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).

Silica mobility and replaced evaporites: 3 - Archean cherts

John Warren - Sunday, August 28, 2016

Introduction

The two previous articles on silica mobility in evaporitic settings emphasised Phanerozoic examples and discussed silica textures largely tied to the replacement of sulphate evaporite nodules. This article will extend the time frame back to the Archean and also discuss scale controls on massive marine-derived evaporite beds in the early earth. The next article after this focuses on the Proterozoic. In order to extend our discussion into saline Precambrian successions, we must consider changes in ionic proportions and temperatures of the world’s oceans that this involves, and also include the background context of biological evolution of silica-extracting organisms.

Chert deposits clearly preserve a record of secular change in the oceanic silica cycle cross the Precambrian and the Phanerozoic (Maliva et al., 2005), with the chert nodule-evaporite association most obvious in alkaline brine-flushed areas in Phanerozoic sediments (previous 2 articles). Many silicified Phanerozoic evaporite examples co-occur with significant volumes of salts deposited in marine-fed megahalite and megasulphate basins. The evolutionary radiation of silica-secreting organisms across a deep time background is reflected in the transition from abiogenic silica deposition, characteristic of marine and nonmarine settings in the Archean and Proterozoic eons, to the predominantly biologically-controlled marine silica deposits of the Phanerozoic.

Silica levels in the Archean ocean

Estimated silica concentration in Precambrian seawater is 60 ppm SiO2 or more, while silica concentration of much of the modern ocean is controlled by silica-secreting organisms at values of 1 ppm or less to a maximum of 15 ppm (Perry and Lefticariu, 2014). There is no conclusive fossil evidence that such organisms were present in the Precambrian in sufficient abundance to have had a significant influence on the silica cycle, although some later Neoproterozoic protists likely had scales that were siliceous, and Ediacaran sponges certainly produced siliceous spicules. This contrasts with the Phanerozoic, during which the appearance of radiolaria and diatoms changed the locus of silica precipitation (both primary and replacement) from the peritidal and shallow shelf deposits characteristic of the Neoproterozoic, Mesoproterozoic, and much of the Paleoproterozoic, to the deep ocean biogenic deposits since the mid to late Phanerozoic. Comparative petrography of Phanerozoic and Precambrian chert shows an additional early change in nonbiogenic chert deposition occurred toward the end of the Paleoproterozoic era and was marked by the end to widespread primary and early diagenetic silica precipitation in normal marine subtidal environments (Table 1; ca. 1.8 Ga Maliva et al., 2005). Interestingly, the Precambrian transition corresponds to the onset of a plate tectonic regime resembling that of today (Stern, 2007). It was also the time when sulphate levels in the world’s oceans had risen to where gypsum became a primary marine evaporite, as evidenced by large silicified anhydrite nodules (with anhydrite relics) in the late Paleoproterozoic Mallapunyah Fm in the McArthur Basin, Australia (Warren, 2016). Paleoproterozoic early diagenetic “normal marine” cherts generally formed nodules or discontinuous beds within carbonate deposits with similar depositional textures. It seems these “normal marine” cherts formed primarily by carbonate replacement with subsidiary direct silica precipitation. In saline settings cauliflower cherts are also obvious from this time onwards.

 

Some of these Paleoproterozoic peritidal cherts were associated with iron formations and are distinctly different from younger cherts and appear to have formed largely by direct silica precipitation at or just below the seabed. These primary cherts lack ghosts or inclusions of carbonate precursors, have fine-scale grain fracturing (possibly from syneresis), exhibit low grain-packing densities, and are not associated with unsilicified carbonate deposits of similar depositional composition (Perry and Lefticariu, 2014). Cherts in some Paleoproterozoic iron formations (e.g., the Gunflint Formation, northwestern Lake Superior region) are composed of silica types similar to those in Phanerozoic sinters (e.g., the Devonian Rhynie and Windyfield chert sinters, Scotland, both of which preserved fine-scale cellular detail of Devonian plants, fungi and cyanobacteria, as well as elevated gold levels in the fault feeder system). Such “normal marine cherts lie outside the evaporite focus of this series of articles and for more detail the reader is referred to Perry and Lefticariu, 2014 and references therein.

Archean crustal tectonics and silicification of world-scale evaporites

Archean evaporites were not deposited as saline giants within subsealevel restricted basins created by sialic continent-to-continent proximity setting. In the greenstone terranes that typified the early Archean these tectonic settings simply could not yet exist (Warren, 2016, Chapter 2). Stern (2007) defines plate tectonics as the horizontal motion of Earth’s thermal boundary layer (lithosphere) over the convecting mantle (asthenosphere), and so it is a world-scale system or set of processes mostly driven by lithosphere sinking (subduction pull). He argues that the complete set of processes and metamorphic indicators, associated with modern subduction zones, only became active at the beginning of the Neoproterozoic (≈ 1 Ga). Stern interprets the older record to indicate a progression of tectonic styles from active Archaean tectonics and magmatism (greenstone belts), to something akin to modern plate tectonics at around 1.9 Ga (Figure 1). If so, then modern world-scale plate tectonics only began in the early Neoproterozoic, with the advent of deep subduction zones (blueschists) and associated powerful slab pull mechanisms. Flament et al. (2008) argue that the world’s continents were mostly flooded (mostly covered with shallow ocean waters) until the end of the Archaean and that only 2–3 % of the Earth’s area consisted of emerged continental crust by around 2.5 Ga (aka “water-world”).


It is very likely that the Archaean Earth’s surface was broken up into many smaller plates with volcanic islands and arcs in great abundance (greenstone terranes). Small protocontinents (cratons) formed as crustal rock was melted and remelted by hot spots and recycled in subduction zones. There were no large continents in the Early Archaean, and small protocontinents were probably the norm by the MesoArchaean, when the higher rate of geologic activity (hotter core and mantle) prevented crustal segregations from coalescing into larger units (Figures 1 and 3 ). During the Early-Middle Archaean, Earth’s heat flow was almost three times higher than it is today, because of the greater concentration of radioactive isotopes and the residual heat from the Earth’s accretion, hence the higher ocean temperatures (Figure 2; Eriksson et al. 2004). At that time of a younger cooling earth there was considerably greater tectonic and volcanic activity; the mantle was more fluid and the crust much thinner. This resulted in rapid formation of oceanic crust at ridges and hot spots, and rapid recycling of oceanic crust at subduction zones with oceanic water cycling through hydrothermally active zones somewhat more intensely than today (Zegers and van Keken 2001; Ernst 2009; Flament et al. 2008).


In the Pilbara craton region of Australia significant crustal-scale delamination occurred ≈ 3.49 Ga, just before the production of voluminous TTG (tonalite, trondhjemite, and granodiorite) melts between 3.48 and 3.42 Ga and the accumulation sonic evaporites (Figure 3; Zegers and van Keken 2001). Delamination resulted in rapid uplift, extension, and voluminous magmatism, which are all features of the 3.48–3.42 Ga Pilbara succession. As the delaminated portion was replaced by hot, depleted mantle, melts were produced by both decompressional melting of the mantle, resulting in high-MgO basalts (this is the Salgash Subgroup in the Pilbara craton), and melting of the gabbroic and amphibolitic lower crust, so producing TTG melts. Partial melting of the protocrust to higher levels can be envisaged as a multistep process in which heat was conducted to higher levels and advection of heat occurs by intrusion of partial melts in subsequently higher levels (indicated by purple arrows in Figure 3). TTG melt products that were first intruded were subsequently metamorphosed and possibly partially melted, as can be inferred from the migmatitic gneisses of the Pilbara. This multistep history explains the complex pattern of U-Pb zircon ages of gneisses and granodiorites found within the Pilbara batholiths and the range in geochemical compositions of the Pilbara TTG suite.


Key to the formation of early Archaean evaporites, which indicate a sodium bicarbonate ocean at that time (see next section), is the observation that crustal delamination and the creation of TTG melts led to up to 2 km of crustal uplift (Figure 3). This would have driven some regions of what were submarine sedimentary systems into suprasealevel positions in the Archean waterworld, so creating the potential for hydrographically-isolated subsealevel marine seepage sumps in those portions of the uplifted crust above the zones of delamination. It also explains the centripetal nature of much shallow marine sedimentation of that time. This is cardinal at the broad tectonic scale when comparing the distribution of Archaean and Phanerozoic evaporites (Warren, 2016). Most Archaean evaporite are remnants that are pervasively silicified and underlain by layered igneous complexes, which were dominant across the greenstone seafloor and are associated with bottom-nucleated baryte beds tied to hydrothermal seeps.

Felsic protocontinents (suprasealevel cratons) hosting silicified evaporite remnants probably formed atop Archaean hot spots from a variety of sources: mafic magma melting more felsic rocks, partial melting of mafic rock, and from the metamorphic alteration of felsic sedimentary rocks. Although the first continents formed during the Archaean, rock of this age makes up only 7% of the world’s current cratons; even allowing for erosion and destruction of past formations, evidence suggests that only 5–40 % of the present volume continental crust formed during the Archaean. 

Archean oceans and silicified sodic evaporites 

Chert styles and occurrences in saline settings across deep time clearly show that we cannot carry Phanerozoic silica mobility models in saline lacustrine or CaSO4 evaporite associations directly across time into the deep Precambrian. Rather, comparisons must be made in a context of the evolution of the earth’s atmosphere and associated ocean chemistry, both of which are in part related to the earth's tectonic evolution.

Levels of early Archaean sulphate in the world ocean were probably less than a few percent of the current levels and probably remained so until the evolution of an oxygen-reducing biota into the Proterozoic (Habicht and Canfield 1996; Kah et al. 2004; Warren, 2016). Grotzinger and Kasting (1993) argue that high levels of atmospheric CO2 meant HCO3/Ca ratios were much higher in the Archaean and the Paleoproterozoic oceans than today. All the calcium in seawater was deposited as marine cement-stones and other alkaline earth precipitates well before bicarbonate was depleted and there was no Ca left over to precipitate as gypsum. The early Archaean waterworld ocean was likely a Na–Cl–HCO3 sea, and not the Na–Cl ocean of today (Kempe and Degens 1985; Maisonneuve 1982). This early Archaean hydrosphere had a chemistry similar to that found in modern soda lakes like Lake Magadi and Lake Natron (pathway I brines) and hence the term “soda-lake oceans.” This rather different marine brine chemistry would have precipitated halite and trona/nahcolite, not halite/gypsum. It probably meant that if gypsum/anhydrite did ever precipitate directly from evaporating Archaean seawater it did so only in minor amounts well after the onset of halite precipitation.

 

The case for nahcolite (NaHCO3) as a primary evaporite (Figure 4a-d), along with halite, in the 3.42 Ga rocks of the Barberton greenstone belt was first documented by Lowe and Fisher-Worrell,1999), both the nahcolite and the halite are silicified. Beds of these silicified sodic evaporite define 5 types of precipitates: (1) large, pseudohexagonal prismatic crystals as much as 20 cm long that increase in diameter upward; (2) small isolated microscopic pseudohexagonal crystals; (3) small, tapering-upward prismatic crystals as much as 5 cm long; (4) small acicular crystallites forming halos around type 1 crystals; and (5) tightly packed, subvertical crystal aggregates within which individual crystals cannot be distinguished. Measurement of interfacial angles between prism and pinacoid faces on types 1 and 2 crystals show four interfacial angles of about 63° and two of about 53°. The morphologies and interfacial angles of these crystals correspond to those of nahcolite, NaHCO3 (Figure 4e). There is no clear evidence for the presence of gypsum in these beds. Sugitani et al. (2003) reported silicified nahcolite (the high CO2 form of sodium carbonate salts; see Warren, 2016, chapter 2) in ≈ 3.2 Ga rocks in the northern part of the Eastern Pilbara block, Western Australia (Figures 4, 5). Coarse, upward-radiating, silicified evaporite crystals in the ca. 3.47–3.46 Ga Strelley Pool Chert (Lowe 1983) show the same habit, geometry, and environmental setting as silicified nahcolite pseudomorphs in the Kromberg Fm. in the Barberton belt, South Africa, and also probably represent silicified NaHCO3 precipitates (Lowe and Tice 2004). Depositional reconstructions in both regions imply a strong hydrothermal association to the silicification of the evaporites in both regions as do bottom-nucleated baryte layers that define seafloor seeps fed by hydrothermal waters moving up faults (Figure 4f; Nijman et al., 1999; van den Boorn et al., 2007).

The pervasive presence of type 1 brines as ocean waters in the early Archean, along with elevated silica levels in most surface ocean waters, compared to the Phanerozoic, implies a significant portion of Archean cherts may also have had a volcanogenic sodium silicate precursor, much like the silicification seen in the modern African rift valley lakes (Eugster and Jones, 1968 and article 1 in this series of articles on silica mobilisation). So in order to decipher possible evaporite-silicification associations we must include aspects of hydrothermal fluid inherent to the Archean, as well as the likely higher surface temperatures that typified highly reducing (anoxic) waters of the early Archean ocean (Figure 3).


Archean evaporite deposition and silicification

Worldwide, the most widespread Archaean depositional environment, especially in early Archaean greenstone terranes, was the mafic plain environment (Condie 2016; Lowe 1994). In this setting, large volumes of basalt and komatiite were erupted to form widespread mostly submarine mafic plains characteristic by ubiquitous pillow structures in the lava interlayers. A second significant sedimentary environment was a deepwater, nonvolcanic setting, where chemical and biochemical cherts, banded iron formation, and carbonate laminites were deposited. The typical lack of evaporite indications in these mostly deepwater sediments indicates an ongoing lack of hydrologic restriction while the sediments were accumulating (waterworld association). The third association, a greywacke-volcanic association becomes more widespread in later Archaean greenstones, which typically sit stratigraphically atop mafic plain units. This association is composed chiefly of greywackes and interbedded calc-alkaline volcanics, hydrothermal precipitates and, in some shallower parts, silicified evaporites. It was perhaps mostly an island arc system and dominantly more open marine as it typically lacks widespread indicators of former marine evaporites. However, more locally it also preserves fluvial and shallow-marine detrital sediments, that were probably deposited locally in Archaean pull-apart basins, and associated with mineralogically mature sediments (quartzarenites, etc.). These more continental associations typified the shallowest to emergent parts of these continental rifts.

Unlike the other two early Archean  greenstone terranes this third terrane type can in places, such as the Pilbara, be tied to sedimentary indicators of a surfacing seafloor, indicated by particular chert and volcaniclastic layers showing mud cracks, wave ripples, tidalites interbedded with hyaloclastics, vuggy cherts, banded iron formations, carbonates and thick now-dissolved and altered type 1 evaporite masses (breccias), perhaps residues of beds formerly dominated by sodium carbonate and halite salts (Figure 5). The Warrawoona Group, preserves many such silicified examples that retain fine detail of primary textures such as mud cracks, oolites, and evaporite crystal casts and pseudomorphs, all indicating shallow-water to emergent deposition atop the mafic plain. In terms of crystal outlines there few if any casts of possible gypsum crystals, more typically, they indicate bladed pseudo-hexagonal, bottom-nucleated nahcolite, trona and in some instances, halite pseudomorphs (Figure 4).

Depositionally, to acquire the needed high salinities, these cherty evaporite units must have risen, at least locally, to shallow near-sealevel depths and at time become emergent, allowing local hydrographically-isolated lacustrine/rift evaporite subaqueous deposition or precipitation of local seepage drawdown salts. Associated primary-textured carbonate and baryte layers interbedded with the cherts are typically minor, bottom-nucleated baryte textures that may likely indicate hydrothermal vent deposits (Figure 4f; Nijman et al., 1999).

Inherent high solubility of any sodium bicarbonate and/or halite salts in what was a hotter burial system, more strongly influenced by hydrothermal circulation than today, meant most of the original sodic evaporite salts were not preserved, unless silicified in early burial. But their presence as silicified pseudomorphs in less-altered greenschist terranes intercalated with volcanics (Figure 4), such as in the Yilgarn, Pilbara and Kaapvaal cratons, clearly shows two things; (1) at times in the early Archaean waterworld there was sufficient hydrographic restriction to allow marine sodian carbonate and sodian chloride evaporites to form and (2) this marine restriction/seepage inflow was probably driven by ongoing volcanism and associated uplift, with evaporites restricted to particular basinwide stratigraphic indicator levels. In the East Pilbara, the early Archaean evaporite stratigraphic level is the Strelley Pool chert, in the Warrawoona group (Figure 5). This is also the level with some of the earliest indications of cellular life-forms (Wacey 2009).

For the original sodic evaporites, it marks the hydrological transition from open marine seafloor to a restricted hydrographically-isolated marine-fed sump basin, surrounded by granite-cored highs with the required uplift likely driven by delamination at the level of the mantle transition (Figures 1 and 3). Given the intimate association of chemical sediments to volcanism in early Archaean greenstone basins, and the sodium bicarbonate ocean chemistry then, compared to the Phanerozoic evaporite hydrochemistries, we can expect a higher proportion of CO2 volatilisation, a higher boron content (tourmalinites) in early Archaean, and a higher level of silicification.

Is the present the key to the past?

The study of silicified evaporites and associated sediments, formed in the early stages of the Earth’s 3.5 Ga sedimentary record, shows that not only has ocean chemistry evolved (see August 24, 2014 blog), the earth’s lithosphere/ plate tectonic character has also evolved (Eriksson et al. 2013). The further back in time, the less reliable is the application of the current plate tectonic paradigm with its strongly lateral movements of crustal blocks and associated plate-scale evaporite basin controls. Phanerozoic evaporites, and the associated silicified sulphate nodules, define a marine-fed seep system where subsealevel continental rifts and continent-continent collision belts favour the formation of mega-evaporite basins (Warren, 2010). Instead, in a substantial portion of the earlier part of the 2 billion year earth history that is the Archaean, shows early-earth evaporite deposition was favored by hydrographic isolation created by strong vertical movement of earth’s crust related to upwelling mantle plumes and crustal delamination with more intense hydrothermal circulation and silicification. There is still no real consensus as to actual time when plate tectonics, as it operates today, actually began, but there is consensus that the present, in terms of plate tectonics, plate-edge collision and evaporite distribution, is not the key to much of the Archaean (Stern 2007; Rollinson 2007).

Uplift and the local accumulation of sodium carbonate Archean evaporites occurred in a depositional setting that was dominated by volcaniclastics,hydrothermal vents and extensional tectonics. Tectonic patterns in these settings have a strongly vertical flavor. In contrast, Phanerozoic salts formed from marine waters with a NaCl dominance with minor bicarbonate compared to calcium, and located mostly in subsealevel sumps formed at interacting sialic plate margins where the dominant tectonic flavor is driven the lateral movement of plates atop a laterally moving asthenosphere and the relative proportion of vilified salts is lower.

Whatever and wherever the onset of Archaean evaporite deposition, all agree that the mechanisms and aerial proportions world-scale plate tectonics were different in early earth history compared to the Phanerozoic. The current argument as to how different is mostly centred on when earth-scale plate tectonic processes became similar to those of today. Given much higher crustal heat flows, it is likely that hydrographically isolated subsealevel depressions, required to form widespread marine evaporites were more localized in the Archaean than today and were more susceptible to hydrothermal alteration, metamorphism and silicification. Appropriate restricted brine sumps would have tended to occur in magmatically-induced uplift zones atop incipient sialic segregations, with crestal subsealevel grabens, which were hydrographically isolated by their surrounds created by supra-sealevel uplift. Once deposited, the higher heat flow in Archaean crust and mantle would also have meant any volumetrically significant evaporites masses were more rapidly recycled, silicified and replaced via diagenetic and metamorphic processes than today.

Some authors have noted that there are no widespread marine evaporites in the Archaean and in the sense of actual preserved salts, this is true. But when one considers that the Archaean crust was much hotter than today and hydrothermal circulation was more active and pervasive, then widespread burial preservation of the primary salts seems highly unlikely. Even in the Neoproterozoic, lesser volumes of the original salt masses remain (Hay et al. 2006). The lack of preserved salts in earlier Precambrian strata is perhaps more a matter of great age, polycyclic metamorphic alteration and the typical proximity to shallow hydrothermal fluids in emergent evaporite forming regions of the Archean waterworld. However we must also ask if the onset of modern styles of plate tectonics also played a role in the relative absence of preserved saline giants in strata older than 1Ga, In the next article we shall look how cooling and the onset of sialic plate tectonics similar to today, altered the types, styles and distributions of silicified and other evaporite salts as the world's oceans moved toward a chemistry more akin to that of today.

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chert Zaragoza hydrological indicator base metal deep seafloor hypersaline anoxic basin collapse doline Pilbara silicified anhydrite nodules Belle Isle salt mine organic matter Stebnik Potash sepiolite mine stability vanished evaporite Lop Nur Musley potash Kara bogaz gol magadiite methanotrophic symbionts saline clay climate control on salt Paleoproterozoic Oxygenation Event carbon oxygen isotope cross plots Salar de Atacama water on Mars HYC Pb-Zn mass die-back gas in salt Bathymodiolus childressi eolian transport Schoenite flowing salt perchlorate Dead Sea karst collapse capillary zone lot's wife cauliflower chert geohazard Danakhil Depression, Afar dissolution collapse doline hydrohalite Evaporite-source rock association Pangaea lazurite Precambrian evaporites Deep Neutron Log halophile Lake Magadi jadarite Mesoproterozoic lapis lazuli salt leakage, dihedral angle, halite, halokinesis, salt flow, namakier Crescent potash Corocoro copper solikamsk 2 hectorite basinwide evaporite North Pole salt mine source rock Hell Kettle sulphate Weeks Island salt mine Deep seafloor hypersaline anoxic lake halotolerant Thiotrphic symbionts K2O from Gamma Log Hyperarid authigenic silica GR log brine pan sodium silicate evaporite-metal association salt periphery evaporite karst cryogenic salt water in modern-day Mars meta-evaporite marine brine Karabogazgol High Magadi beds sedimentary copper dihedral angle ancient climate 13C enrichment gassy salt gem hydrogen Turkmenistan sinkhole halite-hosted cave methanogenesis solar concentrator pans sulfur astrakanite silica solubility stevensite Realmonte potash sinjarite Red Sea Badenian Ethiopia potash ore price bischofite salt seal waste storage in salt cavity causes of glaciation methane doline Mega-monsoon nitrogen Archean wireline log interpretation Lomagundi Event knistersalz auto-suture MOP tachyhydrite potash ore blowout lunette Hadley cell: African rift valley lakes brine lake edge salt trade Warrawoona Group brine evolution nacholite salt karst McArthur River Pb-Zn RHOB recurring slope lines (RSL) stable isotope epsomite trona Muriate of potash lithium brine Calyptogena ponderosa evaporite intrasalt NPHI log gypsum dune gas outburst MVT deposit subsidence basin Koppen climate Dead Sea saltworks Koeppen Climate antarcticite mummifiction dark salt Boulby Mine black salt Gamma log CaCl2 brine crocodile skin chert DHAB Sumo halite evaporite-hydrocarbon association well blowout sulfate evaporite dissolution kainitite Five Island salt dome trend anthropogenically enhanced salt dissolution Quaternary climate DHAL endosymbiosis salt tectonics hydrothermal potash vestimentiferan siboglinids salt ablation breccia Ingebright Lake venice Kalush Potash palygorskite oil gusher SedEx rockburst sulphur intersalt Magdalen's Road well logs in evaporites Lop Nor carbon cycle Ripon Platform evaporite Proterozoic NaSO4 salts carnallitite bedded potash anomalous salt zones Density log 18O enrichment Great Salt Lake hydrothermal karst snake-skin chert 13C Clayton Valley playa: Lamellibrachia luymesi deep meteoric potash Dallol saltpan anthropogenic potash Lake Peigneur seal capacity salt suture freefight lake mirabilite nuclear waste storage Zabuye Lake 18O CO2 SOP alkaline lake zeolite lithium carbonate potash supercontinent York (Whitehall) Mine lithium battery well log interpretation Stebnyk potash Jefferson Island salt mine Seepiophila jonesi vadose zone circum-Atlantic Salt Basins allo-suture extrasalt Sulphate of potash Messinian Neoproterozoic Oxygenation Event Dead Sea caves halokinetic CO2: albedo Ure Terrace H2S natural geohazard Catalayud Atlantis II Deep Neoproterozoic

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