Showing posts with label Carbon Dioxide. Show all posts
Showing posts with label Carbon Dioxide. Show all posts

Friday, 11 December 2020

Understanding the formation of the Yamal Peninsula Gas-Emission Crater.

Methane is a powerful greenhouse gas, and the recent abrupt events of degassing and crater formation on the Yamal and Gydan Peninsulas have caused major concern that a warming Arctic may lead to increased thawing of permafrost and gas emissions. In addition, exploration and development of oil and gas fields in northern West Siberia, with construction of production, transportation and support facilities upon permafrost, face problems due to the harsh Arctic climate, low negative temperatures of air and ground and complex periglacial processes like frost heaving, thermokarst, thermal erosion. Processes in shallow permafrostmaylead to the formation of gas-emission craters, a phenomenon discovered during exploration for the past decade in the Arctic West Siberia. The first methane-leaking crater (Yamal Crater) was found in the Yamal Peninsula 42 km from the Bovanenkovo gas field and that discovery was followed by several more from the Yamal and Gydan Peninsulas. The Yamal Crater has been better documented than the others, which are only imaged in few photographs, but the available data are insucient to concede about the conditions and causes of its origin. The crater origin has been unanimously attributed to an explosive gas emission event, but the origin of the gas remains a subject of discussions.

In a paper published in the journal Geosciences on 8 May 2020, Evgeny Chuvilin of the Center for Hydrocarbon Recovery at the Skolkovo Institute of Science and Technology, Julia Stanilovskaya of Total, Aleksey Titovsky of the Department of Science and Innovation of the Yamal-Nenets Autonomous District, Anton Sinitsky of the Arctic Research Center of the Yamal-Nenets Autonomous District, Natalia Sokolova, Boris Bukhanov, Mikhail Spasennykh, Alexey Cheremisin, Sergey Grebenkin, and Dinara Davletshina, also of the Center for Hydrocarbon Recovery at the Skolkovo Institute of Science and Technology, and Christian Badetz, also of Total, present a summary of the proposed hypotheses for the formation of the Yamal Crater.

 
Location map of the Erkuta Crater and oil and gas fields in the Yamal Peninsula. Chuvilin et al. (2020).

The proposed hypotheses explaining the formation of the Yamal Crater, and other craters in the Yamal and Gydan Peninsulas, can be divided into two main groups that invoke either deep-seated or shallow causes. The deep-seated causes of crater formation include increased deep heat flux, upward migration of deep gaseous fluids through fault zones and fault intersections to shallow permafrost and dissociation of intrapermafrost gas hydrates driven by ascending heat and gas flows. These processes can produce reservoirs of pressurized gas in shallow permafrost which can release explosively, break up the frozen cap and form a crater.

 
Helicopter view of the Erkuta crater and adjacent territory in summer 2017. Chuvilin et al. (2020).

The crater was discovered in June 2017 by people from the Erkuta Polar Station on the floodplain of the Erkuta River, 30 km east of the station. The area is of interest to biologists for its proximity to the nesting-place of falcons. Two years before, the terrain was absolutely flat, as witnessed by Alexander Sokolov in a TV broadcast (Vesti Yamal) of 30 June 2017.

The team of biologists led by Sokolov observed heaving of the previously flat surface, as well as cracks in soil, during field works in July 2016, a year before the crater was first discovered in June 2017. The newly formed crater had a cylindrical shape, 10 to 12 m in diameter, with smooth walls was 20 m deep. The original heave mound was not fully eliminated: the crater was encircled by a 2–3 m high parapet-like ridge, with its slopes covered with silt and clay silt ejected during the explosive gas emission.

In December 2017, a field trip to the Erkuta Crater was organised jointly by the Government of the Yamal–Nenets Autonomous District, Total SA and the Skolkovo Institute of Science and Technology. The field work included sampling of soil, ice and water from the crater rim. By that time, the southern wall of the crater had collapsed and the diameter increased to 17.5 m. The crater was partly filled with water which made an up to 8-m-deep lake covered by about 1-m-thick ice under approximately 0.8 m of snow. A part of the parapet-like ridge remained around the crater next to a lake.

 
(Top) Panoramic view of the Erkuta cCrater in December 2017. (Bottom left) Lake next to the remnant parapet-like ridge around the Erkuta Crater in December 2017. (Bottom right) Panoramic view of the Erkuta Crater in summer 2018. Julia Stanilovskaya, Evgeny Chuvilin, and Alexander Sokolov in Chuvilin et al. (2020).

In June 2018, the crater was imaged by a drone survey, which showed further degradation of its wall. The deep crater of a year before became almost fully filled with water and transformed into a lake semi-circled by a remnant 2–3 m parapet. The crater wall was deformed by thermal erosion and slumping in its outer part but remained vertical in the inner part.

Field studies in December 2017 revealed a layer of massive ground ice, 3–4 m of visible thickness, in the inner wall of the crater.

 
Sampling points (red circles) in the inner wall of the Erkuta crater, December 2017. (left) Fragment of the sampling sight, (right). Red dashed line in left panal delineates the ice line. Evgeny Chuvilin in Chuvilin et al. (2020).

Ice at the sampling site was generally transparent and pure, but locally enclosed 1-2 cm thick layers of fine grained soil and a minor amount of intricately shaped 1-3 mm gas bubbles. The clear massive ice was topped by a dirty gray ice layer of a few centimtres thick with abundant soil inclusions.

 
Massive ground ice in the crater wall, December 2017. (left) The surface of the ice, (right) fresh cut of ground ice with soil inclusions. Evgeny Chuvilin in Chuvilin et al. (2020).

The ground ice was overlain by frozen silt with organic inclusions (plant remnants). The sediments had cross and wavy stratification common to aluvial facies. Some organic layers on lenses were a few centimeters thick and a few cm to tens of centimetres long.

The sandy crater wall was locally cut by discontinuous branching fractures partly filled with ice, often within zones of iron impregnation. The fractures possibly formed under stress produced by fluid (water or gas) pressure from underlying sediments.

 
Interbedded sandy and silty soils with inclusions of organic matter in the crater wall (December 2017). (left) Discontinuous branching fractures, (right) wavy stratification of organic material. Evgeny Chuvilin in Chuvilin et al. (2020).

The ejected clay silt on the outer crater wall was originally wet and was deposited in a floodplain environment; it di ered markedly from the overlying organic-rich alluvial sand.

Shrubs on the remnant slope facing the lake do not di er much from the surrounding lowland vegetation. Therefore, heaving shortly preceded the gas emission event and caused substantial changes to the vegetation. Otherwise, at years-long heaving, vegetation would have adapted to new conditions. Shrubs on Arctic tundra are usually lower on topographic highs than on the plainland and are absent in many areas where only grass can grow.

The samples collected in the December 2017 field trip to the crater included frozen soil from the northern wall, fine-grained material ejected from the crater and ice.

The particle size distribution of soil samples and soil inclusions in ground ice was analyzed in the laboratory of Fundamentproekt. The particles sizes were determined by the pipette method in silt and clay and by sieve analysis in sand.

The particle sizes of soil over the ground ice mainly correspond to silty sand while the ejected material is mainly light clay silt and silt, with particle sizes similar to those of soil inclusions in visible ground ice.

The mineralogy of soil samples was analyzed at the Geological Faculty of the Lomonosov Moscow State University on a Rigaku ULTIMA-IV X-ray di ractometer. The samples consist mainly of quartz and feldspar minerals (microcline and albite), about 80%–90% in total. Quartz percentages reach 61.8% and 74.3% in silty sand samples 8 and 9, respectively, notably more than in clay silt sample 2 (about 45.2%). The feldspar minerals are 32.3% in sample 2, 23.9% in sample 8 and about 15.4% in sample 9. Clay minerals are mainly mixed-layer illite–smectite, from 5.8% in sample 9% to 10.2% in sample 2. Other minerals occur in minor amounts (1% or less). Samples 2 and 8 share similarity in mineralogy, with similar amounts of microcline, illite, smectite and kaolinite, and thus were originally involved in similar deposition processes.

The soil and ice samples were analysed for the contents of soluble salts by using soil–water extracts prepared from 100 g of dry substance. Soil-free massive ground ice was analysed in the molten state. The total percentage of salts did not exceed 0.1% in soil samples and was in a range of 40–173 mg per litre in ice samples. The predominant major ions were alkaline metals sodium, potasium and magnesium as cations and sulphate and chlorine as anoins. 

The contents of unfrozen pore water in samples of erupted material (sample 2) and sand from the crater wall (sample 9) were determined from pore water activity. The amount of liquid water in the sand samples decreased abruptly at temperatures below -1°C and was less than 1% at -4°C. The clay silt sample (2) contained more unfrozen water than the sand sample (9): about 4% at -4°C and around 3% at -10°C.

Chuvilin et al. compared major-ion chemistry and stable isotopes of water in ice samples from the crater wall and in crater lake water. The ice samples (11 and 13) were recovered from the middle part of the ice lens free from visible soil inclusions. Prior to analyses, ice samples were melted, and the obtained water was collected without filtering.

The salinity of lake water is higher than that of ground ice: contents of some major ions are 7 to 11 times higher, especially sulphate, magnesium and calcium.

The oxygen and hydrogen isotope compositions of water from the lake and ice are also diff erent: those of ground ice are more depleted than in surface water from the crater. These compositions indicate that the mean annual temperature was 7 to 10°C lower than now when the ice was forming. 

The structure and texture of soil and ice samples were analyzed at Skoltech. The microstructure of frozen soil was studied in replica samples (imprints of fresh fracture planes on a plexiglass film) under an optical microscope (at the Skolkovo Institute of Science and Technology) and a scanning electron microscope (at Moscow University). The techniques for preparing replica samples and their optical and electron microscopy were reported in a number of publications. Ice structure and texture were studied in thin sections between crossed Polaroids; the thin sections were prepared following the standard procedures.

Soil microstructure was studied in sand from the crater wall (sample 9) and in ejected clay silt (sample 2). According to reflected light optical microscopy, the sand sample (9) mostly consists of 0.1–0.25 mm subrounded isometric quartz particles, with lesser amounts of fine-grained material, lenses and layers of more or less strongly degraded organic remnants, distinct 1–2 mm brown organic inclusions, as well as black organic–mineral concretions of silty sand and decayed organics.

Scanning electron microscope images highlight the morphology of quartz grains, with signatures of brittle fracture and dissolution and with organic inclusions of di erent sizes, shapes and decay degrees. Finer silt or clay particles make continuous or discontinuous films and clusters on the surface of sand particles.

 
Scanning electron microscope images of sand sample 9 at di erent magnification factors, with signatures of fracture and dissolution (left) and organic inclusions (right). Chuvilin et al. (2020).

The microstructure of clay silt ejected from the crater (sample 2) was also examined under the optical and electron microscopes. Reflected light optical microscopy revealed quite uniform silt and clay particles with rare sand grains and fuzzy dark brown organic inclusions. Scanning electron microscope images of di erent magnifications resolve fine sand and coarse silt particles (and their replica imprints) cemented by clay silt at a magnification of x 500 and 5 μm to 20 μm particles at x 2000. The x 2000 images reveal orientations of mineral matrix particles delineated by sericite flakes, as well as organic inclusions easily spotted due to their particular shapes.

 
Scanning electron microscope images of clay silt sample 2 at diff erent magnification factors: general view (left) and detail image (right). Chuvilin et al. (2020).

The ice macrostructure was studied in samples 6, 8 and 11 of ground ice and sample 22 from the top of the ice lens, at the ice-soil contact. Samples 6 and 11 are generally similar: massive transparent ice with chains of rare 0.3-0.5 cm air bubbles and thin flaky layers of silt and clay particles. Clusters of mineral particles occur at ice crystal boundaries. Mineral inclusions more numerous than air bubbles. Ice crystals in samples 6 and 11 appear as exceeding 5–7 cm in size, but the actual size is difficult to estimate because only crystal fragments fit into the thin sections.

 
Ice sample 6: general view (left) and structure under polarised light (right). Chuvilin et al. (2020).

Unlike samples 6 and 11, ice sample 8 encloses a layer of silty sand in pure ice almost free from soil particles and air bubbles. The ice crystals are fine (few mm) along the soil layer and coarser (2–3 cm) away from it. Although the true size of the ice crystals remains unknown because of the limited thin section size, they may be commensurate with those in samples 6 and 11. The soil layer, in its turn, encloses numerous small 3–5-mm-long, and up to 2-mm-thick lenses of ice with fine crystals (fractions of mm).

 
Ice sample 8: general view (left) and structure under polarised light (right). Chuvilin et al. (2020).

Ice sample 22 from the top of the ice lens differs markedly in colour from the other ice samples. It encloses numerous scattered small soil particles and air bubbles which make it look like dirty opaque ice. The ice crystals are 2-4 mm and generally isometric. The sand-silt material occurs both along the boundaries of ice crystals and inside them. The ice crystals in this sample are finer than in the three other samples possibly because they nucleated and grew in the presence of mineral components in the medium which provide numerous centres of crystallisation but is unfavorable for the formation of large ice crystals.

 
Ice sample 22: general view (left) and structure under polarized light (right). Chuvilin et al. (2020).

The gas component was analysed in sample 9 of sandy permafrost samples 6, 21, 22, and 23 of ground ice. Intrapermafrost gas from sample 9 was extracted by 150 ml syringes from thawing, roughly 50 g specimens in a concentrated salt solution following a standard technique, using pure nitrogen or helium as carrier gas.

Methane was present in all samples: mostly a few cm³ per 1 kg of soil or ice. Its content reached 94 cm³/kg at the top of ground ice (sample 22) but was about 10 times less in sample 21 from the middle of the ground ice lens. All samples except for 21 contained much more carbon dioxide than methane, which may be evidence of cryogenic concentration in frozen sand, e.g. during freezing of a talik. The contents of ethane and propane (methane homologs) varied from fractions to 2–3 cm³/kg. The ratios of methane to its homologs in ice samples were generally from 2 to 40 and indicated the presence of both biogenic methane and a component associated with sediment maturation (deep gas). The carbon isotope composition of methane in ground ice, analysed at the Hydroisotope Laboratory (Germany) likewise suggests biogenic origin of the gas.

The obtained results have implications for the formation mechanism of the Erkuta Crater, which formed on the site of the palaeo-channel of the Erkuta–Yakha River. The contours of the dried riverbed can be seen in a photograph of 2017, as well as in a satellite image of 2013. As a result of evolution, the palaeo-channel gradually turned into an oxbow lake, which continued to degrade and split up into several small drying lakes. Then a heaving mound began to form within one of these dried-up lakes. Contour of a mound is a bright spot (probably slightly elevated and drained soils) against the background of a dark thawed water-saturated soils, which can be distinguished in a satellite image of the beginning of summer 2013. 

 
Satellite image of the Erkuta crater area at the beginning of summer 2013. Chuvilin et al. (2020).

The thermal e ect of such lakes often produces a zone of unfrozen rocks (a talik) underneath. The lake sediments within the taliks contain organic matter recycled by microorganisms with release of biogenic methane. Additionally, gases can penetrate into the lake sediments from deep subsurface through permeable deformed zones. The talik beneath the Erkuta crater was most likely closed, given that the permafrost thickness in the area is about 200 m deep and the lake was small. The lake was gradually shoaling and shrinking whereby the talik was freezing from below and from the sides, which caused stress buildup inside the remaining confined talik. talik [19,20]. The stress released explosively by eruption of the gas–water–soil mixture from the freezing talik and the ensuing formation of the crater in its place.

Based on our results and available information, Chuvilin et al. propose the following conceptual model for formation of the Erkuta Crater.

 
Formation of the Erkuta crater in several stages: I: a lake and a talik underneath; II: onset of talik freezing after the lake has dried out; III: confined freezing of the talik and buildup of cryogenic pressure. Arrows show the expulsion direction of gas (blue dots); IV stratification of gas, water, and soil in the freezing talk and frost heaving; V: collapse of the frozen cap above the talik by pressurised gas (cryovolcanism); VI: active eruption of the gas-water-soil mass and onset of crater formation; VII: end of eruption and crater formation; VIII: lake formation as crater becomes filled with water. Chuvilin et al. (2020).

Stage I: A lake is underlain by a talik, with periodic inputs of organic matter into the lake in summer seasons. The organic matter in the lake sediments is recycled microbially with generation of biogenic methane which is accumulated in winter and emitted into the air in spring. The gaseous component of the sediments in the talik increases additionally due to migration of deeper thermogenic gases along faults and fractures in the crust. Emission of deep-seated gases from Arctic lakes is known from several other areas.

Stage II: Onset of talik freezing takes place after the lake had dried out. The talik undergoes confined freezing and becomes saturated with biogenic and deep-seated thermogenic gas.

Stage III: Confined freezing of the talik and buildup of cryogenic pressure takes place. Freezing of gas-saturated pore moisture under gas pressure at this stage has been studied previously by thermodynamic modeling in laboratory experiments.

As the lake is drying, the sub-lake unfrozen sediments are freezing from the top and from the sides, which leads to cryogenic gas concentration and stress buildup in the freezing closed talik. Gas-bearing sediments in the latter are confined by the surrounding ice-rich sediments, which increases gas pore pressure in the talik. The pressure may lead to ductile deformation of the permafrost cap above the talik if it exceeds the overburden pressure. At this stage, gas, water and soil in the residual talik can start to stratify.

Stage IV: Stratification of gas, water and soil in the residual talik and heaving. This process occurs in fairly homogeneous alluvial deposits. represented by sandy and silty sediments. As a result of stratification, heavier and denser soil stays on the bottom, while the light volatile gas component rises to the top; liquid water is in the middle. The layers of predominant soil, water and gas components are separated by dash lines in the figure, which are drawn tentatively because each layer contains some amounts of other components. If the pressure buildup is slow, the frozen cap can deform ductily, producing long-lasting heaves on the surface, pingo-like structures. However, if pressure increases rapidly, no slow loss heaving occurs before the stress release.

Stage V: Pressure increase in the talik saturated with water and gas and explosive pressure release breaking through the frozen cap. This phenomenon is known as cryovolcanism; eruption of water, fluids and liquefied soil triggered by overpressure in a freezing confined or open water-bearing system. The collapse of the frozen cap may be accompanied by outpouring of water or mud. No explosion occurs if the amount of gas in the talik is small, but the gas–water–soil mass from the talik erupts explosively and becomes dispersed, together with the frozen cap debris, in the presence of a gas cap.

Stages VI and VII: Progress of cryovolcanism. At stage VI, the gas–water–soil mixture erupts vigorously, and a crater starts to form. The explosive gas emission breaks up the meters thick frozen cap and disperses its material around the cryovolcano vent. A part of the ejected material falls near the crater and produces a parapet-like ridge rising above the surface around the crater, while some other part obviously falls back into the crater and gradually sinks to the bottom. As the eruption continues, the ejected unfrozen soil falls over the debris of the frozen cap. The soil, water and gas components of the talik, which were previously stratified during the confined freezing, mix again when erupting. (Stage VI). The level of the gas–water–soil mixture in the crater gradually decreases and the crater walls emerge. At stage VII, the eruption stops and leaves a crater, with its diameter commensurate with that of the residual closed talik prior to the emission. The ice-rich debris of the cap and the ejected talik sediments are scattered around the crater and cover its bottom.

Note that stages V, VI and VII follow one after another in a few hours to days.

Stage VIII: Stable evolution of the crater and its gradual transformation into a di erent landform. As the ejected material becomes involved into seasonal freezing–thawing cycles, the crater becomes filled with water in a few months and transforms into a circular lake surrounded by ejected material.

The suggested model explains the crater formation as a result of gas generation and accumulation in a sub-lake talik and the evolution of the talik exposed to confined freezing as the lake is drying out. Gas accumulation in the talik is additionally maintained by ascend of deep fluids migrating upwards through permeable faulted and fractured bedrock.

The data on the structure and composition of soil samples from the crater wall, as well as the proposed conceptual model for formation of the Erkuta crater, characterize it as a feature of explosive gas emission. Apparently, the crater formed in the place of a freezing closed talik under a dried lake by explosion of pressurized gas in the confined unfrozen sediments. The formation of the crater was preceded by rapid heaving within one or two years, judging by remnants of a mound detected in the first helicopter view of the area. The crater had a shape of a vertical cylinder with smooth walls, possibly because the explosion broke the frozen cap above the talik and mobilized the unfrozen soil–water–gas mass from the talik. A similar process of cryovolcanism has been proposed for formation of the Yamal Crater. Chuvilin et al. also consider the talik zone freezing. However, the essential role in the gas accumulation process (unlike the model for the Yamal crater) is played not by the biogenic gas generated in the bottom sediments of the thermokarst lake, but by the deep gas entering through the permeable zones.

The presence of fractures partly filled with ice on the crater walls also indicates that the freezing talik underwent buildup and partial release of stress. Our results indicate that the gas accumulated in and emitted from the talik came from two sources: it was biogenic gas resulting from microbially mediated decay of organic matter in lake sediments and thermogenic gas that migrated from deeper hydrocarbon reservoirs through permeable deformed bedrock. The proposed formation model of the Erkuta crater, unlike that of cryovolcanism suggested for the Yamal Crater, includes the contributions of thermogenic gas that had migrated along faults and fractures from deeper hydrocarbon reservoirs in addition to biogenic gas that formed within the talik.

In general, proposed formation model for the Erkuta crater associated with the emission of gas, which is accumulated in shallow permafrost. Its main feature is the consideration of the combined influence of deep-seated (deep gas migration) and shallow (oxbow lake evolution and closed talik freezing) causes in the process of Erkuta gas-emission crater formation. This vision is fundamentally di erent from the models of other authors, where only one prerequisites type of crater formation is considered: either deep-seated causes or only shallow ones.

The study presents exceptional data on the Erkuta gas-emission crater which was discovered in the summer of 2017 in the floodplain of the Erkuta–Yakha River on the Yamal Peninsula, south of all other craters of this kind found in the North of West Siberia for the past decade.

The main value of the research was the timely organized field trip to the crater in December 2017, which allowed collecting field data and sampling soil, ice and water before the crater became fully filled with water. The lifetime of these features being very short (less than 2 years), the soil and ground ice collected in December 2017 are the only samples suitable for laboratory analyses.

The study provides field data on the crater evolution in 2017–2018 and laboratory results for samples of frozen soil and ground ice from the crater walls. The crater formation was preceded by rapid heaving (within 1–2 years) detectable in aerial photographs. The presence of fractures partly filled with ice on the crater walls records buildup and partial release of stress in the freezing talik.

The carbon isotope composition of the gas component in ground ice proves the biogenic origin of methane in the surrounding permafrost. The presence of ethane and propane indicates that deep-seated gases generated during sediment maturation processes may have been involved into the gas-emission event. The higher contents of carbon dioxide compared to methane in several samples confirms the assumption of cryogenic concentration, which usually occurs during freezing of taliks.

The results are used to model the formation of the Erkuta gas-emission crater in shallow permafrost caused by the evolution of a talik under a dry lake, assuming a deep gas flow into the unfrozen zone. The model describes the crater evolution in several stages from geological prerequisites to the formation of a new lake-like landform.

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Friday, 26 June 2020

Carbon Dioxide emissions from the Central Atlantic Magmatic Province, and their implication for the End-Triassic Extinction.

Volatile elements affect the behaviour of magmas during their rise through the crust, and control the timing and energy of volcanic eruptions. When rapidly released into the atmosphere, volcanic gases such as carbon monoxide, carbon dioxide, methane, sulphur dioxide, hydrogen sulphide, hydrochloric acid, and chloromethane, can have a devastating impact on the global climate and biota. The best example from the geologic record is the emplacement of large igneous provinces, which are synchronous with several major Phanerozoic mass extinctions, indicating large igneous provinces as potential triggers of global-scale climatic and environmental changes via the release of volatiles. Large igneous provinces, often volumetrically dominated by continental flood basalts, are exceptional intraplate magmatic events involving huge magma volumes (up to 10 million cubic kilometres), that are emplaced episodically, leading to a pulsed release of their volatile phases. This potentially results in rapid rise of atmospheric carbon dioxide and global climate warming.

In addition to perturbing the climate, volcanic carbon dioxide plays a key role in the storage, ascent and eruption of magma, and drives the stability and evolution of magma reservoirs, regulating flood basalt magmatism and associated degassing fluxes. The importance of exsolved volatile phases (e.g., carbon dioxide-rich fluids) is highlighted by recently developed models of magmatic plumbing systems. In these new models, magma reservoirs are dominated by a crystalline mush, forming a multi-phase (i.e., solid, liquid and gas) system in which crystals, melt, and exsolved volatiles can interact and ascend independently towards the surface. Due to the low solubility of carbon dioxide in silicate melts, exsolution of carbon dioxide-rich fluids from melts occurs deep in the crust (i.e., within magmatic plumbing system) or even in the upper mantle, whereas at shallow depths the fluids typically become more water-rich. Since the exsolution of carbon dioxide changes the physical properties (e.g., density, viscosity and buoyancy) of magmas, it may therefore play a crucial role in their ascent, and could explain the pulsed eruptive style observed for large igneous provinces. However, direct evidence of carbon dioxide abundance in the deep magmas of large igneous provinces is lacking.

In a study published in the journal Nature Communications on 7 April 2020, Manfredo Capriolo and Andrea Marzoli of the Department of Geosciences at the University of Padova, László Aradi of the Lithosphere Fluid Research Lab at Eötvös Loránd University, Sara Callegaro, also of the Department of Geosciences at the University of Padova, and of the Centre for Earth Evolution and Dynamics at the University of Oslo, Jacopo Dal Corso, Robert Newton, Benjamin Mills, and Paul Wignall of the School of Earth and Environment at the University of Leeds, Omar Bartoli, again of the Department of Geosciences at the University of Padova, Don Baker of the Department of Earth and Planetary Sciences at McGill University, Nasrrddine Youbi of the Department of Geology at Cadi Ayyad University, the Instituto Dom Luiz at the University of Lisbon, and the Faculty of Geology and Geography at Tomsk State University, Laurent Remusat of the Muséum National d’Histoire Naturelle, Richard Spiess, once again of the Department of Geosciences at the University of Padova, and Csaba Szabó, also of the Lithosphere Fluid Research Lab at Eötvös Loránd University, investigate the history of volatiles in the magmas of the Central Atlantic Magmatic Province, of Earth’s largest large igneous provinces, by analysing volatiles in melt inclusions, particularly carbon dioxide.

Capriolo et al. examine the implications of these findings for magma eruption history and subsequent impact on the global climate. The emplacement of the Central Atlantic Magmatic Province (with (peak activity at 201.6–201.1 million years ago) occurred during the early stages of the Pangaea supercontinent break-up, leading to the opening of the Central Atlantic Ocean, and is synchronous with the End-Triassic Extinction, one of the five most severe biotic crises during the Phanerozoic. At least 3 million cubic kilometres of Central Atlantic Magmatic Province basaltic magmas were erupted or intruded into the continental crust over an area of 100 million square kilometres in brief pulses, from a few centuries to a few millennia each, characterised by high eruption rates. Such short and powerful eruptions may have had a severe impact on global climate by limiting the time in which negative feedback processes, such as the weathering of calcium-magnesium silicates, can abate warming and acidification. Central Atlantic Magmatic Province magmatism coincided in time with three marked negative carbon isotope excursions bracketing the main extinction period, and with an inferred strong rise of atmospheric carbon dioxide. In general, the pulsed magmatic and degassing activities of large igneous provinces can cause a rapid rise of atmospheric carbondioxide and greenhouse conditions, which are reflected by rapid carbon¹³ negative excursions recorded in both organic matter and carbonates, testifying to a global perturbation of the exogenic (i.e., superficial) carbon cycle. A rapid input of carbon¹³-depleted volatile phases into the atmosphere–hydrosphere system is possibly triggered by the emission of volcanic carbon dioxide, enhanced by the emission of carbon dioxide and methane derived from the thermal metamorphism of intruded organic matter-rich sediments.

Capriolo et al. screened a suite of over 200 intrusive and effusive samples from Central Atlantic Magmatic Province basaltic lava flows and sills in North America (USA and Canada), Africa (Morocco) and Europe (Portugal), and combined several in situ analytical techniques to investigate the presence of carbon dioxide within melt inclusion bubbles and constrain their formation depth. Capriolo et al.'s multidisciplinary analytical approach reveals that gas exsolution bubbles trapped in melt inclusions are a previously unappreciated direct proxy of volatile species degassed during large igneous province magmatic activity. In the case of the Central Atlantic Magmatic Province, Capriolo et al.'s analysis confirms the abundance of carbon dioxide (up to 10 000 gigatonnes of volcanic carbon dioxide degassed during Central Atlantic Magmatic Province emplacement) and indicates that at least part of this carbon has a middle- to lower-crust or mantle origin, suggesting that Central Atlantic Magmatic Province eruptions were rapid and potentially catastrophic for both climate and biosphere.

Map of Central Atlantic Magmatic Province in central Pangea at about 200 million years ago. The black symbols indicate the provenance of the studied samples: triangle for Portugal, circle for Morocco, square for New Jersey, USA, and diamond for Nova Scotia, Canada. Capriolo et al. (2020).

About 10% of the over 200 investigated intrusive and effusive Central Atlantic Magmatic Province basaltic rocks show gas exsolution bubble-bearing melt inclusions, hosted mainly in clinopyroxene and occasionally in plagioclase, orthopyroxene and olivine. The studied Central Atlantic Magmatic Province basaltic rocks are mainly porphyritic and microcrystalline, and the principal mineral phases are labradoritic-bytownitic plagioclase, augitic (abundant) and pigeonitic (scarce) clinopyroxene, rare magnesium-rich orthopyroxene, and rare and mostly altered magnesium-rich olivine. As accessory mineral phases, magnetite is common, while ilmenite is rare. In effusive rock samples (from USA, Canada, Morocco and Portugal), glomerocrystic aggregates of augitic clinopyroxene and plagioclase are commonly present, and are interpreted as clots of partially crystallised mineral mush from the transcrustal magmatic plumbing system. In the only studied intrusive sample (from Palisades sill, USA), olivine is abundant and usually well preserved.

Representative analysed samples at transmitted light optical microscopy. (a) Porphyritic and microcrystalline texture with phenocrysts of clinopyroxene and plagioclase (Cpx and Pl; sample NEW31, New Jersey, USA). (b) Glomerocrystic aggregate of clinopyroxene (Cpx; sample NEW31, New Jersey, USA). (c) Large phenocryst of plagioclase (Pl; sample AN156A, Morocco). (d) Crystals of plagioclase, clinopyroxene and well-preserved olivine (Pl, Cpx and Ol; sample NEW136B, New Jersey, USA). Capriolo et al. (2020).

Melt inclusions are nearly ubiquitous in glomerocrystic aggregates of clinopyroxene and plagioclase. The bubble-bearing melt inclusions usually have irregular shapes, can be singleor multi-bubble melt inclusions, and contain up to 25 bubbles per inclusion, displaying a large range of glass/bubble ratios even within the same host crystal or crystal clot (i.e., there is no proportionality between the volume of glass and the volume/number of bubbles). In detail, the estimated volume fraction of bubbles within each melt inclusion ranges from less than 0.1 to more than 0.5 approximately. Moreover, melt inclusions present a great variability in size, approximately from 5 to 50 μm on the principal axis. Bubbles within them usually have spherical shape and generally range from 1 to 15 μm in diameter. Sometimes bubbles are aggregated in the melt inclusions, probably due to post-entrapment coalescence. Some melt inclusions are partially crystallised, containing μm-sized daughter minerals in addition to, or instead of, bubbles. These crystals, likely formed from the melt after the entrapment, are mainly opaque mineral phases, such as sulphides and oxides (e.g., magnetite). The melt inclusion glass has a more silicic (mainly andesitic) and more differentiated composition compared to the host basaltic rocks, and is clearly different from typical Central Atlantic Magmatic Province basalts or basaltic andesites. The melt inclusion glass is generally enriched in silicon dioxide and aluminium oxide, and depleted in iron oxide, magnesium oxide, and calcium oxide compared to the host rocks, and would correspond to a residual melt after fractionation of about 40%vaugitic clinopyroxene, 10% plagioclase and 5% magnetite from a typical Central Atlantic Magmatic Province basalt. Such differentiation can only partly be due to post-entrapment crystallisation of the few tiny crystals within the melt inclusions or of the host clinopyroxene, which displays constant augitic composition, shows only faint chemical zonation towards the glass, and is substantially out of equilibrium with it. The most evident compositional zoning of the host clinopyroxene consists of a decrease in calcium oxide content and a slight increase in both magnesium oxide and iron oxide content close to the contact with the melt inclusions. Hence, the local thin rim around the melt inclusions of slightly calcium-depleted and iron and/or magnesium-enriched clinopyroxene suggests the probable presence of augite–pigeonite exsolution lamellae close to the boundary of melt inclusions, which likely formed at subsolidus conditions from an intermediate composition clinopyroxene that crystallized from the entrapped melt (i.e. post-entrapment crystallisation). However, the chemical disequilibrium between the melt inclusion glass and the host clinopyroxene, and the lack of significant chemical zoning within the host clinopyroxene at the contact with melt inclusions are not consistent with substantial diffusive re-equilibration within the host clinopyroxene and suggest a rapid cooling after melt entrapment. This indicates that a previously differentiated bubble-bearing melt was entrained between interstices of growing crystals, and rapidly cooled down, forming melt inclusions.

Representative single- and multi-bubble melt inclusions at transmitted light optical microscopy. The black arrows indicate the bubble-bearing melt inclusions. (a) Multi-bubble melt inclusions characterised by a highly variable range in bubble size, hosted in augitic clinopyroxene (Cpx; sample NS12, Nova Scotia, Canada). (b) Coalescent bubbles within melt inclusion, hosted in augitic clinopyroxene (Cpx; sample AN18, Morocco). (c)-(f) Single- and multi-bubble melt inclusions hosted in augitic clinopyroxene (Cpx) at increasing depth in the same crystalline aggregate, displaying different ratios between the volume of glass and the volume/number of bubbles (sample NS9, Nova Scotia, Canada). Capriolo et al. (2020).

The bubbles within melt inclusions were investigated in all the samples by confocal Raman microspectroscopy looking for carbon species (carbon monoxide, carbon dioxide, methane and elemental carbon), as well as for other important volatile compounds in volcanic systems (sulphur dioxide, hydrogen sulphide and water). In almost all analysed bubbles, carbion dioxide (within 54 bubbles of 9 samples) or elemental carbon (within 41 bubbles of 2 samples) were detected in both single- and multibubble melt inclusions of rock samples collected from all over the Central Atlantic Magmatic Province. In detail, Raman spectra show that carbon dioxide in Central Atlantic Magmatic Province bubbles is characterized by low density (roughly 0.1 g/cm³), and elemental carbon in Central Atlantic Magmatic Province bubbles is characterized by low crystallinity (i.e. it is present as disordered graphite and amorphous carbon). Carbion dioxide concentrations from 0.5 to 1.0 percent by weight in whole melt inclusions (i.e. glass plus bubbles) were calculated from the density of gaseous carbon dioxide within the bubbles and from the estimated volume fraction of these bubbles within melt inclusions. Other volatiles such as carbon monoxide, methane, sulphur dioxide and hydrogen sulphide were not detected, while water was often found within the glass of melt inclusions, but never in the bubbles. The melt inclusion glass, investigated through nanoscale secondary ion mass spectrometry, contains about 0.5–0.6 percent by weight water and 30–90 parts per million carbon dioxide.

Chemical maps of glomerocrystic clinopyroxene aggregates. Backscattered electrons image (a) and corresponding scanning electron microscopy with energy-dispersive X-ray spectroscopy maps (b)–(f) of a thin section area including melt inclusions and the hosting glomerocrystic clinopyroxene aggregates. In the backscattered electrons image image the brighter portions of clinopyroxene have augitic (Aug) composition and the darker ones have pigeonitic(Pgt) composition. In the scanning electron microscopy with energy-dispersive X-ray spectroscopy maps the brighter regions correspond to higher concentrations of the analysed element. These maps were acquired on sample NEW31 (New Jersey, USA). The scale bar is shown in (a). (a) Backscattered electrons image, (b) aluminium map, (c) calcium map, (d) iron map, (e) magnesium map, and (f) titanium map. Capriolo et al. (2020).

The analysed bubble-bearing melt inclusions strongly suggest that the Central Atlantic Magmatic Province magmatic system was rich in carbon dioxide. Most of the analysed bubbles contains carbon dioxide or, less frequently, elemental carbon, and no detectable amounts of any other investigated volatile phase. In particular, confocal Raman microspectroscopy allowed Capriolo et al. to distinguish and characterize both carbon dioxide and elemental carbon. The Raman spectrum of carbon dioxide is characterised by two sharp bands, usually called Fermi diad or Fermi doublet, associated to two symmetrical weak bands, usually called hot bands. Instead, the first-order Raman spectrum of elemental carbon is characterised by two different bands, the composite D band, activated in disordered graphite by lattice defects and typical of non-crystalline structures. and the single G band, typical of graphite. This last band was employed by Capriolo et al. in a crossplot to characterise the different types of elemental carbon, distinguishing disordered graphite and amorphous carbon Interestingly, carbon dioxide and elemental carbon within gas exsolution bubbles are never present together in the same samples. The elemental carbon, which is likely present as a thin film coating the inner spherical surface of the bubbles, replaces carbon dioxide in some samples, probably due to a change in the oxidation state within melt inclusions, for instance related to a diffusive loss of oxygen from the bubbles to the melt, when the latter crystallized oxides during cooling. The large variability in volume and number of bubbles observed in coexisting MIs (ranging from 1 to 25 bubbles per melt inclusion, approximately occupying from less than 0.1 to over 0.5 of the melt inclusion volume, as optically estimated in thin and thick sections) reveals heterogeneous entrapment of melt inclusions. Therefore, the bubbles within melt inclusions are interpreted as gas exsolution bubbles, formed during exsolution of a carbon dioxide-rich fluid phase likely from the silicate melt prior to, or during, their entrapment. Gas exsolution within melt inclusions after melt entrapment was probably of minor importance, particularly for melt inclusions with large bubbles, because the trapping of a bubble-free melt would have produced homogeneous melt inclusions, displaying very similar glass/bubble ratios, which were not observed in this study. The volatile-saturated melt and the volatiles may have a cogenetic origin (i.e., the melt was entrapped along with volatiles immediately after, or during, gas exsolution), or may have different origins (i.e., the melt was entrapped along with volatiles exsolved from deeper magmas, or degassed and fluxed from intruded crustal rocks).

Bubble-bearing melt inclusions at transmitted light optical microscopy and confocal Raman microspectroscopy. Left column: transmitted light photomicrographs at optical microscope of the analysed areas, bordered by dotted lines. Right column: Raman hyperspectral maps of the corresponding areas. (a), (c), (e) Photomicrographs of elemental carbon-bearing single- and multi-bubble melt inclusions (a) and (c) sample NEW31, New Jersey, USA; (e) sample AN39, Morocco. (b), (d), (f) Raman hyperspectral maps of the same samples area. (g) Photomicrograph of an irregular-shaped carbon dioxide-bearing multi-bubble melt inclusion, sample NS12, Nova Scotia, Canada. (h) Raman hyperspectral map of the same sample area. The Raman signal of carbon dioxide is weak due to its low density. However, spot analyses confirmed the presence of carbon dioxide in all bubbles. Capriolo et al. (2020).

Clinopyroxene compositions and volatile element concentrations suggest that carbon dioxide entrapment occurred within the deep magmatic roots of Central Atlantic Magmatic Province. The pressure of crystallisation of host clinopyroxene crystal clots can be calculated from mineral compositions using methods developed for magmatic systems, The geothermobarometer based on the equilibrium between clinopyroxene and a magmatic liquid was applied using whole rock composition as proxy for the original magmatic liquid composition, because the melt inclusion glass is in chemical disequilibrium with the host clinopyroxene. The calculated crystallization pressure ranges from 0.1 to 0.7gigapascals (at temperatures from 1150 to 1230°C) and is consistent with previous estimates from clinopyroxene crystallisation pressures (from 0.2 to 0.8 gigapascals) in basalts from the entire Central Atlantic Magmatic Province. These results suggest that the crystallisation of clinopyroxene in the investigated Central Atlantic Magmatic Province samples occurred predominantly within the middle continental crust (on average 12 km for a pressure/depth gradient of about 0.03 gigapascals/km). The deep origin of melt inclusions is consistent with observed volatile concentrations in both their glass and bubbles. The presence of sulphides within some melt inclusions shows that the entrapped melt became sulphide-saturated with sulphur concentrations likely exceeding 1500 parts per million. Sulphur concentrations of the same order of magnitude were estimated for Central Atlantic Magmatic Province basalts. Moreover, about 0.5–0.6 percent by weight water was detected in the melt inclusion glass through nanoscale secondary ion mass spectrometry analysis, revealing hydrated conditions for these melts. Despite the presence of water and sulphur in the melt inclusion glass, these volatiles were not detected in the bubbles. Hence, considering a realistic maximum primary concentration of about 1 percent by weight water and ca. 0.1 percent by weight sulphur dioxide in tholeiitic within-plate basaltic melts, most water and sulphur dioxide are expected to exsolve at pressures lower than 0.1 gigapascals (i.e. less than 3 km depth). Even considering that hydrogen ions may move from the bubbles into the glass, and carbon dioxide from the glass into the bubbles after melt inclusion entrapment, the observed distribution of volatile species between glass and bubbles within melt inclusions suggests the dominant occurrence of gas exsolution and bubble formation at relatively high pressures from a carbon dioxide-rich melt.

The inferred depth of carbon dioxide exsolution and entrapment indicates that this volatile species has a deep origin (at least 12 km on average). It therefore reveals that the entire carbon dioxide budget involved in Central Atlantic Magmatic Province emplacement could not have originated exclusively from assimilation and degassing of shallow intruded sediments, because sediments in the circum-Atlantic basins only reach a thickness of 5 km in eastern North America and less than 1 km in Morocco and Portugal. On the contrary, at least part of the carbon dioxide most probably derived from assimilation of deep to middle-crustal metasedimentary rocks (e.g. metacarbonates or graphite-bearing amphibolites/granulites) or from the mantle source of the Central Atlantic Magmatic Province basalts, containing significant amounts of recycled sedimentary material.

Sketch of the transcrustal plumbing system of Central Atlantic Magmatic Province basaltic magmas from the mantle to the surface. The evolution of basaltic magmas occurs at variable depth by crystallisation of minerals, which then form aggregates in crystalline mushes and entrain bubble-bearing melt, forming melt inclusions. Different volatile species exsolve at variable depth. In particular, carbon dioxide-rich fluids (white bubbles) start exsolving at great depth, whilst water-rich fluids (blue bubbles) and S-rich fluids (yellow bubbles) start exsolving at shallow depth. The black dashed arrows indicate the potential sources for the carbon inCentral Atlantic Magmatic Province magma: the mantle, the deep crust and the Palaeozoic or Triassic sedimentary basins in which Central Atlantic Magmatic Province sills intruded. The carbon within the studied melt inclusions derives from the deep sources as demonstrated with clinopyroxene geobarometry data. Capriolo et al. (2020).

The calculated depth of entrapment (roughly 12 km) allows an estimation of the carbon dioxide concentration originally present in Central Atlantic Magmatic Province magmas. The carbon dioxide saturation in basaltic melts is achieved at about 1000 parts per million at 0.2 gigapascals, increasing by ca. 500 parts per million for each 0.1 gigapascals. Considering the calculated crystallisation depths, the minimum estimate for the carbon dioxide concentration of Central Atlantic Magmatic Province magma, before gas exsolution, is between about 500 and 4000 parts per million. Such values are consistent with the carbon dioxide concentrations in the melt inclusions, calculated from carbon dioxide density within the bubbles, which range from 0.5 to 1.0 percent by weight. Moreover, starting from the minimum calculated values of the carbon dioxide concentration within melt inclusions (i.e. 0.5–0.6 percent by weight) as representative of Central Atlantic Magmatic Province magma, assuming an average density of 2.90 g/cm³ for basaltic rocks and considering 5–6 million km³ for the total volume of Central Atlantic Magmatic Province (in order to take into account the deep plumbing system), the total amount of degassed volcanic carbon dioxide during Central Atlantic Magmatic Province mplacement would be up to 100 000 gigatonnes. Interestingly, the values estimated for the carbon dioxide concentration of Central Atlantic Magmatic Province magma (0.5–1.0 percent by weight) and for the total amount of degassed volcanic carbon dioxide during Central Atlantic Magmatic Province emplacement (up to 100 000 gigatonnes) are consistent with those assessed in several other large igneous provinces, using different approaches

The high-volume fractions of carbon dioxide and elemental carbon-bearing bubbles within Central Atlantic Magmatic Province melt inclusions, along with the inferred depths of formation, reveal the high abundance (0.5–1.0 percent by weight) of carbon dioxide in the Central Atlantic Magmatic Province transcrustal magmatic plumbing system. The carbon dioxide-bearing bubbles identified in Central Atlantic Magmatic Province melt inclusions can be interpreted as batches of ascending volatiles entrapped in crystalline mush shortly prior to its mobilization and prior to eruption. This evidence for carbon dioxide saturation in the basaltic magmas at depth can explain the pulsed eruptive style of Central Atlantic Magmatic Province, where carbon dioxide acts as propellant for magma ascent, causing rapid and violent eruptive pulses. For instance, carbon dioxide-rich Hawaiian basalts have been shown to rapidly rise from over 5 km depth and to cause high fountaining eruptions. 

The presence of large amounts of carbon dioxide-bearing bubbles, the pulsed eruption and the efficient degassing of carbon dioxide from the basaltic magmas, strengthens the role of Central Atlantic Magmatic Province in triggering end-Triassic extreme greenhouse conditions The rate of volatile release plays a fundamental role in determining the severity of the surface environmental response; more rapid release increases the maximum transient concentration of atmospheric carbon dioxide and the subsequent severity of any environmental cascade. Assuming 0.5–1.0 percent by weight carbon dioxide in Central Atlantic Magmatic Province basalts, as suggested by the average carbon dioxide density and most common glass/bubble ratio within melt inclusions, and considering its efficient rise to the atmosphere through the magmatic transcrustal roots, it is possible that just a single Central Atlantic Magmatic Province volcanic pulse may have severely affected the end-Triassic climate. In fact, a single short-lived Central Atlantic Magmatic Province magmatic pulse (roughly  100 000 km³ erupted over 0.5 thousand years may emit about the same total amount of projected anthropogenic carbon dioxide emissions over the 21st century, according to the Representative Concentration Pathway 4.5 (a Representative Concentration Pathway is a greenhouse gas concentration trajectory adopted by the Intergovernmental Panel on Climate Change; four pathways were used for climate modeling and research for the Intergovernmental Panel on Climate Change Fifth Assessment Report in 2014.). This scenario for rapid carbon dioxide emissions predicts a global temperature increase of about 2 °C and an oceanic pH decrease of about 0.15 units over 100 years, and suggests that the end-Triassic climatic and environmental changes, driven by carbon dioxide emissions, may have been similar to those predicted for the near future.

See also...

https://sciencythoughts.blogspot.com/2020/06/ptychites-embreei-new-species-of.htmlhttps://sciencythoughts.blogspot.com/2020/03/dynamosuchus-collisensis-new-species-of.html
https://sciencythoughts.blogspot.com/2019/10/pseudotherium-argentinus-possible.htmlhttps://sciencythoughts.blogspot.com/2019/08/clevosaurus-hadroprodon-new-species-of.html
https://sciencythoughts.blogspot.com/2019/07/first-discovery-of-horsetail.htmlhttps://sciencythoughts.blogspot.com/2019/05/pachypleurosaurs-from-triassic-of.html
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Tuesday, 14 April 2020

Calculating the possibility of a phosphorus cycle on an early anoxic Earth or exoplanet.

Phosphorus is a critical component of the genetic and energetic machinery of all life and plays key structural roles in most organisms. Recent debate has bolstered the case that phosphorus is not only essential for life on Earth but is also likely central for recognisable biochemistry more broadly. Recent biogeochemical modeling and reconstructions of the evolution of marine phosphate concentrations from Earth’s rock record have bolstered the case that phosphorus has been the ultimate limiting nutrient throughout Earth’s history. It has also been argued that phosphorus would be expected to limit the extent of life on exoplanets where oxygenic photosynthesis has evolved. Therefore, a mechanistic understanding of how the global phosphorus cycle has changed through time is crucial both for a basic understanding of the history of life on our planet and in the development of predictive frameworks for the production and maintenance of exoplanet biosignatures.

In a paper published on the  arXiv database at Cornell University Library on 18 February 2020, Drew Syverson of the Department of Geology and Geophysics at Yale University, Christopher Reinhard of Earth and Atmospheric Sciences at the Georgia Institute of Technology, the Alternative Earths Team at the NASA Astrobiology Institute, and the NASA Nexus for Exoplanet System Science, Terry Isson, also of the Department of Geology and Geophysics at Yale University, and of the Faculty of Science & Engineering at the University of Waikato (Tauranga), Cerys Holstege and Joachim Katchinoff, again of the Department of Geology and Geophysics at Yale University, Benjamin Tutolo of the Department of Geosciences at the University of Calgary, Barbara Etschmann and Joël Brugger of Earth, Atmosphere & Environment at Monash University, and Noah Planavsky, again of the Department of Geology and Geophysics at Yale University, and the Alternative Earths Team at the NASA Astrobiology Institute, consider the posibility of the presence of bioavailable free phosphorus being available on an anoxic early Earth or exoplanet as a result of the weathering of mafic oceanic crust, and develop an experimental proceedure to test this idea.

Continental weathering, an important long-term carbon dioxide sink regulating planetary climate, is also the only significant source of phosphorus to the modern oceans. Submarine weathering of basaltic oceanic crust, while also serving as a long term carbon dioxide sink, currently acts a significant removal process of phosphorus from marine systems. For example, roughly 20% of the phosphorus entering the oceans today is removed through basalt alteration. The remainder is removed in association with the burial of authigenic apatite, organic phosphorus, and iron oxides in marine sediments. Marine phosphate concentrations are controlled through time by the interplay between the efficiency of phosphorus burial and the magnitude of the phosphorus source(s). It has been proposed that anoxic and iron-rich (ferruginous) oceans, which were widespread on the early Earth led to enhanced phosphate scavenging through adsorption onto iron oxide minerals formed near the oxygenated ocean-atmosphere interface and through the precipitation of reduced iron-phosphate minerals directly from seawater.

Phosphorus removal during basalt alteration may have also been enhanced in Earth’s past, given that it is likely that oceanic crust weathering played a more significant role in weathering and carbon dioxide sequestration prior to the emergence of continents above sea level and the proliferation of land. However, previous work has neglected the possibility that dissolved phosphorus may become liberated into seawater during marine weathering of oceanic crust in the absence of dissolved oxygen, as a natural result of limited iron oxidation and subsequent phosphorus scavenging. Although mid-ocean ridge basalts typically do not contain igneous apatite, phosphorus substitutes for silicon in primary silicate minerals and this phosphorus may be released during submarine basalt alteration. If operative, this process would reshape our view of the evolution of the phosphorus cycle on Earth Plants in terrestrial ecosystems and would become an important component of attempts to predict planetary phosphorus cycling on habitable exoplanets. Syverson et al. provide direct experimental support for the idea that basalt weathering under anoxic marine conditions can be a significant source of bioavailable phosphorus to aqueous systems.

The experiments utilised dissolved silicon dioxide enriched in the isotope Silicon²⁹ as a tracer to directly and accurately correlate the extent of primary silicate mineral dissolution with the amount of phosphate mobilized into seawater upon reaction with natural submarine basalt under anoxic conditions. Two sets of experiments are presented, one utilising fresh submarine basalt and one in which the fresh submarine basalt was treated with a reductive dissolution procedure designed to remove pre-existing iron oxides associated with partial oxidation during recovery from the seafloor. Mineral characterisation of the reactant basalt is combined with time-series changes in dissolved phosphate and Silicon²⁹ enriched silicon dioxide to allow determination of the efficacy of basalt weathering as a source of critical nutrients under the anoxic conditions characteristic of the early Earth and reducing exoplanet waterworlds. 

Phosphorus has two valencies, phosphorus³⁺ and phosphorus⁵⁺. Phosphorus³⁺ compounds will typicallt form when phosphorus is exposed to oxygenising elements, such as halogens, and can subsequently form free phosphorus³⁺ ions if such compounds are disolved in water. However. phosphorus⁵⁺ already bound into phosphate ions is considered thermodynamically stable under most conditions; it will not break down into phosphorus³⁺ and oxygen when disolved in water without considerable additional energetic input. The reduced dissolved phosphorus³⁺ ion is therefre not considered in Syverson et al.'s study, since the prescribed conditions of the experiments dictate that phosphorus⁵⁺ species, specifically phosphate, are thermodynamically stable and that phosphorus derived from the dissolution of primary silicate minerals of the reactant basalt exists as phosphorus⁵⁺ . 

Oxygenated basalt weathering experiments were also conducted in order to demonstrate the removal and retention of dissolved phosphate as a consequence of the formation of iron oxide minerals upon reaction, providing a comparative analysis of phosphate mobility with the anoxic experiments.

Two sets of long term basalt-seawater alteration experiments were conducted for over 2000 hours to better quantify the mobility of dissolved inorganic phosphate under a range of dissolved oxygen concentrations: Firstly anoxic experiments, (BA-1) and (BA-2), where it was expected that phosphate adsorption would be limited due to the lack of iron oxide mineral formation, both of which were conducted at 25°C. Secondly oxygenated experiments, (BA-3), (BA-4), and (BA-5), with concentrations of oxygen at present atmospheric level, in which Syverson et al. demonstrate the process of phosphate adsorption onto iron oxides is associated with oxidative alteration of basalt. Experiments (BA-3), (BA-4), and (BA-5) were conducted at 75, 50, and 15°C, respectively. All of the experiments were conducted at temperatures elevated with respect to bottom seawater but within the range of temperatures associated with carbonate precipitation in subseafloor upon chemical weathering of the oceanic crust.

The anoxic experiments were prepared, initiated, and maintained under anoxic conditions inside an anaerobic chamber with an atmosphere composed of 95% nitrogen and 5% helium. Each anoxic basalt alteration experiment was conducted in a gas-tight 250 mL Pyrex reactor with two gas-tight sampling ports, allowing for direct time-series sampling of the reactor solution without termination of the experiment and for keeping the reaction system closed to external environmental changes. Additionally, each reactor was wrapped in aluminum foil to shield from ultraviolet radiation, effectively preventing photo-oxidation of dissolved iron liberated from the dissolution of reactant basalt. Commencement of each experiment began by combination of the reactant basalt with the synthetic seawater and immersion into a temperature-regulated circulating oil bath set at 25°C. Solution samples were taken with time to assess the change in the composition of reactant seawater solution over the course of approximately 1500 hours. A typical sampling mass of solution for each sampling session can range between 4 - 8 grams. The first sample, through the sampling line of the reactor, is used as a 'bleed' to effectively wash out the sampling tube with experimental solution. The second sample is taken for cations/anions and pH analysis. A third sample may be taken for additional sample solution for additional analysis. In exchange with experimental solution taken from the reactor, an equivalent volume of 95% nitrogen and 5% helium atmosphere enters the experimental reactor. After the sampling session, both the intake and extraction valves are closed to keep the experimental system closed to any external changes in the chamber throughout thereaction progress.

The reactant solution for each anoxic experiment, (BA-1) and (BA-2), was prepared with deoxygenated ultrapure water and designed to have concentrations of dissolved components to simulate seawater, but with elevated concentrations of dissolved Silicon²⁹ enriched silicon dioxide. The pH was buffered at 6.5 to effectively preclude changes in pH as a consequence of basalt dissolution and acidity produced from secondary mineral formation. The reactant basalt was recovered from near the axis of the Juan de Fuca Ridge and was separated from the basalt glass and the crystalline fraction, where the crystalline fraction was powdered to achieve maximum reactive surface area to enhance reaction progress, sieved to achieve a distribution between 5-50 μm in grain size. A fraction of the crystalline powdered basalt reactant was treated with a citrate-bicarbonate-dithionite reductive dissolution step prior to commencement of the experiments. The citrate-bicarbonate-dithionite method specifically removes pre-existing iron-oxides from the natural reactant basalt, which may have a significant effect on the mobility of phosphate liberated from basalt upon alteration under anoxic conditions. The citrate-bicarbonate-dithionite method does not react with and or dissolve the primary reactant basalt silicate minerals. Thus, the primary phospherous, which resides as a trace element within the primary silicate minerals will remain unreactive (as lattice-bound phosphorus⁵⁺ within silicates) upon citrate-bicarbonate-dithionite treatment of the reactant basalt. Further, if any of the phosphorus⁵⁺ associated with the secondary iron oxide minerals were to become reduced to phosphorus³⁺ he highly soluble phosphorus³⁺ would have dissolved within the citrate-bicarbonate-dithionite leachate solution. Once the citrate-bicarbonate-dithionite procedure was terminated, the citrate-bicarbonate-dithionite treated basalt minerals were immediately filtered, cleaned by washing with copious amounts of ultrapure water, and then dried under an anoxic nitrogen atmosphere, with the result that any liberated phosphorus³⁺ would not have been measured by Syverson et al.'s procedure as being liberated during primary basalt dissolution.

The two experiments, basalt with and without the citrate-bicarbonate-dithionite treatment, (BA-1) and (BA-2), respectively, were designed to have an elevated water/rock ratio (approximately 250 g of solution to 3.8 g of basalt), where the mass balance of silica dioxide in the experimental system is dominated by reactant basalt. Specifically, the Silicon²⁹ enriched silicon dioxide spike introduced with the anoxic synthetic seawater was utilized to quantify the degree of silicate dissolution within basalt with reaction progress. The change in the abundance of Silicon²⁹ relative to Silicon²⁸ between the dissolved and solid reservoirs (seawater and basalt) was monitored with time, where it was expected that the Silicon²⁹/Silicon²⁸ ratio of the solution will decrease with increasing degrees of basaltic silicate dissolution, ultimately approaching the natural Silicon²⁹/Silicon²⁸ ratio (about 5%) due to mass balance constraints in the experimental system. This approach was advantageous since the change in the Silicon²⁹/Silicon²⁸ ratio in the solution was not affected by secondary mineral formation effects in contrast to observed changes in the total concentration of dissolved silicon dioxide.

Three oxygenated experiments, (BA-3), (BA-4), and (BA-5 )were conducted by reacting ground crystalline basalt (~20-250 μm grain size) with a synthetic seawater solution that is enriched in dissolved phosphate relative to natural bottom seawater to illustrate the effect of adsorption onto pre-existing and incipiently formed iron oxide surfaces upon alteration of the reactant basalt. For each experiment, eight identical 30 mL Teflon reactors were designed to have identical water/rock ratios (10 g of seawater solution: 1 g of basalt) and all have a headspace (approximately 20 mL) composed of modern atmosphere. The oxygenated reactant seawater was prepared to have a solution chemistry which closely resembles the composition of modern seawater.These particular experiments did not implement the Silicon²⁹ enriched silicon dioxide spike in the experimental solution but rather used natural abundance reagent-grade silicon dioxide. In addition, these particular experiments did not use a pH buffer but rather allowed the pH to change as a consequence of mineral dissolution and secondary mineral formation. Each reactor was maintained at 75, 50, and 15°C, in (BA-3), (BA-4), and (BA-5), respectively, in a shaking water bath, to maintain the experiment at a constant temperature throughout the course of basalt alteration. Over the course of approximately 4000 hours, individual reactors were terminated sequentially with reaction progress to determine the change in composition of the reactant seawater and to monitor changes in mineral speciation and element distribution of the altered basalt relative to the reactant material.

The enriched dissolved Silicon²⁹ enriched silicon dioxide tracer approach was utilised in Syverson et al.'s study since the change in Silicon²⁹/Silicon²⁸ ratio of the reactant seawater is a reflection only of the dissolution of reactant basalt and not by secondary mineral formation processes. The initially elevated dissolved silicon dioxide concentration of the anoxic experiments, (BA-1) and (BA-2), was designed to prevent rapid mineral dissolution artifacts during reaction initiation, while the observed changes in the dissolved silicon dioxide concentration over time is a result of secondary mineral formation. Indeed, the latter is precisely why Syverson et al. monitored the Silicon²⁹/Silicon²⁸ ratio of the solution rather than solely the dissolved silicon dioxide concentrations, because the Silicon²⁹/Silicon²⁸ tracer is not affected by secondary mineral formation while the dissolved net silicon dioxide mass balance is reflective of dissolution and precipitation effects. Through conservative mixing relationships and by implementation of time-series changes in the concentration of dissolved silicon dioxide and the associated Silicon²⁹/Silicon²⁸ ratio compared with the statistically constant composition of reactant basalt, the total amount of basaltic silicate dissolution can be quantified.

Characterisation of the reactant crystalline basalt, recovered from the axis of the Juan de Fuca Ridge, by electron microprobe analysis demonstrated that phosphate is present in primary silicates and secondary minerals at trace levels, between 0.01-0.4 percent by weight, and electron microprobe maps indicate that phosphorus is also concentrated within secondary minerals along the reaction rims around primary silicates. Electron microprobe imaging and X-ray fluorescence maps coupled with iron X-ray absorption spectroscopy measurements demonstrate that the reaction rims of the primary silicates are composed of secondary iron oxide minerals that are intermixed with clay minerals. The citrate-bicarbonate-dithionite reductive dissolution treatment, specifically designed to remove pre-existing iron oxides associated with the partial oxidation of the reactant basalt at the seafloor, indicates that phosphate and other components highly associated with iron oxides, such as manganese, vanadium, and nickel, are concentrated in the leachate. Dissolved aluminium is also concentrated in the leachate, suggesting that the dissolution of iron bearing clays also occurred upon the citrate-bicarbonate-dithionite leach of the reactant basalt. The combination of these results suggests that the observed differences in the mobility of dissolved phosphate with reaction progress between the anoxic experiments, (BA-1) and (BA-2), is likely attributable to the presence of pre-existing iron oxide minerals associated with the reactant basalt. To circumvent this effect on dissolved phosphate mobility, the anoxic experiment (BA-1) used reactant basalt that had pre-existing secondary iron oxide minerals removed by the citrate-bicarbonate-dithionite reductive dissolution treatment prior to commencement of the experiment.

Electron microscopy maps of aluminium, iron and phosphorus from grains derived from the ground basalt sampled from the Juan de Fuca Ridge used in the experimental study. Phosphorus is concentrated along areas of the altered grains that are concentrated in iron, which is attributed to a mixture secondary iron oxide minerals and clays. Syverson et al. (2020).

The oxidation state of the experimental system determines the fate of iron, either dissolved in solution or as aniron oxide mineral, and is critical with respect to the mobility and bioavailability of phosphate liberated from primary silicates upon partial dissolution. In the oxygenated basalt weathering experiments, (BA-3), (BA-4), and (BA-5), the mobility of dissolved iron and phosphate was limited, where dissolved iron, ultimately derived from the dissolution of primary silicate minerals, remained below the detection limit while the initially elevated concentration of dissolved phosphate decreased with reaction progress as a consequence of adsorption onto pre-existing and incipiently formed iron oxide minerals. Interestingly, the quantitative removal of dissolved phosphate is not complete as a consequence of the surface sites of the iron oxide minerals becoming increasingly saturated with respect to other competing adsorbed dissolved species, such as silicon dioxide.

The most significant difference between the anoxic and oxygenated experiments is the increase in concentration of dissolved iron and phosphate into the synthetic anoxic seawater, in stark contrast to the oxygenated experiments, where the mobility of dissolved iron is limited due to quantitative oxidation as iron-oxide minerals and the effective removal of dissolved phosphate by adsorption. Comparison between the separate anoxic experiments, (BA-1) (with citrate-bicarbonate-dithionite) and (BA-2) (without citrate-bicarbonate-dithionite), suggests that pre-existing iron oxide minerals, formed from partial alteration of primary basalt minerals by seawater, have retained a fraction of adsorbed phosphate prior to the experiment. Further, phosphate and the trace redox-sensitive metals, vanadium and manganese, are all highly concentrated in the citrate-bicarbonate-dithionite leachate, consistent with the high affinity of these elements for adsorption and incorporation within iron oxide minerals, respectively. These observation may help elucidate the observed differences in dissolved phosphate and iron mobility between (BA-1) and (BA-2), as shown by the enhanced release of these components into solution upon commencement of the reaction for experiment (BA-2).

The change in the Silicon²⁹/Silicon²⁸ ratio for experiments (BA-1) and (BA-2) are consistent with each other, where the proportion of disolved Silicon²⁹ in both decrease from approximately 100% to values between 11% and 14% due to the dissolution of reactant basalt and mixing of isotopically natural silicon dioxide into the enriched Silicon²⁹ enriched silicon dioxide-bearing synthetic seawater solution. The consistency between the experiments lends confidence, despite the dynamic changes in the bulk concentration of the dissolved components, magnesium, calcium, and silicon dioxide with reaction progress, that the change in the Silicon²⁹/Silicon²⁸ ratio is reflective only of primary mineral dissolution. Interestingly, both experiments asymptotically approach an elevated Silicon²⁹ value of 11-13%, relative to what is predicted by silicon dioxide mass balance constraints of the system, where it is expected for the Silicon²⁹/Silicon²⁸ in solution to ultimately approach the natural abundance of Silicon²⁹ of 5%. This limited mixing of silicon dioxide derived from basalt into the synthetic seawater is likely due to the formation of a passivating layer of secondary minerals on the primary minerals in the basalt, effectively hindering continued reaction.

Experiment (BA-1) demonstrates a 1:1 linear relationship with the calculated amount of total phosphate liberated from basalt into solution with respect to the observed changes in total phosphate with reaction progress. These time-series data, together with thermodynamic constraints, demonstrate that iron-phosphorous minerals, such as vivianite, do not reach a critical saturation state required for nucleation and dissolved phosphate concentrations are not limited by adsorption partitioning onto clays upon primary silicate mineral dissolution. Experiment (BA-2) however, which did not utilize the reductive dissolution pre-treatment, demonstrates significant scatter of phosphae time-series data relative to what is expected for phosphate released from Silicon²⁹/Silicon²⁸ mass balance calculations, indicating an additional source of phosphate to the experimental solution from the basalt reactant, likely attributed to chemical exchange of the reactant solution with the adsorbed species associated with pre-existing alteration product.

Both anoxic basalt weathering experiments demonstrated significant mobility of both dissolved iron and phosphate with continued reaction progress. The dissolved Silicon²⁹/Silicon²⁸ ratio systematically decreased with reaction progress in both experiments, indicating release of phosphate to seawater upon partial dissolution of primary silicate minerals within the basalt substrate. These results are in stark contrast to the oxygenated basalt weathering experiments, in which dissolved iron, derived from primary silicate minerals, remained below the detection limit while phosphorus was either removed from solution (despite high initial dissolved phosphorus levels) or remained at steady state levels throughout reaction progress as a consequence of adsorption onto pre-existing and incipiently formed iron oxide minerals. This suggests an important dichotomy between oxygenated and anoxic deep oceans in the mobilisation of phosphorus to bioavailable forms during submarine basalt weathering.

The experimental data can be used to evaluate the potential of submarine basalt weathering under anoxic conditions to serve as a source of bioavailable phosphate to the deep ocean by using the timeseries Silicon²⁹/Silicon²⁸ data to quantify the total amount of atmospheric carbon dioxide that would be consumed upon dissolution of primary silicate minerals in basalt. Syverson et al. assume a silicon dioxide/Alkalinity ratio indicative of the composition of tholeiitic basalt, represented here for simplicity as enstatite (magnesium-silica oxide), which would react with carbon dioxide to form magnesium carbonate and silicon dioxide. By combining the time-series changes in Silicon²⁹/Silicon²⁸ with the total dissolved silicon dioxide of the experimental solution, Syverson et al. use mass balance to quantify the total carbon dioxide consumed throughout the reaction progress. Specifically, for both anoxic experiments, (BA-1) and (BA-2), the time-series changes in the dissolved concentration of silicon dioxide and Silicon²⁹/Silicon²⁸ ratio are coupled with the silicon dioxide concentration and isotopic composition of basalt through conservative mixing relationships to calculate the amount of released silicon dioxide into solution from basalt upon dissolution.The total carbon dioxide consumed is determined through stoichiometric relations in the reaction and the calculated total silicon dioxide released upon basalt dissolution.

Syverson et al.'s experimental results indicate that the total phosphate/total carbon dioxide value characteristic of submarine basalt weathering under anoxic conditions is similar to that estimated for modern weathering of the continental crust. This suggests that submarine basalt weathering under anoxic conditions should in many cases be roughly similar in its effectiveness at exporting bioavailable phosphorus during carbon dioxide consumption as the weathering of continental crust above sea level.

To gain insight into the large-scale implications of their experimental results, Syverson et al. used their derived total phosphate/total carbon dioxide value as an input parameter for a global phosphate=carbon dioxide-oxygen steady state mass balance model for a water-rich silicate planet on which basalt alteration is the primary carbon dioxide sink; such that the long-term carbon cycles are buffered entirely by weathering of the oceanic lithosphere. They envisioned this scenario as being applicable to portions of Earth’s early history and to Earthlike volatile-rich exoplanet ‘waterworlds’ on which oxygenic photosynthesis has evolved. Conceptually, phosphateis released to the ocean as volcanic/metamorphic carbon dioxide is consumed during submarine basalt weathering, and some fraction of this bioavailable phosphate passes through the biosphere while the remainder is scavenged. This in turn leads to organic carbon burial and a release of oxygen to the ocean-atmosphere system. Syverson et al. explored a wide range of carbon dioxide outgassing rates, relative phosphorus mobilities, burial (sedimentary) phosphorus to organic carbon ratios, and phosphorus scavenging efficiencies in order to compute net oxygen production by the biosphere. Because the values of many of these parameters are uncertain, Syverson et al. used a stochastic approach in order to compute a statistical distribution for possible global biospheric oxygen fluxes.

Schematic of the biogeochemical model. A specified volcanic flux contributes carbon dioxide to the ocean-atmosphere system. Some fraction of this carbon dioxide input is removed via low-temperature ocean crust alteration, which releases inorganic bioavailable phosphorus (Pi). This bioavailable phosphorus can be recycled through the biosphere and buried in marine sediments (green), which releases oxygen to the atmosphere, or can be scavenged by iron-bearing mineral phases in the ocean interior (red). In the model, the fraction of bioavailable phosphorus that is removed by scavenging and the dynamics of internal phosphorus recycling (e.g., the overall ratio between phosphorus burial in sediments and oxygen release) are denoted by the scavenging efficiency of bioavailable phosphate in the ocean interior and rthe global net carbon/phosphorus, respectively. Syverson et al. (2020).

The parameters of the model are: (1) the volcanic carbon dioxide outgassing rate, which at steady state must be balanced by carbon dioxide removal through either submarine weathering  or photosynthetic uptake; (2) the mobility ratio derived from Syverson et al.'s experiments (total phosphate/total carbon dioxide), which describes the molar ratio between carbon dioxide consumed and phosphate released during submarine weathering; (3) the scavenging efficiency of bioavailable phosphate in the ocean interior; and (4) the global net carbon/phosphorus ratio for material buried from the oceans (in effect corresponding to a ratio between phosphorus buried and oxygen released to the ocean-atmosphere system). 

Results of  Syverson et al.'s simulation indicate that fluxes of phosphate from oceanic crust weathering can support a wide range of biospheric oxygen release rates. However, biospheric oxygen fluxes are generally high across a wide range of parameter space unless volcanic/metamorphic carbon dioxide outgassing is assumed to be very low. Syverson et al.'s results strongly suggest that biospheres sustained entirely by bioavailable phosphorus released during submarine basalt weathering under anoxic conditions, including that of the earliest Earth, are potentially capable of generating extremely high biogenic gas fluxes that rival or exceed even those of the modern Earth.

Studies of Earth system evolution and conceptual models used to forecast the emergence and maintenance of biosignatures on volatile-rich exoplanets have neglected the differences in hydrothermal phosphorus cycling between oxic and anoxic systems, and have instead implicitly invoked conditions under which phosphorus is effectively scavenged through adsorption onto iron oxide minerals formed from the hydration and oxidation of primary silicates in submarine basalt. Syverson et al.'s results stand in strong contrast to this prevailing conceptual model, and thus provide impetus to revisit mechanistic models for Earth’s early oxygen cycle and the factors regulating the oxygen cycles of volatile-rich silicate planets more generally. In particular, it will be important for future work to establish the ocean-atmosphere oxygen ‘threshold’ above which oxygenation of the deep oceans attenuates bioavailable phosphorus fluxes by initiating widespread iron oxidation within the ocean interior.

Intriguingly, existing model results indicate the possibility that atmospheric oxygen could be present at abundances that would potentially be remotely detectable without fully ventilating the deep oceans, with the implication that Earth-like terrestrial planets with water inventories greater than that of Earth could be very promising targets in the search for exoplanet biosignatures. Syverson et al.'s experimental results provide strong evidence that fluxes of bioavailable phosphorus on terrestrial planets dominated by submarine basalt weathering under anoxic conditions are likely to be very robust and in some cases may surpass those of even the modern Earth system. Anoxic submarine weathering should thus be considered an important component of the large-scale redox balance of terrestrial planets.

See also...

https://sciencythoughts.blogspot.com/2020/04/estimating-potential-for-life-to-have.htmlhttps://sciencythoughts.blogspot.com/2020/01/understanding-influence-of-large-bolide.html
https://sciencythoughts.blogspot.com/2019/06/evaluating-possibility-that-iron-oxides.htmlhttps://sciencythoughts.blogspot.com/2019/01/could-microbes-from-earth-have-reached.html
https://sciencythoughts.blogspot.com/2018/12/evidence-for-connection-between-large.htmlhttps://sciencythoughts.blogspot.com/2017/08/estimating-possibility-of-all-life.html
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