methyl chloride (CH3Cl) and methyl bromide (CH3Br) although many other species of halogenated hydrocarbons are present both naturally and anthropogenically (Schwandner, 2002; Visscher et al., 2004).

    The average Cl concentration of the Earth has been estimated to be 17 ppm (Worden, 2018 and references therein). Chlorine is the dominant anion in seawater, most modern and ancient evaporite beds and associated brines. Chlorine is present in most igneous rocks at low concentrations with little difference in level shown between granite and basic igneous rocks (both have a Cl- concentration of about 0.02%). However, igneous glass typically has higher Cl concentrations (≈0.08%). Chlorine is concentrated within any residual vapour phase during volcanic eruptions so can be independent of the volatiles created by heating of saline giants. Without the latter, the contribution of volcanically-erupted Cl to the atmosphere is still considerable. For example, the estimated current global volcanic emission of Cl is between 0.4 and 170 mt/year, while individual eruptions can produce hundreds of kilotons of Cl. For example, in 1980, St Helens emitted 670 kt of Cl into the atmosphere.

    In crystalline igneous rocks Br is found at low concentrations, typically <1 ppm in mid-ocean ridge basalts (MORB) (Worden, 2008 and references)). The average Br concentration of the Earth has been estimated to be 0.05 ppm. Chlorine/Bromine ratios are typically between 200 and 1000 in igneous rocks. Bromine is, however, found at relatively high concentrations (up to 300 ppm) in melt inclusions and matrix glass in acid igneous rocks since it is a highly incompatible element that does not easily sit within silicate, oxide or sulphide minerals. Bromine is concentrated within any residual vapour phase during volcanic eruptions. Based on experimentally-derived fractionation factors for halogens in volcanic materials, crustal average halogen concentrations, and measured amounts of Cl emitted from volcanoes, it can be concluded that the contribution of volcanically-erupted Br to the atmosphere is considerable. For example, the estimated current global volcanic emission of Br is between 2.6 and 78 kt while individual eruptions (e.g., St Helens in 1980) can emit 2.4–5.6 kt.

    The hinterlands of sedimentary basins that predominantly enriched in primary igneous rocks will provide only small quantities of Br into the sediment supply but rocks enriched in glass-bearing igneous rocks may supply relatively greater amounts of Br (Worden, 2018). Bromine is found in sedimentary basins as dissolved Br-, in solid solution in halite (NaClxBr1−x), or in less common salts resulting from potash-facies evaporites, such as sylvite. Bromine is also associated with organic-rich sediments, especially in marine settings, including organic-rich mudstone and coal. At a concentration of 65 mg/L, Br- is the second most abundant halogen in modern seawater.

    Organic matter and its more evolved forms –kerogen and hydrocarbons– are typical of most large evaporite basins. Mesohaline carbonates interlayered with anhydrite and halite beds can entrain high levels of organic matter to form high-yield source rocks, while the brine inclusions in some halites contain high amounts of volatile hydrocarbons and pyrobitumens. Evaporite beds composed of anhydrite or halite make excellent seals holding back large volumes of hydrocarbons (for literature documentation of these observations see Warren, 2016, Chapters 9 and 10). In combination, saline giants and their heat-responsive lithologies will contain vast volumes of potential volatiles, including halocarbons.

    Ozone (O3) destruction

    When halocarbons enter the stratosphere, they decimate the ozone layer, allowing harmful levels of ultraviolet (UV) radiation to reach the earth's surface (Figures 7a, 9a). Ozone is destroyed by the entry of a number of free radical catalysts into the stratosphere; today the most important catalysts are the hydroxyl radical (OH), nitric oxide radical (NO), chlorine radical (Cl) and the bromine radical (Br). Each radical is characterised by an unpaired electron in its molecular structure and is thus extremely reactive. All of these radicals have both natural and man-made sources; at present, most of the OH and NO in the stratosphere is naturally occurring, but human activity has drastically increased the levels of chlorine and bromine.

    The elements that form radicals in the stratosphere are found in stable organic compounds, especially halocarbons, which reach the stratosphere without being destroyed in the troposphere due to their low reactivity. Once in the stratosphere, the Cl and Br atoms are released from the parent halocarbon by the action of ultraviolet light.


    Ozone (O3) is a highly reactive molecule that quickly reduces to the more stable oxygen (O2) form with the assistance of a catalyst (radical). Cl and Br atoms destroy ozone molecules through a variety of catalytic cycles. The simplest example of such a reaction is when a chlorine atom reacts with an ozone molecule, taking an oxygen atom to form chlorine monoxide (ClO) and leaving behind an oxygen molecule (O2) (Figure 9b). The ClO can then react with another molecule of ozone, once more releasing the chlorine atom as ClO, so far yielding two molecules of oxygen. This ClO reaction can be repeated until the ClO is flushed from the stratosphere (Figure 9b, Fahey, 2007)

    Thus the overall effect of halocarbons entering the stratosphere is a decrease in the amount of ozone. A single chlorine radical can continuously destroy ozone for up to two years (this the time scale for its transport back down into the troposphere; Figure 7a). But there are other stratopheric reactions that remove CLO from this catalytic cycle by forming reservoir species such as hydrogen chloride (HCl) and chlorine nitrate (ClONO).

    Bromine radicals are even more efficient than chlorine at destroying ozone on a per-atom basis, but at present there is much less bromine than chlorine in the atmosphere. Laboratory studies have shown that fluorine and iodine atoms can participate in similar catalytic cycles. However, fluorine atoms react rapidly with water and methane to form strongly bound HF in the Earth's stratosphere, while organic molecules containing iodine react so quickly in the lower atmosphere that they do not reach the stratosphere in significant quantities.

    Halocarbon concentrations below the tropopause are always higher by several orders of magnitude than in the stratosphere, which contains the seasonally and locally variable ozone layer responsible for absorption of incident solar UV radiation (Schwandner, 2002). Penetration of the tropopause allows the ascent of long-lived halocarbons and today occurs primarily as a result of rising tropical air masses in a Hadley cell, rare turnover events, or large Plinian volcanic eruptions.

    Over the two to three years a chlorine or bromine radical can remain in the stratosphere, it reacts with ozone and converts it to oxygen. It has been estimated that a single chlorine atom can react with an average of 100,000 ozone molecules before it is removed from the catalytic cycle (Figure 8b. Other halocarbon-enabled reactions drive ozone destruction (these catalysts are derived from anthropogenic CFCs and other industrial halocarbons). Over the past half-century, our anthropogenic focus on ozone destruction from industrial chemicals has driven the public's understanding into to the much-needed legislated prevention of the entry of additional industrial halocarbons (especially CFCs) into the stratosphere.


    Implications

    However, there are additional deep-time implications for the health of the Earth's biota when natural events of the past drastically increased the amount of halocarbons entering the stratosphere, along with increased levels of sulphurous volatiles and greenhouse gases. We know modern volcanic exhalations containing relatively high levels of chlorine and bromine. But times of intense magmatic/volcanogenic or bolide heating of evaporites in a saline giant will contribute even greater volumes of halocarbons to the stratospheric levels of the atmosphere (Figure 10). If coals and peats are also present (typically not in the saline portion of the basin's sediment fill), then the heating of these additional organic-rich sediments will contribute even more carbon to the vast volumes of the halocarbons created by heating of the evaporites. Heating reactions in the saline giant and associated deposits can also supply elevated levels of the greenhouse gases CO2 and CH4. Explosive volcanism tied to the emplacement of LIPs in the region of a saline giant or the atmosphere-scale disturbance linked to the impact of a large bolide in an area underlain by a saline giant are efficient mechanisms to move large volumes of halocarbons, sulphurous volatiles and greenhouse gasses to the troposphere. The third article in this series will document the specific evaporite geology that contributed to four of the five major Phanerozoic extinction events (Figure 10).

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    Stable isotopes in evaporite systems: Part II - 13C (Carbon)

    John Warren - Thursday, May 31, 2018

     

    Introduction

    13C interpretation in most ancient basins focuses on carbonate sediment first deposited/precipitated in the marine realm. Accordingly we shall first look here at the significance of variations in 13C over time in marine carbonates and then move our focus into the hypersaline portions of modern and ancient salty geosystems. In doing so we shall utilize broad assumptions of homogeneity as to the initial distribution of 13C (and 18O) in the marine realm, but these are perhaps oversimplifications and associated limitations need to be recognized (Swart, 2015)

    In the next article we shall look at the utility of crossplots of carbon and oxygen isotopes. Stable oxygen isotope values (d18O) crossplotted with respect to carbon isotope values (d13C) from, the same sample creates one of the most widely applied proxies used to infer palaeo-environmental conditions (depositional and diagenetic) in Holocene and ancient carbonate sediments. This is in large part due to kinetic fractionations that occur during evaporation (Leng and Marshall, 2004). It has long been known that as any liquid evaporates, the residual fluid becomes enriched in the less abundant heavy isotope(s) (see Horton et al., 2016 for detailed discussion).

    Interpreting 13C

    Over the Phanerozoic the standard paradigm for interpreting variations in variations in 13C values from modern and ancient marine carbonate is based on an integration of our understanding of the carbon cycle with the following arguments. Most of the carbon in Earth’s near-surface systems is stored in sedimentary rocks with only about 0.1% in living organisms and the atmosphere-hydrosphere (Figure 1). Oxidized carbon occurs primarily as marine carbonates and reduced carbon as organic matter in sediments. In the carbon cycle, CO2 from the oceans and atmosphere is transferred into sediments as carbonate carbon (Ccarb) or organic carbon (Corg), the former of which monitors the composition of the oceans (Figure 1). The cycle is completed by uplift and weathering of sedimentary rocks and by volcanism, both of which return CO2 to the atmosphere.


    There are two stable carbon isotopes, carbon 12 (6 protons and 6 neutrons) and carbon 13 (6 protons and 7 neutrons). Photosynthetic organisms incorporate disproportionately more CO2 containing the lighter carbon 12 than the heavier carbon 13 (the lighter molecules move faster and therefore diffuse more easily into cells where photosynthesis takes place). During periods of high biological productivity, more light carbon 12 is locked up in living organisms and in resulting organic matter that is being buried and preserved in contemporary sediments. Consequently, due the metabolic (mostly photosynthetic) activities of a wide variety of plants, bacteria and archaea, the atmosphere and oceans and their sediments become depleted in carbon 12 and enriched in carbon 13 (Figure 2)


    It is assumed that the carbon isotopic ratio in calcareous shells of marine organisms is in equilibrium with that of seawater. So as more carbon 12 is held in biomass during times of high primary productivity, and increased burial of organic carbon, calcareous (CaCO3) skeletal materials become enriched in carbon 13. In contrast during periods of low biological productivity and decreased burial of organic carbon, for example following mass extinctions, marine calcareous skeletal materials become enriched in carbon 12.

    Hence plotting variations in carbon isotopes in marine carbonates and organic matter over time offers a way to trace the growth of the crustal reservoir of reduced carbon (Des Marais, 1997). That is, the relative abundance of carbon isotopes is controlled chiefly by: 1) equilibrium isotopic effects among inorganic carbon species, 2) fractionation associated with the biochemistry of organic matter, and 3) the relative rates of burial of carbonate and organic carbon in sediments (Condie 2016).

    Because organic matter preferentially incorporates 12C over 13C, there should be an increase in the 13C/12C ratio (as measured by δ13C) in buried carbon with time, and indeed this is what is observed (Des Marais, 1997; Worsley & Nance, 1989). δ13Corg increases from values < -40‰ in the Archaean to modern values of -20 to -30‰. On the other hand, seawater carbon as tracked with δ13Ccarb remains roughly constant with time, with δ13Ccarb averaging about 0%.

    Variation in fluxes over time within the carbon cycle can be monitored by an isotopic mass balance (Des Marais, 1997), whereby;

    δin = fcarbδ13Ccarb + forgδ13Corg

    δin represents the isotopic composition of carbon entering the global surface environment comprised of the atmosphere, hydrosphere, and biosphere. The right side of the equation represents the weighted-average isotopic composition of carbonate (δ13Ccarb) and organic (δ13Corg) carbon buried in sediments, and fcarb and forg are the fractions of carbon buried in each form (fcarb = 1 - forg). For timescales longer than 100 Myr, δin = -5‰, the average value for crustal and mantle carbon (Holser et al., 1988). Thus, where values of sedimentary δ13Ccarb and δ13Corg can be measured, it may be possible to determine forg for ancient carbon cycles. Higher values of δ13Ccarb indicate either a higher value of forg or a greater negativity of average δ13Corg.


    During the Phanerozoic, there are several peaks in δ13Ccarb, the largest at about 110, 280, 300, 400, and 530 Ma (Figure 3). These peaks are widely interpreted to reflect an increase in burial rate of organic carbon (Des Marais et al., 1992; Frakes et al., 1992). This is because organic matter selectively enriched in 12C depletes seawater in this isotope, raising the δ13C values of seawater. In the late Paleozoic (300-250 Ma), the maxima in δ13Ccarb correspond to the rise and spread of vascular land plants, which provided a new source of organic debris for burial (Condie 2106, Berner, 1987, 20 01). Also conducive to preservation of organic remains at this time were the vast lowlands on Pangea, which appear to have been sites of widespread swamps where bacterial decay of organic matter is minimized. The drop in δ13Ccarb at the end of the Permian is not understood. Perhaps, large amounts of photosynthetic O2 generated by Carboniferous forests led to extensive forest fires that destroyed large numbers of land plants in the Late Permian (Condie, 2016). However, the reasons for the oscillations in δ13Ccarb are not yet unequivocally resolved and, as in all sciences, the tenet "...perceived correlation does not necessarily equate to causation"must always be at the forefront in the scientific mindset.


    Across the Precambrian and the Phanerozoic, the initiation of glaciation on a global scale, as in the Cryogenian ‘Snowball Earth’, has been interpreted to be dependent on parameters like the latitudinal extent of continents and oceanic circulations (Figure 4; Condie, 2016). The main drive for an onset of global glaciation is believed to be the lowering of atmospheric CO2. It likely also requires a continental landmass to be covering one of the earth's polar positions. More recently, cooling related to an increase in the earth's albedo due to widespread evaporites (saline giants) has been added to the list of possible drivers to the onset of glaciation.

    Climate modelling studies imply that CO2 concentrations as low as 100–150 ppm are required to initiate global glaciation (e.g. Liu et al., 2013; Feulner and Kienert, 2014). One potential cause of lowered CO2 is drawdown of CO2 during intense silicate weathering in equatorial regions (Hoffman and Schrag, 2002; Goddéris et al., 2003). Photosynthesis provides another mechanism for CO2 drawdown, via conversion of CO2 to O2 and rapid burial of organic carbon, which is reflected in a positive δ13C excursion for carbonates (Pierrehumbert et al., 2011). Additionally, long term cloud cover (Feulner et al., 2015), fluctuations in atmospheric-ocean heat transport, the earth's albedo, or solar luminosity (Pierrehumbert et al. (2011) are also proposed as potential causes of the onset of glaciation (ice-house mode climate).

    In a recent paper, Schmid 2017 focused on the cause of the Bitter Springs carbon isotope anomaly, she argues the cause of the pre-glacial, globally recognised, carbon and oxygen isotope variations in carbonate sediments tied to the Bitter Springs anomaly is a response to widespread fractional evaporation of dissolved CO2. This carbon isotope anomaly ties to a well defined correlation with the distribution of Neoproterozoic evaporite basins. She also shows volcanism occurred during the onset of the Bitter Springs Stage (811–788 Ma) and associated widespread evaporite distribution across Australia.


    Schmid (op. cit.) argues that the albedo effect began with of the widespread deposition of Rodinian supercontinent evaporites in very shallow marine to epicontinental sedimentary successions beginning ≈810 Ma, increased siliciclastic redbed weathering. This and continuing evaporite deposition and exposure between ≈780 and 720 Ma drove a worldscale increase in Earth's albedo. Such highly reflective salt deposits defined a saline giant across an area that today covers one-third of the Australia continent. Thus, this and other penecontemporaneous saline giants over the Rodinian supercontinent played a potentially significant role in the onset of atmospheric cooling via a significant increase in albedo (Figure 5). These salt beds occur in periods that typify the onset of local (750 Ma) and then global glaciation (720 Ma).


    Schmid (2017) goes on to note that the degree of evaporation in the Bitter Springs group sediments is related to the δ13C signature in variably concentrated waters (Figure 6). That is the Tonian Bitter Springs Group (≈830–750 Ma), within the Amadeus Basin in central Australia consists of thick halite and sulphate evaporite accumulations and associated carbonates. The deposition of halite occurred in shallow marine, lagoon (salina) environment (Gillen Formation), and developed into sulphate-dominated supratidal sabkha during sea level regression (Johnnys Creek Formation). The overall regression was interrupted by a transgressive phase lasting at least 20 Ma and leading to deposition of basin-wide stromatolitic dolostone (Loves Creek Formation). The salinity and high evaporation is reflected in positive δ13C in the intercalated carbonates (+4 to +6‰ VPDB) of the evaporitic units, while the shallow marine stromatolitic incursion of the Loves Creek Formation (−2‰ δ13C) show typical marine carbonate isotopic values (Figure 7).

    This salinity controlled isotopic separation supports the observations of Stiller et al. (1985) who noted extreme enrichment of 13C in the dissolved inorganic carbon pool in evaporating brines up with δ13C values of up to + 16.5‰ under natural abiotic, oxic conditions in Dead Sea evaporation ponds (Figure 7). The systematic increase in 13C values in highly evaporated waters from the various bittern ponds of the Dead Sea Saltworks is thought to result from a nonequilibrium gas-transfer isotope fractionation. The process of ongoing evaporation leads to CO2 loss within the evaporative brine as less and less gas can held in solution (see Warren 2016, Chapter 9). CO2 exchange in a concentrating surface brine occurs directly between the water column and air, resulting in direct CO2 loss through evaporation. In a sabkha environment. CO2 is released from the hypersaline groundwater through sediments before being released to air as evaporites may form intrasediment precipitates. Overall, atmospheric CO2 uptake in hypersaline settings fed by shallow marine water is diminished compared to the normal marine settings.


    Precipitated carbonates modern salinas and sabkhas are mainly aragonite, and formed in association with such evaporative brine, are consistently13C enriched, as seen in nearby Solar Lake and Sabkha Gavish (Figure 2; Stiller et al., 1985; Schidlowski et al., 1984). In a similar fashion, Palaeoproterozoic interbedded shallow marine carbonates, redbeds and evaporites have values up to δ13C + 17.2‰ (Melezhik et al., 1999). Permian and Triassic (Schmid et al., 2006a) redbeds and evaporite sequences also have 13C-rich carbonates (up to +7‰) and enrichment is partly attributed to evaporation and associated CO2 loss (Beauchamp et al., 1987). In modern oceans, atmospheric CO2 is consumed by biological activity and carbonate production originates from mainly marine organisms, leading to near atmospheric to organic negative δ13C signatures in the precipitated sediment(Andersson, 2013).

    If increasing salinity leads to unfavourable conditions for photosynthesising organisms to survive (Lazar and Erez, 1992), carbonate through to bittern precipitation becomes increasingly abiotic and evaporation driven, especially at the upper end of the evaporation series. The loss of Ca during evaporation of a brine, via aragonite and calcium sulphate precipitation, leads to an increase in Mg/Ca ratio and an increase in residual brine density. This can result in primary dolomite precipitation or widespread reflux dolomitisation (Schmid et al., 2006, Warren 2000, 2016.

    In summary, the typical δ13C signature in normal marine carbonate sediment across much of geological time centres around 0 ‰ and ranges between a few parts per mille on either side of the zero line reflecting precipitation by calcifying and photosynthesising organisms (e.g. algae), while abiotic, evaporation induced carbonates tend to have δ13C values above +1‰. More positive δ13C values (+4 to +6‰) tend to typify dominantly abiotic carbonates (and local methanogenic carbonates with even more positive values) and support the notion of evaporation-driven 13C-enrichement in times of widespread evaporitic epeiric and basinwide carbonates. In the Precambrian, widespread marine stromatolitic units such as, algal Loves Creek Formation reflects δ13C values for biogenic carbonate precipitation under shallow marine, non-hypersaline conditions. The change from a shallow hypersaline lagoon towards evaporitic mudflats and salterns suggests an increase in aridity and continentality/hydrographic isolation, with associated more positive δ13C values.

    Implications for some types of 13C anomaly

    The Bitter Springs Group chemostratigraphy has been correlated globally and the negative excursion was named previously after this unit (Bitter Springs Stage anomaly). However, the mechanism of evaporation-driven fractionation of δ13C is different from the commonly proposed inorganic-organic carbon fractionation, and challenges the views on interpreting global chemostratigraphic anomalies or excursion and their cause. Evaporite basins covered vast regions worldwide prior to the Sturtian glaciation, e.g. the Australian evaporites would have covered a third of the continent. The light surface of evaporites and associated carbonates would have had a high albedo and effectively cause less surface heat absorption. This subsequently would have triggered temperature decrease on a continental and possibly global scale. The Schmid paper hypothesises that the deposition of evaporites worldwide would have contributed to global cooling starting ≈100 Ma prior to Snowball Earth and would have played an important role in the onset of global glaciation.

    References

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    Berner, R.A., 1987. Models for carbon and sulfur cycles and atmospheric oxygen; application to Paleozoic geologic history. American Journal of Science, 287: 177-196.

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    Des Marais, D.J., 1997. Isotopic evolution of the biogeochemical carbon cycle during the Proterozoic Eon. Organic Geochemistry, 27(5): 185-193.

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    Feulner, G., Hallmann, C. and Kienert, H., 2015. Snowball cooling after algal rise. Nat. Geosci. , 8: 659-662.

    Feulner, G. and Kienert, H., 2014. Climate simulations of Neoproterozoic snowball Earth events: similar critical carbon dioxide levels for the Sturtian and Marinoan glaciations. Earth Planet. Sci. Lett., 404: 200-205.

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    Goddéris, Y., Donnadieu, Y., Nédélec, A., Dupré, B., Dessert, C., Grard, A., Ramstein, G. and François, L.M., 2003. The Sturtian ‘snowball’ glaciation: fire and ice. Earth Planet. Sci. Lett. , 211: 1-12.

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    Holser, W.T., Schidlowski, M., Mackenzie, F.T. and Maynard, J.B., 1988. Geochemical cycles of carbon and sulfur. In: C.B. Gregor, R.M. Garrels, F.T. Mackenzie and J.B. Maynard (Editors), Chemical cycles in the evolution of the earth. John Wiley, New York, pp. 105–173.

    Horton, T.W., Defliese, W.F., Tripati, A.K. and Oze, C., 2016. Evaporation induced 18O and 13C enrichment in lake systems: A global perspective on hydrologic balance effects. Quaternary Science Reviews, 131: 365-379.

    Lazar, B. and Erez, J., 1992. Carbon geochemistry of marine-derived brines: I. 13C depletions due to intense photosynthesis. Geochim. Cosmochim. Acta, 56: 335-345.

    Leng, M.J. and Marshall, J.D., 2004. Paleoclimate interpretation of stable isotope data from lake sediment archives. Quaternary Science Reviews, 23(811-831).

    Liu, Y., Peltier, W.R., Yang, J. and Vettoretti, G., 2013. The initiation of Neoproterozoic ‘‘snowball” climates in CCSM3: the influence of paleocontinental configuration. Climate Past, 9: 2555-2577.

    Melezhik, V.A., Fallick, A.E., Medvedev, P.V. and Makarikhin, V.V., 1999. Extreme 13Ccarb enrichment in ca. 2.0 Ga magnesite-stromatolite-dolomite-‘red beds’ association in a global context: a case for the world-wide signal enhanced by a local environment. Earth Sci. Rev., 48: 71-120.

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    Gases in Evaporites Part 3 of 3; Where do gases generate and reside at the scale of a salt mass or salt bed

    John Warren - Saturday, December 31, 2016

    So far we have looked at gas distribution and origins in evaporites at micro and mesoscales and have now developed sufficient understanding to extrapolate to the broader scale of architecture for a large body of salt in an evaporite. We shall do this in a classification framework of extrasalt versus diagenetic periphery versus intrasalt gas in a halokinetic salt mass (Figure 1).


    Extrasalt gas and brine intersections

    This type of gas intersection is perhaps the most damaging to a salt mine operation and tends to occur when a gas release is encountered in an expanding mining operation, or a drill hole, that lies near the salt body edge and intersects nonsalt sediments. Extrasalt fluids can be either normally pressured or overpressured depending on the connectivity of the plumbing in the extrasalt reservoir. Salt because of its excellent seal potential tends not to leak or leak only slowly, so facilitating significant pressure buildup (Warren, in press)

    The gas inflow from this type of extrasalt breach in a salt mine is typically accompanied, or followed by, a brine release that sometimes cannot be plugged, even by a combination of grouting and brine pumping. Brine inflow rates in this scenario tend to increase with time as ongoing salt dissolution is via ongoing undersaturated water crossflows and the mine or the shaft is ultimately lost to uncontrollable flooding of gas blowouts in an oil well with poor pressure control infrastructure and planning. This type of edge intersection is why a number of early attempts to construct shafts for potash mines in western Canada failed in the middle of last century. It is why freeze curtains are considered the best way to contract a shaft for a potash mine. Examples of this type of gas/brine intersection are usually tied to telogenetic fluid entry from substantial aquifer reservoirs outside the main salt mass and are discussed in detail in Warren, (2016, Chapter 13) and as a type of salt anomaly association discussed in Warren (in press).

    The extrasalt source and potential inflow volume of this form of gas (mostly methane and co-associated brine) is largely tied to maturity of hydrocarbon source rocks located external to the salt mass in both suprasalt and subsalt positions (Figure 1). In the past, unexpected extrasalt intersections of pressurised gas reservoirs during oil well drilling lead to spectacular blowouts or “gushers”, especially in situations where the salt held back a significant volume of fluid held in open fractures beneath or adjacent to a salt seal (Table 1). The fluid-focusing effects of suprasalt dome drape and associated extensional falling and gas leakage also mean “gas clouds” are common above salt domes (Warren, 2016, in press). Low σhmin leads to upward gas migration through fracturing (Dusseault et al., 2004). So, in the supradome extrasalt position, simultaneous blowout and lost circulation conditions can be encountered, as well as the problem of severely gas-cut drilling fluids. The volumes of gassy liquids held in pressurised extrasalt reservoirs can be substantial so blowouts or “gushers” can be difficult to control, as was the case with the world-famous subsalt Qom (1956) and suprasalt Macondo (2010) blowouts (Table 1). Methane and gassy liquids generated by organic maturation tend to be the dominant gases found in this situation.

     

    Caprock and other salt periphery-held gases

    This style of gas occurrence is in part related to gases sourced in maturing extra-salt sediments but also taps gases that are the result of the diagenetic processes that create caprocks. Caprocks are alteration and dissolution haloes to both bedded and halokinetic salt masses and so are distinct gas reservoirs compared to extrasalt sediments (Warren, 2016; Chapter 7). They are compilations of fractionated insolubles left behind at the salt dissolution interface as the edge of halite mass liquefies. Accordingly, caprocks are zoned mineralogically according rates of undersaturated fluid crossflow and in part responding to variable rates of salt rise and resupply. Anhydrite (once suspended in the mother salt) accretes at the dissolution front. Ongoing undersaturated crossflow at the outer contact of the anhydrite residue carapace alters anhydrite to calcite via bacterially- or thermochemically-driven sulphate reduction, with hydrogen sulphide as a by-product. Additional sulphate reduction can occur in the extrasalt sediment both at or near the caprock site, but also deeper or more distal positions in the extrasalt, so sulphate reduction can be a major source of the H2S gas found in the salt periphery. H2S can also migrate in a c from sulphate reduction in maturing sediments located some depth below the salt.

    Dissolution that facilitates caprock also drives the creation of vugs and fractures in the caprock, and is one of the primary controls on reservoir poroperm levels in various caprock oil and gas reservoirs discovered in the 1920s in the US Gulf Coast. Methanogenic biodegradation of the same hydrocarbons, which facilitate sulphate reduction, can generate CO2 in the caprock and extrasalt sediments (Clayton et al., 1997)

    Many salt mine problems in Germany in the early days of shaft sinking for salt mining were related to unexpected shallow gas outflows confronted within caprock-hosted gas-filled vugs and fractures encountered by the mine shaft on the way to a potash ore target (Gropp, 1919; Löffler, 1962; Baar, 1977). Likewise, the highly unpredictable distribution of gases in the shallow caprocks and salt peripheries of the US Gulf Coast were the cause of some spectacular blowouts such as Spindletop (1901) (Table 1). Because the volume of held liquids is more limited in the vugs and fractures in a caprock compared to fractured subsalt reservoirs, the rate of fluid escape in a “caprock-fed” gusher tends to lessen and even self-bridge more rapidly than when salt is sealing a fractured overpressured subsalt reservoir (days or weeks versus months). As such these intersections, if isolated from extrasalt reservoirs as not such a problem in the drilling of oil wells. In simpler, less environmentally conscious, early days of oilwell drilling in East Texas in the 1920s, “gushers” were often celebrated, tourist spots and considered a sign of the potential wealth coming to the country being drilled.

    Intrasalt gas

    This type of accumulation/intersection is often described as an intrasalt gas pocket and is typified by a high rate of gas release, that in a mine is accompanied by a rockburst, followed by a waning flow that soon reaches negligible levels as the pocket drains (see article 1 in this series). Intrasalt gas pockets can create dangerous conditions underground and lives can be lost, but in many cases after the initial blowout and subsequent stabilisation, the mine operations or oil-well drilling can continue. Gas constituents and relative proportions are more variable in intrasalt gas pockets compared to gases held in the extrasalt and the periphery. Extra-salt gases are typically dominated by methane with lesser H2S and CO2, periphery gases by H2S and methane, while intrasalt gases can be dominated by varying proportions of nitrogen, hydrogen or CO2. Methane can be a significant component in some intrasalt gas pockets, but these occurrences are usually located in salt anomalies or fractures that are in current or former connection with the salt periphery.

    Gas types and sources at the local and basin scale

    The type of gas held within and about a salt mass in a sedimentary basin is broadly related to position in the mass and proximity to a mature source rock. Herein is the problem, most of the gases that occur in various salt-mass related positions (intrasalt, extrasalt and periphery) can have multiple origins and hence multiple sources.

    Accumulations of gas with more than 95 vol.% N2 are found in most ancient salt basins and the great majority of these accumulations are hosted in intersalt and subsalt beds, with the gas occurring in both dispersed and free gas forms in the salt, as in many Zechstein potash mines of Germany and the Krasnoslobodsky Mine in the Soligorsk mining region of Russia (Tikhomirov, 2014). Nitrogen gas today constitutes around 80% of earth atmosphere where it can result from the decay of N-bearing organic matter (proteins). Ultimately, nitrogen speciates from aqueous mantle fluids in oxidised mantle wedge conditions in zones of subduction and in terms of dominance in planetary atmospheres it indicates active plate tectonics (Mikhail and Sverjensky, 2014). Nitrogen in the subsurface is large unreactive compared to oxygen and so tens to stay in its gaseous form while oxygen tens to combine into a variety of minerals. When held in a salt bed, nitrogen can be captured from the atmosphere during primary halite precipitation and stored in solution in a brine inclusion so creating a dispersed form of pressurised nitrogen. When buried salt recrystallizes during halokinesis, with flow driven by via pressure solution, inclusion contents can migrate to intercrystalline positions and from there into fractures to become free gas in the salt.

    Methane gas captured in and around a salt mass as both dispersed and be gas typically mostly comes from organic maturation. The maturing organic matter can be dispersed in the salt during primary halite precipitation, it can be held in intersalt source beds (as in the Ara Salt of Oman), or it can migrate laterally to the salt edge, along with gases and fluids rising from more deeply buried sources. Thus, the presence of oil, solid bitumen and brine inclusions, with high contents of methane in halite, does not unequivocally point to the presence of oil or gas in the underlying strata, it can be locally sourced from intersalt beds as in the Ara Salt. However, a geochemical aureole can be said to occur if hydrocarbons in the halite-hosted inclusions can genetically be linked with reservoired oil or gas. The presence of methane in salt anomalies in Louann Salt mines in the US Gulf Coast and some mines in Germany is likely related to organic maturation of deeply buried extrasalt source rocks with subsequent entrapment during halokinesis and enclosure of allochthon-suture sediments.

    Hydrogen sulphide gas (H2S) is a commonplace free gas component in regions of bacterial and thermogenic sulphate reduction. Like methane, much of its genesis is tied to organic maturation products (and sulphate reduction processes), and like methane, it can be held in salt seal traps, or in peripheral salt regions, or in intrasalt and intersalt positions and like metyhane if it escapes and ponds in an air space its release can be deadly (Table 1; Luojiazhai gas field, China). Because both bacterial and thermochemical sulphate reduction requires organic material or methane, there is a common co-occurrence of the two gases. Caprock calcite phases are largely a by-product of bacterial sulphate reduction, so there is an additional association of H2S with caprock-held occurrences. This form of H2S, along with CO2, created many problems in the early days of shaft sinking in German salt mines. More deeply sourced H2S tend to be a production of thermochemical sulphate reduction in regions where pore fluid temperatures are more than 110°C.

    Detailed study of CO2 and its associated geochemical/mineralogic haloes shows much of the CO2 held in Zechstein strata of Germany has two main sources; 1) Organic maturation and 2) carbonate rock breakdown especially in magmatic hydrothermal settings (Fischer et al., 2006). The organic-derived CO2 endmember source (with δ13C near -20‰) is present in relatively low concentrations, whereas large CO2 concentrations are derived from an endmember source with an isotope value near 0‰. Although the latter source is not unequivocally defined by its isotopic signature, such “heavy” CO2 sources are most likely attributed to heating-related carbonate decomposition processes. This, for example, explains the CO2-enriched nature of salt mines in parts if the former East Germany where Eocene intrusives are commonplace (Shofield et al., 2014).

    Hydrogen (H2) gas distribution as a major component varies across salt basins and is especially obvious in basins with significant levels of carnallite and other hydrated potassic salts. This association leads to elevated radiogenic contents tied to potassic salt units, with hydrogen gas likely derived from the radiogenic decomposition of water (see article 2 in this series). The water molecules can reside in hydrated salts or in brine inclusions in salt crystals.

    Summary

    Various proportions of gases (N2, CH4, CO2, H2S, H2) held in salt as dispersed and free gas occur in all salt basins. But at the broad scale, certain gases are more common in particular basin and tectonic positions. Methane is typically enriched in parts of a basin with mature source rocks, but can also have a biogenic source. Likewise, H2S is tied to zones of organic breakdown, especially in zones of either bacterial or thermochemical sulphate reduction. CO2 can occur in salt in regions of organic degradation, but is most typical those of parts of a salt basin where igneous processes have driven to thermal and metamorphic decomposition of underlying carbonates (including marbles). Nitrogen because of its inert nature is a commonplace intrasalt gas and comes typically from zones of organic decomposition with dispersed nitrogen becoming free gas with subsequent halokinetic recrystallisation. Ongoing salt flow can drive the distribution of all dispersed salt stored gases into free gas (gas pocket) positions.

    References

    Baar, C. A., 1977, Applied salt-rock mechanics; 1, The in-situ behavior of salt rocks: Developments in geotechnical engineering. 16a.

    Clayton, C. J., S. J. Hay, S. A. Baylis, and B. Dipper, 1997, Alteration of natural gas during leakage from a North Sea salt diapir field: Marine Geology, v. 137, p. 69-80.

    Dusseault, M. B., V. Maury, F. Sanfilippo, and F. J. Santarelli, 2004, Drilling around salt: Stresses, Risks, Uncertainties: Gulf Rocks 2004, In 6th North America Rock Mechanics Syposium (NARMS), Houston Texas, 5-9 June 2004, ARMA/NARMS 04-647.

    Fischer, M., R. Botz, M. Schmidt, K. Rockenbauch, D. Garbe-Schönberg, J. Glodny, P. Gerling, and R. Littke, 2006, Origins of CO2 in Permian carbonate reservoir rocks (Zechstein, Ca2) of the NW-German Basin (Lower Saxony): Chemical Geology, v. 227, p. 184-213.

    Gropp, 1919, Gas deposits in potash mines in the years 1907-1917 (in German): Kali and Steinsalz, v. 13, p. 33-42, 70-76.

    Löffler, J., 1962, Die Kali- und Steinsalzlagerstätten des Zechsteins in der Dueutschen Deomokratischen Republik, Sachsen: Anhalt. Freiberg. Forschungsh C, v. 97, p. 347p.

    Mikhail, S., and D. A. Sverjensky, 2014, Nitrogen speciation in upper mantle fluids and the origin of Earth's nitrogen-rich atmosphere: Nature Geoscience, v. 7, p. 816-819.

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

    Tikhomirov, V. V., 2014, Molecular nitrogen in salts and subsalt fluids in the Volga-Ural Basin: Geochemistry International, v. 52, p. 628-642.

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

    Warren, J. K., in press, Salt usually seals, but sometimes leaks: Implications for mine and cavern stability in the short and long term: Earth-Science Reviews.

     

     

    Gases in Evaporites, Part 2 of 3: Nature, distribution and sources

    John Warren - Wednesday, November 30, 2016

    This, the second of three articles on gases held within salt deposits, focuses on the types of gases found in salt and their origins. The first article (Salty Matters October 31, 2016) dealt with the impacts of intersecting gassy salt pockets during mining or drilling operations. The third will discuss the distribution of the various gases with respect to broad patterns of salt mass shape and structure (bedded, halokinetic and fractured)

    What’s the gas?

    Gases held in evaporites are typically mixtures of varying proportions of nitrogen, methane, carbon dioxide, hydrogen, hydrogen sulphide, as well as brines and minor amounts of other gases such as argon and various short chain hydrocarbons (Table 2). There is no single dominant gas stored in salt across all evaporite deposits, although a particular gas type may dominate or be more common in a particular region. For example, CO2 is commonplace in the Zechstein salts of the Wessen region of Germany (Knipping, 1989), methane is common in a number of salt dome mines in central Germany and the Five-Islands region in Louisiana, USA (Kupfer, 1990), nitrogen is dominant in other salt mines in Germany and New Mexico, while hydrogen can occur in elevated proportions in the Verkhnekamskoe salt deposits of the Ural foredeep (Savchenko, 1958).

    Before considering the distribution of the various gases, we should note that older and younger sets of gas analyses conducted over the years in various salt deposits are not necessarily directly comparable. Raman micro-spectroscopy is a modern, non-destructive method for investigating the unique content of a single inclusion in a salt crystal. There is a significant difference in terms of what is measured in analysing gas content seeping from a fissure in a salt mass or if comparisons are made with conventional wet-chemical methods which were the pre Raman-microscopy method that is sometimes still used. Wet chemical methods require sample destruction, via crushing and subsequent dissolution, prior to analysis. This can lead to the escape of a variable proportion of the volatile compounds during the crush stage, such as methane, hydrogen, ethane and aromatic hydrocarbons, especially of those components held in fissures and more open intercrystalline positions. Any wet chemical technique gives values that represent the average of all the inclusion residues and intercrystalline gases left in the studied sample, post preparation. In contrast, Raman Microspectroscopy indicates content and proportion within a single inclusion in a salt crystal. So, free gas results and wet chemical compositions, when compared to Raman microscopy determinations from inclusions, are not necessarily directly comparable. With this limitation in mind, let us now look at major gas phases occluded in salt.


    Nitrogen

    Gassy accumulations in salt with elevated levels of N2 occur in many salt basins in regions not influenced by magmatic intrusions (Table 1). In an interesting study of spectroscopic gases held in inclusions in the Zechstein salt of Germany, Siemann and Elendorff (2001) document a bipartite distribution of inclusion gases. With rare exceptions, the first group, made up of N2 and N2-O2 inclusions reveals N2/O2 ratios close to that of modern atmosphere, which they interpret as indicating trapped paleoatmosphere (Figure 1). Similar conclusions are reached in earlier studies of nitrogen gas held in Zechstein salts, using wet chemical techniques (Freyer and Wagener, 1975). The second group documented by Sieman and Elendoorff (2001) is represented by inclusions that contain mixtures of N2, CH4 occasionally H2 or H2S. The most abundant subgroups in this second group are N2-CH4 and N2-CH4-H2 mixtures, that is, the methane association (Figure 1). Siemann and Elendorff (2001) argue that these methanogenic and hydrogenic gas mixtures of the second group are the product of decomposition of organic material under anoxic subsurface conditions. They note that the methane and hydrogenic compounds, as well as some portion of the nitrogen, are not necessarily derived from decomposing organics held within the salt. They could have been generated by degassing of underlying Early Permian (Rotliegendes) or Carboniferous organic-rich sedimentary rocks with subsequent entrapment during early stages of fluid migration, possibly driven by Zechstein halokinesis.


    Different origins and timings of both main nitrogen gas groupings in inclusions in the salt host is supported by stratigraphic correlations (Siemann and Elendorff, 2001). In the stratigraphic layers which contain mainly mixtures of N2 and O2 or pure N2, inclusions of the N2-CH4-H2-H2S-group are rare (A in Figure 1) and vice versa: layers which are rich in N2-CH4-H2-H2S do not contain many pure N2-O2inclusions (B in Figure 1). The majority of layers investigated in the salt mostly contain inclusions of the N2-O2 group, sans methane. Only two anhydrite-rich layers of Zechstein 3 (Main Anhydrite and Anhydrite-intercalated Salt) contain mainly inclusions of the second group (i.e. with abundant methane) as seen in B in Figure 1. The Zechstein 3 potash seams, as well as secondary halites, contain more or less the same population of inclusions from every main group (C in Figure 1). A comparison of the gas-rich inclusions and the gases in the brine-rich inclusions of the Zechstein 2 layer, Main Rock Salt 3, also shows distinct differences. Whereas, the gas-rich inclusions are mostly of the N2-O2 grouping, the gases from the brine-rich inclusions are mostly of the N2-CH4 group, emphasizing different origins for the gas-rich and brine-rich inclusions Siemann and Elendorff (2001) conclude that the latter gas group is a product of thermally evolved anhydrite-rich parts or potash seams that have generated hydrocarbons catagenically, with these products migrating into the overlying and deforming Main Rock Salt 3.

          

    Work on the free gas released during mining of the Permian Starobinsky potash salt deposit in the Krasnoslobodsky Mine, Soligorsk mining region, Russia shows that the dominant free gas is nitrogen, along with a range of hydrocarbons, including methane (Figure 2; Andreyko et al., 2013). The compositional plot is based on free gases released from the main pay horizon of the Krasnoslobodsky Mine, which it the Potash Salt Horizon 3. The exploited stratigraphy is 16 to 18 m thick in the centre of the minefield and thins to 1 m thick at the edges of the ore deposit. Depth to the potash horizon varies from 477 to 848 m below the landsurface. It consists of three units: 1) top sylvinite unit, which is classified as non-commercial due to high insoluble residue content; 2) mid clay–carnallite unit, which is composed of alternating rock salt, clay and carnallite; and 3) bottom sylvinite unit, which is the main ore target and is composed of six sylvinite layers (I-VI), alternating with rock salt bands (Figure 3). The distribution of gas across the stratigraphy of units I-VI shows that the free gas yields are consistently higher in the sylvinite bands (Figure 3).

          

    Oxygen levels in salt are not studied in as much detail as the other gas phases due to their more benign nature when released in the subsurface. Work by Freyer and Wagener (1975) focusing on the relative proportions of oxygen to nitrogen held in Zechstein salts was consistent with the inclusions retaining the same relative proportions of the two gases as were present in the Permian atmosphere when the salts first precipitated.

    As well as being held within the salt mass, substantial nitrogen accumulations can be hosted in inter-salt and sub-salt lithologies. For example, the resources of nitrogen in the Nesson anticline in the Williston Basin are ≈53 billion m3 and held in sandstones intercalated with anhydrite in the Permian Minnelusa Fm (Marchant, 1966; Anderson and Eastwood, 1968) and those in Udmurtia in the Volga–Ural Basin are ≈33 billion m3 (Tikhomirov, 2014). In both these non-salt enclosed cases the evolution of the nitrogen gas is related to the catagenic and diagenetic evolution of organic matter. Tikhomirov (2014) concludes that nitrogen in the various subsalt fluids in the Volga–Ural Basin originates from two major sources. Most of the nitrogen in the subsalt has δ15N > 0‰ and is genetically related to concentrated calcium chloride brines, heavy oils, and bitumen in the platform portion of the basin and so ties to a catagenic origin. The other N2 source is seen in subordinate amounts of nitrogen across the basin with δ15N values < 0‰. According to Tikhomirov (2014), this second group seems to be genetically related to methane derived at significant depths in the basement lithologies of Ural Foredeep and Caspian depression (possibly a form of mantle gas?).

    Methane

    Unexpected intersections with gas pockets containing significant proportions of methane can be dangerous, as evidence by the Belle Isle Salt Mine disaster in 1979 as well as others (see article 1). Many methane (earth-damp) intersections and rockbursts in US Gulf Coast salt mines can be tied to proximity to a shaley salt anomaly (Molinda 1988; Kupfer 1990).

    Methane contents of normal salt (non-anomaly salt) in salt domes of the Five-Islands region of the US Gulf Coast were typically low (Kupfer, 1990). For example, the majority of the samples of normal salt, as tested by Schatzel and Hyman, (1984), contained less than 0.01 cm3 methane per 100 g NaCI. Although there can be wide ranges of methane enrichment in normal versus outburst salts, outburst salts are typified by increases in halite crystal size, the number of included methane gas bubbles, contorted cleavage surfaces related to increased overpressured gas contents, and an increase in clay impurities in some of the more methane-rich salt samples.

     

    Probably the most detailed study of controls on methane distribution in domal salt was conducted at the Cote Blanche salt mine in southern Louisiana (Molinda, 1988). Because outbursts were the primary mode of methane emission into the mine, he mapped more than 80 outbursts, ranging in size from 1 to 50 ft in diameter. The outbursts were aligned and elongate parallel to the direction of salt layering and such zones correlate well with high methane content (Figure 4). Halite crystal size abruptly increased upon entry into gassy zones subject to rockburst. The intensity of folding and kinking of the salt layering within the outburst zone also increased. The interlayered sand, shown in Figure 4, also occurred throughout the mine and not just in the mapped area shown, but was not a significant source of methane. Molinda (1988) and Schatzel and Hyman (188) all concluded that not all rockbursts were hosted by coarsely crystalline fine-grained salt, so the absence of coarsely crystalline salt may not be an indication that a rockburst cannot occur, although it is less likely. Sampling the salt for methane levels may be a better approach for rockburst prediction.

    In some methane occurrences in Europe (in addition to generation from clayey intrasalt organic entraining bands) there is a further association with igneous-driven volatilization from nearby, typically underlying, coaly deposits. This igneous association with coals and carbonates likely creates an additional association with CO2 and possibly H2S.

    CO2

    Many CO2 rich gas intersections tie to regions that have been heated or cross-cut with igneous intrusives. For example, many of the CO2-bearing gas mixtures that were encountered in the Werra region during the initial exploratory drillings for potash salts(Table 1 in article 1; Frantzen, 1894). In 1901, shortly after mining at Hämbach had begun, coincident intersections of basalt dykes and releases of gas were observed (Gropp, 1919). Dietz (1928a,b) noted that a fluid phase was always involved in the fixation of the CO2gas mixtures in the Zechstein evaporites, while Bessert (1933) reported on the enrichment of anhydrite, kainite, and polyhalite at the contact with the basaltic intrusive. Accumulations of CO2-rich free gas in many Wessen mines became a safety issue and many subsequent studies underlined the association of CO2 enriched gases with basalt occurrences (Knipping, 1989). In almost all instances in the Zechstein where native sulphur forms the at the contact of a basaltic dyke, knistersalz dominates the evaporite portion of the samples. According to Ackermann et al. (1964) gas-bearing drill core samples collected in the Zechstein K1Th unit (carnallitite, sylvinite) in the Marx-Engels mine (formerly Menzengraben, East Germany) contained up to 0.6 - 14.0 ml gas/100 gm rock, with an average of 3.6 ml of gas fixed in 100 g of salt rock (Table 1)of. On average, the gas inclusions were composed of 84 vol% CO2. Knipping (1989) concludes that quantities of volatile phases (mainly H20 and CO2) penetrated the evaporites during intrusion of basaltic melts. These gases influenced mineral reactions, particularly when intersecting with reactive K-Mg rock layers of the Hessen (K1H) and Thuringen (K1Th) potash seams in the former East Germany. The intensity of this reaction was likely greater when the evaporite layers contain hydrated salts such as carnallite and kainite. Such salts tend to release large volumes of water at relatively low temperatures when heat by a nearby intrusive (Warren, 2016; Chapter 16; Schofield et al., 2014). In doing so, significant volumes of CO2 enriched gases were trapped in the altered and recrystallising evaporites, so forming knistersalz.


    While discussing CO2 elevated levels, it is probably taking a little time to illustrate what makes this area of CO2 occurrence so interesting in terms of the differential levels of reactivity when hydrated versus non-hydrated salt units are intruded and how this process facilitates penetration of volcanic volatiles (including CO2) into such zones. The Herfa-Neurode potash mine is located in the Werra-Fulda Basin in the Hessian district of central Germany (Figure 5a). The targeted ore levels consist of the carnallite-rich Kaliflöz Hessen (K1H) and Kaliflöz Thüringen (K1Th) intervals, which form part of the Zechstein 1 (Z1) bedded Werra salt succession(Warren, 2016). In the mine the K1H and K1Th units range in thickness from 2 m to 10 m, are generally subhorizontal and occur at a depth of 650–710 m below the present-day surface. In the later Tertiary, basaltic melts intruded these Zechstein evaporites as numerous sub-vertical dykes, but only a few dykes attained the Miocene landsurface. Basaltic melt production was related to regional volcanic activity some 10 to 25 Ma. Basalts exposed in the mine walls, where it cuts non-hydrous units of halite or anhydrite, are typically subvertical dykes, rather than subhorizontal sills. The basalts are phonolitic tephrites, limburgites, basanites and olivine nephelinites. Dyke margins are usually vitrified, forming a microlitic limburgite glass along dyke edges in contact with salt (Figure 5b; Knipping, 1989). At the contact on the evaporite side of the glassy rim there is a cm-wide carapace of high-temperature salts (mostly anhydrite and ferroan carbonates). Further out, the effect of the high-temperature envelope is denoted by transitions to clear halite, with higher temperature fluid inclusions (Knipping 1989). All of this metre-scale alteration is an anhydrous alteration halo, the salt did not melt (melting temperature of 804°C), rather than migrating, the fluid driving recrystallisation was largely from entrained brine/gas inclusions. The dolerite/basalt interior of the basaltic dyke is likewise altered and salt soaked, with clear, largely inclusion-free halite typically filling vesicles in the basalt.

    Heating of hydrated salt layers, adjacent to a dyke or sill, tends to drive off the water of crystallisation (chemical or hydration thixotropy) at much lower temperatures than that at which anhydrous salts, such as halite or anhydrite, thermally melt (Figure 5c; Schofield et al., 2014). For example, in the Fulda region, the thermally-driven release of water of crystallisation within particular salt beds creates thixotropic or subsurface “peperite” textures in carnallitite ore layers. These are layers where heated water of crystallisation escaped from the hydrated-salt lattice. Dehydration-driven loss of mechanical strength focuses zones of magma entry into particular subhorizontal horizons in the salt mass, wherever hydrated salt layers were present. In contrast, dyke and sill margins are much sharper and narrower in zones of contact with anhydrous salt intervals and the intrusive is sub-vertical to steeply dipping (Figure 5b versus 5c).

    Accordingly, away from the immediate vicinity of the direct thermal aureole, heated and overpressured dehydration waters can enter a former carnallite halite bed, and drive the creation of extensive soft sediment deformation and peperite textures in the former hydrated layer (Figure 5c). Mineralogically, sylvite and coarse recrystallised halite dominate the salt fraction in the peperite intervals of the Herfa-Neurode mine. Sylvite in these altered zone is a form of dehydrated carnallite, not a primary-textured salt. Across the Fulda region, such altered zones and deformed units can extend along former carnallite layer to tens or even a hundred or more metres from the dyke feeder. Ultimately, the deformed potash bed passes back out into the unaltered bed, which retains abundant inclusion-rich halite and carnallite (Schofield et al., 2014). That is, nearer the basalt dyke, the carnallite is largely transformed into inclusion-poor halite and sylvite, the result of incongruent flushing of warm saline fluids mobilised from the hydrated carnallite crystal lattice as it was heated by dyke emplacement. During Miocene salt alteration/thermal metamorphism in the Fulda region, NaCl-fluids were mixed with fluids and gases originating from thermally-mobilised crystallisation water in the carnallite, as it converted to sylvite. This brine/gas mixture altered the basalts during post-intrusive cooling, an event which numerical models suggest was quite rapid (Knipping, 1989): a dyke of less than 0.5 m thickness probably cooled to temperatures less than 200°C within 14 days of dyke emplacement. The contrast in alteration extent between anhydrous and hydrous salt layers shows alteration effects are minimal wherever the emplacement temperature of the magma is below that of the anhydrous salt body as it is next to a basalt dyke. If this is the mechanism driving entry of igneous-related volatiles (gases and liquids) into a salt body then the distribution of products (including CO2) will be highly inhomogeneous and related to the minerally of the salt unit adjacent to the intrusive.


    Hydrogen

    Many hydrogen occurrences are co-associated with occurrences of potash minerals, especially the minerals carnallite and sylvite. For example, mine gases (free gas) at Leopoldshall Salt Mine (Zechstein, Permian of Stassfurt, Germany) flowed for at least 4.5 years, producing hydrogen at a rate of 128 cubic feet per day (Rogers 1921). Bohdanowicz (1934) lists hydrogen gas as being present in evaporite intersection in the Chusovskie Gorodki well, drilled in 1928 near the city of Perm to help define the southern extent of the Soligamsk potash. Gases in the carnallitite interval in that well contained 33.6% methane and 17.4% hydrogen. More recent work in the same region clearly shows hydrogen is a commonplace gas in the mined Irenskii unit in the Verkhnekamskoe potash deposit within the central part of the Solikamsk depression in the Ural foredeep. Based on a study of free gas and inclusion-held gas in the Bereznikovshii Mine, Smetannikov (2011) found that the elevated H2 levels are consistently correlated with the carnallite and carnallite-bearing layers (Table 2). Other gases present in significant amounts, along with the hydrogen, in the potash zones include nitrogen and methane. Interestingly, methane is present in much higher proportions in the free gas fraction in the ore zones compared to gases held in inclusions in the potash crystals (Table 2).  

    Smetannikov (2011) goes on to suggest that likely H2 source is via radiogenic evolution of released crystallisation water hence the higher volumes of hydrogen in the carnallitite units in the mine (Table 2). He argues the most probable mechanism generating H2 is the radiolysis of the crystallisation water of carnallite (CaMgCl3.6H2O) driven by the effects of radioactive radiation. The most likely radiogenic candidates are 40K and 87Rb, rather than such heavy radiogenic isotopes as 238U, 235U, 234U, 232Th, and 226Ra. His reasons for this are as follows: 1) U, Th, and partly Ra are sources of α radiation. U, Th, and Ra are concentrated in the insoluble residues of the salts, and the chloride masses contain only minor amounts of Th. Hence these components have no radioactive effect on carnallite because of the short distances of travel of α particles. Because of this, Smetannikov concludes these elements and not likely sources of radioactive radiation. He argues it is more likely that crystallisation water is more intensely affected by β and γ radiation generated by 40K and 87Rb. Hence, bombardment by β and γ radiation drives the radiolysis (splitting) of this water of crystallisation, so driving the release of hydrogen and hydroxyls. Free hydroxyls can then interact with Fe oxides to form hydro-goethite and lepidocrocite, i.e., both these minerals occur in the carnallite but are absent in the sylvinite.

    The notion of hydrogen being created by radiolysis of potash salt layers is not new; it was used as the explanation of the hydrogen association with various potash units by Nesmelova & Travnikova (1973), Vovk (1978) and Knape (1989). Headlee (1962) attributed the occurrence of hydrogen in salt mines to the absence of substances with which hydrogen could react within the salt beds once it was generated. It is likely that there are several different origins for hydrogen gas in evaporites: 1) Production during early biodegradation of organic matter, co-deposited with the halite or potash salts and trapped in inclusions as the crystal grew. This can explain some of the associated nitrogen and oxygen; 2) A significant proportion can be produced by radiolysis associated with potassium salts (when present) and 3) the hydrogen may be exogenic and have migrated into the halite formations, along with nitrogen. 

    Temperature and mineralogical effects on gas generation and distribution in salt (in part after Winterle et al., 2012)

    Temperature can affect brine chemistry of volatiles released as natural rock salt is heated (is this an analogue to the generation of some types of free gas and other volatile released as salt enters the metamorphic realm? –see Warren 2013; Chapter 14). Uerpmann and Jockwer (1982) and Jockwer (1984) showed that, upon heating to 350°C [662°F], the gases H2S, HCl, CO2, and SO2 were released from blocks of natural salt collected from the Asse mine in Germany. Pederson (1984) reported the evolution of HCl, SO2, CO2, and H2S upon heating of Palo Duro and Paradox Basin rock salt to 250°C [482°F]. Impurities within the salt apparently contain one or more thermally unstable, acidic components. These components can volatilize during heating and increase the alkalinity of residual brines. For example, pH of brines increased from near neutral to approximately 10 in solutions prepared by dissolving Permian Basin salt samples that were annealed at progressively higher temperature [up to 167°C [333°F]  (Panno and Soo, 1983).

    Zones of igneous emplacement and intrusion of interlayered halite and potash units create a natural laboratory for the study of the generation and migration of free and inclusion gases during the heating of various salts (Figures 5, 6 and Table 1). In the Cambrian succession of the Siberian platform evaporite intervals are dominated by thick alternating carbonate- sulphate and halite beds. Numerous basaltic dykes and sills intrude these beds. In a benchmark paper dealing with the zone of alteration of intrusives in evaporites, Grishina et al. 1992 found that, in potash-free halite zones intersected by basaltic intrusions, the evolution of the inclusion fluid chemistry is described as a function of the thickness of the intrusion (h) and the distance of the sample from the contact with the intrusion (d) and expressed as a response to the measure d/h. The associated gas in the halite is dominated by CO2 (Table 1). Primary chevron structures with aqueous inclusions progressively disappear as d/h decreases; at d/h < 5 a low-density CO2 vapour phase appears in the brine inclusions; at d/h < 2, a H2S-bearing liquid-CO2 inclusions occur, sometimes associated with carbonaceous material and orthorhombic sulphur, and for d/h < 0.9, CaCl2, CaCl2.KCl and n CaCl2.n MgCl2 solids occur in association with free water and liquid CO2 inclusions, with H2S, SCO, and Sg. The d/h values marking the transitions outlined above occur both above and below sills, but ratios are lower below the sills than above, indicating mainly conductive heating below and upward vertical fluid circulation above the sill. The water content of the inclusions progressively decreases on approaching the sills, whereas their CO2 content and density increase.


    Carnallite, sylvite and calcium chloride salts occur as solid inclusions in the two associations nearest to the sill for d/h<2. Carnallite and sylvite occur as daughter minerals in brine inclusions. The presence of carbon dioxide is interpreted to indicate fluid circulation and dissolution/recrystallization phenomena induced by the basalt intrusions. The origin of carbon dioxide is related to carbonate dissolution during magmatism. Similar conclusions as to the origin of the CO2 in heated halite-dominant units were reached by many authors studying gases in the Zechstein salts in the Werra Fulda region of Germany (Figure 6; Table 1; see Knipping et al., 1989, Hermann and Knipping 1993 for a summary).

    When the gas distributions measured in inclusions in potash units, other than the Cambrian salts of Siberia, are compared to those salts that have not experienced the effects of igneous heating, there is a clear separation in terms of the dominant inclusions gases (Table 1; Grishina et al., 1998). For example, inclusions in the Verhnekamsk deposit (Russian platform) are N2-rich, in regions not influenced by magmatic intrusives (Figure 2, 3). It is an area marked by the presence of ammonium in sylvite (0.01-0.15% in sylvinite and 0.5% in carnallite, Apollonov, 1976). Likewise, nitrogen (via crush release of the samples) is the dominant gas according to the bulk analyses of the same salts by Fiveg (1973). 

    Later Raman studies of individual inclusions in these Cambrian salts reveals a more complicated inclusion story. There are three types of inclusion fill; a) gas, b) oil and c) brine + carnallite-bearing inclusions. Fe-oxides are sometimes associated with inclusions containing the carnallite daughter minerals. Detailed work by Grishina et al. (1998) shows there two kinds of gassy inclusion: 3) N2-rich and 2) CH4-rich 3) CO2-rich in the same age salt (Table 1; Figure 6). That is, not all gassy brine inclusion in the Cambrian salts are nitrogenous. N2 gas inclusions that also contain CO2 and are associated with sylvite with a low ammonium content (0.04 mol% NH4C1). In contrast, CH4 inclusions are associated with ammonium-rich sylvite (0.4 mol% NH4Cl) (Table 2). Older bulk analysis studies(Apollonov, 1976) showed that red sylvinite  has a lower molar NH4Cl content (0.01%) than pink and white sylvinites (0.05 to 0.19%)

    Raman studies of inclusions in the potash-entraining Eocene basin of Navarra, (Spain) outside of any region with magmatic influence show that the gaseous inclusions are mostly N2-rich with 10% to 20% methane (Table 1; Figure 6; Grishina et al., 1998). Traces of CO2 are also detected in some of the Spanish inclusions. Sylvite inclusions in CO2-free inclusions in Spain contain up to 0.3 mol% NH4C1 (Table 2). Grishina et al. (1998) notes that salt formations in the Bresse basin (France) and Ogooue delta (Gabon) have no basalt intrusions and both occur in N2-free, oil-rich environments. The inference is that nitrogen in some salt units is not an atmospheric residual.


    To test if there may be a mineralogical association with a gas composition in inclusions in various salt and evaporitic carbonate layers we shall return to the Zechstein of Germany and the excellent detailed analytical work of Knipping (1989) and Hermann and Knipping (1993). This work is perhaps the most detailed listing in the public realm of gas compositions inclusions sampled down to the scale of salt layers and their mineralogies. Figure 7 is a plot I made based on the analyses listed in Table 9 in Hermann and Knipping (1993).  It clearly shows that for  Zechstein salts collected across the mining districts of central Germany this is an obvious tie of salt mineralogy to the dominant gas composition in the inclusions. In this context, it should be noted that all Zechstein salt mines are located in halokinetic structures with mining activities focused into areas where the targeted potash intervals are relatively flat-lying. There is little preservation of primary chevrons in these sediments. Nitrogen is the dominant, often sole gas in the halite-dominant units, CO2 is dominant in carbonate and anhydrite dominant layers, this is especially obvious in units originally deposited near the base of the Zechstein succession. Hydrogen in small amounts has an association with inclusions the same carbonates and anhydrites, but elevated hydrogen levels are much more typical of potash units, clays and in juxtaposed layers.  

    In my opinion, the gas compositions in inclusions that we see today in any salt mass that has flowed at some time during its diagenetic history will likely have emigrated and been modified to varying degrees within the salt mass. This is true for all the gases in salt, independent of whether the gas is now held in isolated pockets, fractures or fluid inclusions, Non of the gas in halokinetic salt is not in the primary position. Movement and modification of various gas accumulations in halokinetic salt is inherent to the nature of salt flow processes. Salt and its textures in any salt structure have migrated and been mixed and modified, at least at the scale of millimetres to centimetres, driven by vagaries of recrystallisation as a flowing salt mass flows (Urai et al., 2008). All constituent crystal sizes and hence gas distributions across various inclusions in the salts are modified via flow-induced pressure fields, driving pressure solution and reannealing (See Warren 2016 Chapter 6 for detail).

    With this in mind we can conclude that for the Zechstein of central Germany, nitrogen was likely the earliest gas phase as it occurs in all units. On the other hand, CO2, with its prevalence in units near the base of the succession or in potash units that  have once contained hydrated salts at the time of igneous intrusion, entered along permeability pathways. This may also be true of carbonates and anhydrites which would have responded in more brittle fashion. Hydrogen is clearly associated with potash occurrence or clays and an origin via radiolysis is reasonable.


    This leaves methane, which as we saw earlier is variable present in the Zechstein, but not studied in detail by Knipping (1989) or Hermann and Knipping (1993). There is another excellent paper by Potter et al. (2004) that focuses on the nature of methane in the Zechstein 2 in a core taken in the Zielitz mine, Northeastern Germany Bromine values show a salting-upward profile with values exceeding 200 ppm in the region of potash bitterns (Figure 8a). This is a typical depositional association, preserved even though textures show a degree of recrystallisation and implying there have not been massive fluid transfers since the time the salt was first deposited. Methane is present in sufficient volumes to be sampled in the lower 10 metres of the halite (Z2NAa) and in the upper halite (Z2Nac) and the overlying potash (Z2Kst). If was variably present in the intervening middle halite. When carbon and deuterium isotope values from the methane in the lower and upper parts of the stratigraphy are cross plotted. Values from the lower few meters of the halite plot in the thermogenic range and imply a typical methane derived via catagenesis and possible entry into the lowermost portion of a salt seal. The values from the upper halite and the potash interval have very positive carbon values so that the resulting plot field lies outside that  typical of a variety of methane sources (Figure 8b). Potter et al. (2004) propose that these positive values show preserve primary values and that this methane was sealed in salt since the rock was first deposited. That is positive values preserve evidence of the dominant isotopic fractionation process, which was evaporation of the mother brines. This generated a progressive 13C enrichment in the carbon in the residual brines due to preferential loss of 12CO2 to the atmosphere. The resulting CH4 generated in the sediments, as evaporation and precipitation advanced, so recording this 13C enrichment in the carbon reservoir. Therefore, the isotopic profile observed in this sequence today represents a relict primary feature with little evidence for postdepositional migration. This is a very different association to the methane interpretation based on gases held the US Gulf coast or the Siberian salts. 

    The most obvious conclusion across everything we have considered in this article is that, at the level of gas in an individual brine inclusion measure, there is not a single process set that explains gas compositions in salt. Any gas association can only be tied back to its origins if one studies gas compositions in the framework of the geological history of each salt basin. We shall return to this notion in the third article in this series when we will lock at emplacement mechanisms that can be tied to depositional and diagenetic features and compositions at the macro scale.

    References

    Anderson, S. B., and W. P. Eastwood, 1968, Natural Gas in North Dakota, Natural Gases of North America, Volume Two, American Association of Petroleum Geologists Memoir 9, p. 1304-1326.

    Andreyko, S., O. V. Ivanov, E. A. Nesterov, I. I. Golovaty, and S. P. Beresenev, 2015, Research of Salt Rocks Gas Content of III Potash Layer in the Krasnoslobodsky Mine Field: Eurazian Mining - Gornyi Zhurnal, v. 2, p. 38-41.

    Apollonov, V. N., 1976, Ammonium ions in sylvine of the Upper Kama deposit. Doklady Akademii Nauk SSSR: Earth Science Section 231, 101. English Translation American Geological Institution.

    Bessert, F., 1933, Geologisch-petrographische Untersuchungen der Kalilager des Werragebietes: Archiv flit Lagerstättenforschung, H. 57, 45 S., Berlin.

    Dietz, C., 1928a, Überblick über die Salzlagerstätte des Werra-Kalireviers und Beschreibung der Schāchte "Sachsen-Weimar" und "Hattorf": Z. dt. Geol. Ges., Mb., v. 1/2, p. 68-93.

    Dietz, C., 1928b, Die Salzlagerstätte des Werra-Kaligebietes. - Archiv für Lagersttättenforschung, H. 40, 129 S., Berlin. .

    Fiveg, M. P., 1973, Gases in salts of Solikamsk deposit (in Russian): Trudi VNIIG 64, 62-63.

    Frantzen, W., 1894, Bericht über neue Erfarungen beim Kalibergbau in der Umgebung des Thüringer Waldes: Jb. kgl. preuB, geol. L.-A. u. Bergakad., v. 15, p. 60-61.

    Freyer, H. D., and K. Wagener, 1975, Review on present results on fossil atmospheric gases trapped in evaporites: pure and applied geophysics, v. 113, p. 403-418.

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

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

    Gropp, 1919, Gas deposits in potash mines in the years 1907-1917 (in German): Kali and Steinsalz, v. 13, p. 33-42, 70-76.

    Headlee, A. J. W., 1962, Hydrogen sulfide, free hydrogen are vital exploration clues: World Oil, Nov, 78-83.

    Herrmann, A. G., and B. J. Knipping, 1993, Waste Disposal and Evaporites: Contributions to Long-Term Safety: Berlin, Heidelberg, Springer, 190 p.

    Jockwer, N., 1984, Laboratory investigations on radiolysis effects on rock salt with regard to the disposal of high-level radioactive wastes: McVay, G. L. Scientific basis for nuclear waste management Vii. Battelle, Pac. Northwest Lab., Richland, Wa, United States. Materials Research Society Symposia Proceedings, v. 26, p. 17-23.

    Knabe, H.-J., 1989, Zur analytischen Bestimmung und geochemischen Verteilung der gesteinsgebundenen Gase im Salinar (Concerning the analytical determination and geochemical distribution of rock-bound gases in salt): Zeitschrift für Geologische Wissenschaft, v. 17, p. 353-368.

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

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

    Marchant, L. C., 1966, Nitrogen gas in five oilfields on the Nesson anticline: US Bureau Mines, Report Invest., no. 6848.

    Molinda, G. M., 1988, Investigation of Methane Occurrence and Outbursts in the Cote Blanche Domal Salt Mine, Louisiana US Bureau of Mines Report of Investigation No. 9186, 31 p.

    Nesmelova, Z. N., and L. G. Travnikova, 1973, Radiogenic gases in ancient salt deposits: Geochemistry International, v. 10, p. 554-555.

    Panno, S. V., and P. Soo, 1983, An evaluation of chemical conditions caused by gamma irradiation of natural rock salt.: Brookhaven National Laboratory Report NUREG-33658.

    Potter, J., M. G. Siemann, and M. Tsypukov, 2004, Large-scale carbon isotope fractionation in evaporites and the generation of extremely 13C-enriched methane: Geology, v. 32, p. 533-536.

    Savchenko, V. P., 1958, The formation of free hydrogen in the earth's crust, as determined by the reducing action of the products of radioactive transformations of isotopes: Geochemistry (Geokhimiya)

    Schatzel, S. J., and D. M. Hyman, 1984, Methane content of Gulf Coast domal rock salt, United States Dept. of the Interior, Bureau of Mines Report of Investigation, No 8889, 18 p.

    Schoell, M., 1988, Multiple origins of CH4 in the Earth: Chemical Geology, v. 71, p. 1-10.

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

    Siemann, M. G., and B. Ellendorff, 2001, The composition of gases in fluid inclusions of late Permian (Zechstein) marine evaporites in Northern Germany: Chemical Geology, v. 173, p. 31-44.

    Smetannikov, A. F., 2011, Hydrogen generation during the radiolysis of crystallization water in carnallite and possible consequences of this process: Geochemistry International, v. 49, p. 916-924.

    Tikhomirov, V. V., 2014, Molecular nitrogen in salts and subsalt fluids in the Volga-Ural Basin: Geochemistry International, v. 52, p. 628-642.

    Uerpmann, E. P., and N. Jockwer, 1982, Salt as a Host Rock for Radioactive Waste Disposal: In: Geological Disposal of Radioactive Waste: Geochemical Progress. Paris, France: Organization for Economic Cooperation and Development, Nuclear Energy Agency.

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

    Vovk, I. F., 1978, On the source of hydrogen in potassium deposits: Geochem. Int., v. 15, p. 86-90.

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


     

    Gases in Evaporites; Part 1 - Rockbursts and gassy outbursts

    John Warren - Monday, October 31, 2016

    The next three articles discuss gases held within salt and is an attempt to address the following questions; 1) What is the scale and location of known rock-bursts/gas-outbursts in salt rock 2) Where do gases reside in a salt mass at the micro- and meso-scale? 3) What are the gases held in salt? 4) How are gassy salts distributed across various salt deposits across the world (macro-scale) and what are the lithological associations? Topics 1 and 2 are the main focus of the first article, topic 3 mostly in the second, while topic 4, where do gases held in salt generate and reside at the scale of a salt mass or salt bed
    is the focus of article 3. Along the way, we shall also discuss whether some of the encapsulated gases in salt can be considered samples of the ambient atmosphere that have been held in brine inclusions since the salt bed was first precipitated? And, as a corollary, we will come to a discussion of how did some of the occluded gases first enter or remobilize through the salt mass during the long history of burial and salt flow (halokinesis) experienced by all ancient evaporite units?


    Gases in evaporites can create problems

    Various gases such as, carbon dioxide, nitrogen, methane, hydrogen and hydrogen sulfide, can occur in significant volumes in and around domal salt masses or bedded evaporite deposits, as seen in numerous documented examples in mines and drilling blowouts in Louisiana, New Mexico, Germany, Poland and China (Figures 1, 2; Table 1). Gases are held in pressurized pockets in the salt that, if intersected, can create stability and safety problems during an expansion of operations in an active salt mine or during petroleum drilling, especially if the pockets contain significant levels of toxic or flammable gases, sufficient to drive rockbursts or gassy outbursts into the adjacent opening. A gas outburst (or rockburst) is defined as an unexpected, nearly instantaneous expulsion of gas and rock salt from a mine production face, normally resulting in an expanded open cavity in the salt. Outburst cavity shapes are generally metre- to tens of metre-scale combinations of conical, cylindrical, hemispherical, or elongated shapes with an elliptical cross section decreasing in diameter away from the opening (Figure 1). Many mapped examples in salt mines of the US Gulf coast have the shape of a cornucopia (Molinda, 1988).


    In the case of blowouts during oil-well drilling, there are two dominant styles of overpressured-salt encounters. The first, and the main focus in blowout discussions this article) is when gassy fluid outbursts occur internally in the salt unit as it is being drilled. Generally, this happens on the way to a test a deeper subsalt target, or less often on the way to test as series of intrasalt beds. Once intersected, pressures in such intrasalt pockets tend to bleed off and so decrease in hours to days as pressure profiles return to normal (Finnie, 2001; Warren 2016; Chapter 8). Providing the drilling system was designed to deal with short-term high-pressure outbursts, drilling can continue toward the target. The other type of gas outburst encountered when drilling salt is located in or near the periphery of a salt mass or bed, especially where the drill bit breaks out on the other side of a salt mass into a highly overpressured and fractured fluid reservoir. Such intersections allow the drill stem to connect with a large highly-overpressured volume of fluids, with the open fractures facilitating extremely high rates of fluid flow into the well bore. This type of breach draws on a significant fluid volume and a resulting blowout can continue unabated for weeks or months.

    Perhaps one the most impressive examples of this type of blowout, and the ability of evaporite unit to seal and maintain an overpressured subsalt pressurized cell, comes from the Alborz 5 discovery in Central Iran (Figure 2; Morley et al., 2013; Gretener, 1982; Mostofi and Gansser, 1957). Earlier wells testing the Alborz Anticline had failed to reach target due to drilling difficulties coming from “an extremely troublesome evaporite section[i] that continually menaced drilling and caused numerous sidetrack operations.” So difficult was drilling through this stressed Upper Red Formation salt unit that it had taken eight months for a previous well to drill through some 170 metres of evaporitic sediments to reach the Qom target. Later wells testing a Qom Fm. target, like Aran-1 to the south of the Alborz anticline, did not intersect thick stressed halite above the Qom Fm., only an anhydrite layer that perhaps was the dissolution residues of former halokinetic salt mass (pers obs.). The discovery well in the Alborz anticline (Alborz 5) had drilled through some 2296 m of middle to late Tertiary clastics and some 381 metres of Oligo-Miocene salines in the lower part of the Upper Red Formation and made up of siliciclastics, banded salt, anhydrite (Figure 3). On its way to the blowout point, the lower part of the well trajectory had penetrated normally to slightly overpressured dirty salt (halokinetic) and then penetrated some 5 cm into the fractured subsalt Qom Limestone (Oligo-Miocene). On August 26, 1956, the entire drill string and mud column were blown back out the hole and many metres into the air. At that time, the mud pressure was 55 MPa (8,000 psi) at a reservoir depth of 2700 m (8,800 ft), a pressure depth ratio of 20.5 kPa/m or 0.91 psi/ft (a lithostatic value!). Over 82 days, the well released 5 million barrels of oil and a large, but unknown quantity of gas before it self-bridged and the flow died on November 18, 1956. The temperature of the oil at the surface was measured at 115°C and at the time of the blowout the mud column density was 2.07 x 103 kg/m3 (129 lb/ft3)(see Figure 3). This type of subsalt overpressured gas occurrence illustrates salt’s ability to act as a highly effective seal holding back huge volumes of highly overpressured fluid. Associated occluding processes are discussed in an earlier series of Salty Matters articles dealing with salt as a seal, especially the article published March 13, 2016.

     

    Gassy salt (knistersalz)

    Much of the occluded gas in a salt body, prior to release into a mine opening or well bore, is held within inclusions within salt crystals or in intercrystalline positions between the salt crystals. Gas-entraining rock salt, was known from salt mines of Poland and in East Germany since the 1830s and described as knistersalz (literally translates as “crackling salt”). In many mines, walking on knistersalz releases gas as little popping sounds from underfoot. The pressure of the shoe adds a little more stress to an already gas-stressed fragment of salt (Roedder, 1972, 1984). Dumas (1830) first described such “popping salt from Wieliczka, Po­land, and concluded that gas was evolved, presumably from compressed gas inclusions, upon dissolving the salt. Further details on the occurrence were given by Rose (1839). As we shall see, this type of salt can cause serious mine accidents when large volumes of salt explo­sively and spontaneously decrepitate into the mine openings as rockbursts. Dumas (1830) and Rose (1839) found the released gas from "popping " salt in Germany to be inflammable. Bun­sen (1851, p. 251) found 84.6 % CH4 in the gas released during the dissolution of Wieliczka salt, while in many early mines in Germany the occluded gas phase is dominated by nitrogen or carbon dioxide (see Article 2). 

    Knistersalz will "pop" sporadically once placed in water, releasing pressurized gas bubbles as the salt matrix dissolves. This simple demonstration of gas presence is also the foundation for one method of determining the gas content of a rock salt sample (Hyman, 1982). The sometimes rather energetic "pops" that can occur as gases are released from a gas-enriched rock salt sample attest to the high pressures under which the gases are occluded. Pressures postulated in knistersalz can be near-lithostatic and even higher depending on local stresses, related to the low creep limits of rock salt, particularly around mine openings. According to Hoy et al. 1962, CO2-bearing gas mixtures in the knistersalz of the Winnfield salt dome (Louisiana, USA) is under a pressure of 490 - 980 bar (49 - 98 MPa) at 0°C. Similar values (500 - 1000 bar or 50 - 100 MPa) are given by Hyman (1982) for gas bubbles held in rock salt in various Louisiana salt domes. For example, during exploratory drilling in one such Louisiana salt dome, methane gas was released from the salt under a pressure of 62 bar (6.2 MPa) at a flow rate of 1.2 m3/hr (Iannachione et al., 1984). 

    Mining causes a pressure drop in the rock salt as it is extracted from a working face and such pressure drops can change the phase of a fluid occluded in salt, or change the solubility of a gas dissolved in such a fluid. Carbon dioxide, in particular, is susceptible to a phase change because its critical point is close to some ambient mining conditions. As long as CO2 is present above 1070 psi (7.4 MPa) and below 31°C (88°F; critical point), it will be in a liquid phase. Such conditions are not typical in salt mines in the US. However, CO2 generally exists as a liquid in rock salt in many German potash mines (Gimm, Thoma and Eckart, 1966). When mining drops the pressure (from lithostatic to near atmospheric) the CO2 phase will change to a gas, causing abrupt expansion. The sudden change also results in a 5 to 6°C cooling, as measured in regions near large outbursts (Wolf, 1966). The solubility of gases dissolved in brine also changes when mining. For example, the solubility of methane in brine is extremely low at atmospheric pressure and so is released as gas bubbles from a brine issuing from rock salt fissures upon mining, as observed in a number of US Gulf Coast salt mines (Iannacchione and Schatzel, 1985).

    Pressures released during an outburst result in velocities at the outburst throat which can be very large and locally approach sonic velocities (Ehgartner et al., 1998). Velocities of more than 152 m/sec (500 ft/s) have been recorded in vertical airways some distance from rockbursts in Germany. Velocities at the rockburst site would be even higher. Narrow throat characteristic of some rockbursts can result in throttling. However, associated pressure waves are not strong enough to cause the observed levels of equipment destruction, since they are of a magnitude similar to those found in blasting. Rather, observed damage associated with rockbursts is due to flying debris in the pressure wave as the quantities of rock thrown out by the burst have high kinetic energy (Wolf, 1966). 

    Given the relatively impermeable nature of bedded and halokinetic salt, occluded gases generally are not released from their containment unless mining or drilling activities intercept (1) a gas-filled fissure zone, an area where the voids between the salt crystals are interconnected, (2) a mechanically unstable zone of gas-enriched salt that disaggregates, releasing its entrained gases (a blowout), or (3) as the mine or the drill bit enters some other relatively permeable geologic anomaly (Kupfer, 1990).

      

    Gassy outbursts and rockbursts in salt

    Outbursts are documented in the U.S., Canada, and throughout northern Europe in various salt and potash mines (Figure 2; Table 1). The salt domes of northern Europe and the US Gulf coast are in particular loaded with pockets of abundant gas inclusions (Ehgartner et al., 1998). Many dangerous pockets of methane and H2S were intersected during the opening of shafts into the domes of Zechstein salts in the Saxony region, Germany and several early potash mines in the area were abandoned because of problems caused by rockbursts and associated gas outflows (Gropp, 1919; Löffler, 1962; Gimm, 1968). Before the current practice of evacuating any gas-prone salt mine prior to blasting, many fatalities resulted from such gas and rock outbursts (Table 1). A significant portion of the deaths was due to secondary factors (post-rockburst), such as methane fires, CO2 suffocation, and H2S poisoning (Dorfelt, 1966). Even with the practice of mine evacuation prior to blasting, outburst gases have in some cases filled a mine, blown out of the mine shafts, and caused fatalities at the surface. This was the case in Menzengraben in 1953, as heavier-than-air CO2 gas, released by a blasting-induced rockburst, blew out of the mine shafts for 25 minutes and flowed downhill into a nearby village, where it ponded and ultimately suffocated 3 people in their sleep (Hedlund, 2012)

    The most frequent and largest rockbursts and gas outflows from subsurface salt occurred in the Werra mining district in former East Germany. Gimm and Pforr (1964) report that rockbursts occurred every day in the Werra region. If one also includes potash mines in the Southern Harz region, more than 10,000 outbursts were recorded up till the 1960s in the German salt mines (Dorfelt, 1966). The 1953 Menzengraben(Potash Mine No. 3) rockburst blew out some 100,000 metric tons of fractured rock salt (approximately 1.6 million cubic feet). This may well be the world’s largest rockburst in terms of cavity size (Gimm, 1968). In an earlier incident in the same region in 1886, the shaft Aschersleben II was flooded with water and gas as it reached a depth of 300 m. A pilot hole drilled from the temporary bottom of the shaft into the underlying Stassfurt rock salt, hit a gas pocket, releasing a combination of H2S—CH4—N2 gases, which then escaped under high pressure for some two hours carrying with it an NaCl brine to the height of a “house” above the shaft floor before the outflow abated. The shaft was abandoned (Baar, 1977).

    In 1887 the shaft Leopoldshall III, at Stassfurt, had been sunk through the caprock, and into the Zechstein salt to a total depth of 412 m subsurface, when it hit a gas pocket containing H2S, and four miners were killed by gas escape. Subsequently, in 1889, seven more were killed during shaft construction in the same mine. In 1895, a large volume of CO2 was released from rock salt at a depth of 206 m during the sinking of the Salzungen shaft (Gimm 1968, p. 547). Numerous other outbursts of gas occurred in the same Werra-Fulda district with most mines operating at depths greater than 300 meters, with outbursts responsible for a number of deaths both below and above ground. According to Gimm (1968, p. 547), since 1856, toxic gases were also encountered during the sinking of a number of other shafts in the Stassfurt area. Gropp (1918) documents 106 gas occurrences in German potash mines for the period 1907 to 1917, at depths of ≈300 meters and greater. Many of these gassy encounters caused casualties, particularly in salt dome mines of the Hannover area where several of the potash mines were abandoned due to dangerous gas intersections (Barr, 1977).

    Less severe examples of gas outbursts and rockbursts transpired in other salt mines around the world (Figure 2). More than 200 gas outbursts with ejected rock salt volumes up to 4500 tons have occurred in the Upper Kama potash deposits of Russia (Laptev and Potekhin, 1989). Baltaretu and Gaube (1966) reported sudden gassy outbursts in potassium salt deposits in Rumania. Outbursts in Polish salt mines were noted by Bakowski (1966). Potash mines in England and Canada also exhibited outbursts (Table 1; Schatzel and Dunsbier, 1988) with the most recent case being a gassy outburst that caused a fatality in the Boulby mine in July 2016.

    Major rockbursts, tied to methane releases, occurred in Louisiana in four of the 5-Island salt mines exploiting the crestal portions of subcropping salt domes (Belle Isle, Cote Blanche, Weeks Island, and Jefferson Island) with the exception of Avery Island. Gassy outbursts, of mostly CO2, also occurred at the Winnfield salt mine, Louisiana (Table 1). Rockburst diameters range from a few inches up to over 50 ft. Cavity heights range from several inches to several hundred feet. Smaller rockburst and cavities in the Five-Island mines were ordinarily not reported (Kupfer,1990). Only the more gas-inclusion-rich salt decrepitates in these mines, and the concave curvatures of the walls are such that the resulting slight additional confining force from the concavity keeps the remaining salt from decrepitating further (Figures 1, 4; Roedder, 1984).


    The larger outburst shapes tended to be cornucopian in shape, whereas the shorter ones were conchoidally shaped with symmetrical dimensions (Figure 4). Outbursts approaching several hundred feet high were documented in the Jefferson Island and Belle Isle mines. The disaster at Belle Isle mine in 1979, in which five miners died, proved that high-pressure methane in large quantities could be released near instantaneously during a rockburst. It was estimated that more than 17,000 m3 (600,000 ft3) of methane was emitted by the 1979 outburst (Plimpton, et al.,1980). At the former Morton mine at Weeks Island, an even larger gas emission apparently occurred in connection with a rockburst. It was estimated that as much as 1,020 m3 (36,100 ft3) of salt was released as 1.4 million m3 (50 million ft3) of gas filled the former Morton Mine (MSHA,1983). If the limited number of sample points represent a well-mixed mine atmosphere, the gas alone would occupy approximately 17,000 m3 (600,000 ft3) in the salt at lithostatic pressure (Plimpton, et al.,1980).

    Outbursts occurred during mining in all three of the mines at Weeks Island - the “old” Morton mine (the site of the now abandoned U.S. Strategic Petroleum Reserve), the Markel mine, and the “new” Morton mine. Perhaps the largest outburst at the “new” Morton mine occurred on October 6, 1982, in the southwest corner of the 1200-ft level, close to the edge of the dome. A balloon with an attached measuring string is typically used to estimate the height of the major vertical outbursts. A balloon went up more than 30 m (100 ft) into an outburst some 10 m (35 ft) wide (MSHA, 1983). Outbursts in the old Morton mine occurred only in the larger lower level (-800 ft) of the two level mine outside the vertically projected boundary of the upper (-600 ft) level. A similar trend was noted at Jefferson Island where no gas outbursts occurred in the upper level of the mine. The outbursts observed at the Jefferson Island mine were in the same relative position at both the 1300-ft and 1500-ft levels. This is attributed to the near vertical orientation of a very gassy zone of salt (Iannacchione, et al., 1984). Structural continuity (banding) is nearly vertical in many Gulf coast salt dome diapirs, except where the top of the dome has mushroomed. As a result, horizontal runs of outbursts have reportedly been small, and unlikely to connect caverns separated by 100 ft or more (Thoms and Martinez, 1978.).

    The geometry of the gas pockets is not well known. Thoms & Martinez (1978) argued that prior to the rockburst the gas is concentrated in vertical, cylindrical zones or pockets, which were created and elongated by the upward movement of the salt. Mapping in the Five-Island mines shows that the rockbursts are often aligned along structural trends . At Winnfield (Hoy et al., 1962), and possibly at Belle Isle (Kupfer,1978), the outbursts occur close to the edge of the dome. In other cases (e.g., Cote Blanche and Belle Isle) the outbursts follow structural trends such as shear zones within the dome (Kupfer, 1978). In all cases, there is an association between methane gas occurrence and other anomalous features such as dirty salt, sediment inclusions and oil or brine seeps (see article 2).

    Rockbursts are not limited to gassy intersections in domal salt. High-pressure pockets of inert gas, typically nitrogen, are documented in bedded potash mines (Carlsbad, NM), and combustible gases (methane)and fluids (brine and oil) in potash mines in Utah (Djahanguiri, 1984). The Cane Creek potash mine (Utah). exploiting halokinetic salts sandwiched by the bedded formations of the Paradox Basin, had a history of fatalities and extensive equipment damage as a result of rockbursts (Westfield, et al., 1963). In contrast, no gassy outbursts were reported during the construction and operation of the Waste Isolation Pilot Plant in the bedded salts of southeastern New Mexico. During WIPP construction, routine drilling ahead of the road-header checked for gas, but found very little (Munson, 1997).

    In my opinion, some gas pockets in domal salt can be related to the diagenetic process creating a caprock, where metahne and H2S are typical byproducts. In others, the gases are related to the burial history and recrystallisation (partially preserving primary nitrogen), while in yet others, the gas release is related to heating and alteration especially of the hydrated salts (hydrogen) and associated fracturing related to igneous intrusion (CO2). In some cases, gases were encountered in fracture systems of cap anhydrite close to the top or edge of the salt dome; such fracture systems apparently had connections to the groundwater as the gassy outbursts were followed by water of varying salinity. In other cases, fracture systems headed by a gas cap connected the expanding mine to overlying aquifers and ongoing salt dissolution was facilitated. But, in most cases of rockburst located within the interior of a salt mass, the majority of the intersected gas pockets are isolated, as once the burst occurred most cavities tended to receive little if any subsequent recharge, so gas and brine outflow rates tended to decrease to zero across hours to days (Loffler, 1962). The relationship between the type of gas, its position in the salt, and possible lithological associations are documented and discussed in detail in articles 2 and 3.

     

    The physics that drives rock and gas outbursts in an expanding mine-face or shaft is relatively straightforward. In the petroleum industry, it constitutes a process set that is already well documented as the cause of many salt-associated gassy blowouts such as Alborz 5 (Figure 3; Warren, 2016 – Chapter 8 for detail on pressure distribution in and about a salt mass). Oilfield blowouts associated with salt occur when pore pressures in fluids in the drilled rock approach or even exceed lithostatic and the weight of mud in the approaching borehole is not sufficient to hold back this overpressured fluids entering and escaping up the borehole (Figure 3). Spindletop and other famous caprock blowouts in the early days of salt dome drilling in Texas and Louisiana are famous examples of this process (Figure 5). Ehgartner et al. (1998) argue that the same pressure release occurs as an expanding mine face approaches a gassy zone in the mined salt. Once the pressure is reduced by the approach of the mine face, the release of gas formerly held in place by lithostatic pressure within a homogenously stressed salt mass will release, the enclosing rock salt will lose cohesion and so a rockburst (gas outburst) occurs (Figure 6).

     

    How is the gas held and distributed within salt at the micro and mesoscale (microns to metres)?

    That free gas and gas in inclusions occur simultaneously in salt masses is undeniable, numerous examples come from salt mines and salt cores (Table 1). Gases are held in evaporite salts in three ways (Hermann and Knipping, 1993); 1) Crack- and fissure-bound gases, 2) Mineral-bound gases, a) intracrystal, b) intercrystal, and 3) Absorption-bound gases. Type 1 occurrences, as the name suggests, are defined by gas accumulations in open fractures and fissures, typically in association with brine. Some occurrences are tied to pressurized aquifers, others are isolated local accumulations within the salt. Intracrystal gas occurs as bubbles, some elongate, some rounded in brine inclusions that are fully enclosed within a crystal (typically halite). At the micro (thin section-SEM scale), intracrystalline gases typically form as a few to aggregates of small bubbles, arranged along crystallographic axes or planes, with bubble diameters in the range 1 to 100 µm. Intercrystalline gases occupy the boundary planes of crystals in contact with one another, that is intercrystalline gases occupy polyhedral porosity. According to Hermann and Knipping (1993), up to 90% of the mineral-bound CO2gas mixtures in the salt rocks of the Werra-Fulda mining district is likely intercrystalline, and the remaining 10% is intracrystalline. Absorption bonding is likely an independent form of gas fixation in salt. Adsorptive bonding describes the ability of solids, especially clays, and crystalline compounds to store gas on their surfaces in the form of layered molecules, most would term this a subset of microporous gas storage in a shale.


    [i]The stresses in and around and in salt structures can be high and troublesome to stabilize, even today and is an indication of the ongoing dynamic nature of salt flow and recrystallisation in the subsurface.Therefore, if borehole fluid pressure is lower than salt strength during drilling, stress relaxation may significantly reduce open-hole diameters. In some cases, relaxation causes borehole restrictions even before drilling and completion operations are finished and casing has been set.

    References 

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