Earth science: Redox state of early magmas

International audienceA study of cerium in zircon minerals has allowed an assessment of the redox conditions that prevailed when Earth's earliest magmas formed. The results suggest that the mantle became oxidized sooner than had been though

Redox evolution of a degassing magma rising to the surface.

Volatiles carried by magmas, either dissolved or exsolved, have a fundamental effect on a variety of geological phenomena, such as magma dynamics1–5 and the composition of the Earth's atmosphere 6. In particular, the redox state of volcanic gases emanating at the Earth's surface is widely believed to mirror that of the magma source, and is thought to have exerted a first-order control on the secular evolution of atmospheric oxygen6,7. Oxygen fugacity (fO2 ) estimated from lava or related gas chemistry, however, may vary by as much as one log unit8–10, and the reason for such differences remains obscure. Here we use a coupled chemical–physical model of conduit flow to show that the redox state evolution of an ascending magma, and thus of its coexisting gas phase, is strongly dependent on both the composition and the amount of gas in the reservoir. Magmas with no sulphur show a systematic fO2 increase during ascent, by as much as 2 log units. Magmas with sulphur show also a change of redox state during ascent, but the direction of change depends on the initial fO2 in the reservoir. Our calculations closely reproduce the H2S/SO2 ratios of volcanic gases observed at convergent settings, yet the difference between fO2 in the reservoir and that at the exit of the volcanic conduit may be as much as 1.5 log units. Thus, the redox state of erupted magmas is not necessarily a good proxy of the redox state of the gases they emit. Our findings may require re-evaluation of models aimed at quantifying the role of magmatic volatiles in geological processes

Atmospheric oxygenation caused by a change in volcanic degassing pressure

International audienceThe Precambrian history of our planet is marked by two major events: a pulse of continental crust formation at the end of the Archaean eon and a weak oxygenation of the atmosphere (the Great Oxidation Event) that followed, at 2.45 billion years ago. This oxygenation has been linked to the emergence of oxygenic cyanobacteria1,2 and to changes in the compositions of volcanic gases3,4, but not to the composition of erupting lavas--geochemical constraints indicate that the oxidation state of basalts and their mantle sources has remained constant since 3.5 billion years ago5,6. Here we propose that a decrease in the average pressure of volcanic degassing changed the oxidation state of sulphur in volcanic gases, initiating themodern biogeochemical sulphur cycle and triggering atmospheric oxygenation. Using thermodynamic calculations simulating gas-melt equilibria in erupting magmas, we suggest that mostly submarine Archaean volcanoes produced gases with SO2/H2S,1 and low sulphur content. Emergence of the continents due to a global decrease in sea level and growth of the continental crust in the late Archaean then led to widespread subaerial volcanism, which in turn yielded gases much richer in sulphur and dominated bySO2. Dissolution of sulphur in sea water and the onset of sulphate reduction processes could then oxidize the atmosphere

The Pleistocene cinder cones surrounding Volcán Colima, Mexico re-visited: eruption ages and volumes, oxidation states, and sulfur content

Located at the volcanic front in the western Mexican arc, in the Colima Rift, is the active Volcán Colima, which lies on the southern end of the massive (∼450 km 3 ) Colima-Nevado volcanic complex. Along the margins of this andesitic volcanic complex, is a group of 11 scoria cones and associated lavas, which have been dated by the 40 Ar/ 39 Ar method. Nine scoria cones erupted ∼1.3 km 3 of alkaline magma (basanite, leucite-basanite, minette) between 450 and 60 ka, with >99% between 240 and 60 ka. Two additional cones (both the oldest and calc-alkaline) erupted <0.003 km 3 of basalt (0.5 Ma) and <0.003 km 3 of basaltic andesite (1.2 Ma), respectively. Cone and lava volumes were estimated with the aid of digital elevation models (DEMs). The eruption rate for these scoria cones and their associated lavas over the last 1.2 Myr is ∼1.2 km 3 /Myr, which is more than 400 times smaller than that from the andesitic Colima-Nevado edifice. In addition to these alkaline Colima cones, two other potassic basalts erupted at the volcanic front, but ∼200 km to the ESE (near the historically active Volcán Jorullo), and were dated at 1.06 and 0.10 Ma. These potassic suites reflect the tendency in the west-central Mexican arc for magmas close to the volcanic front to be enriched in K 2 O relative to those farther from the trench.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/47809/1/445_2005_Article_15.pd

Activity variations attending tungsten skarn formation, Pine Creek, California

An integrated geochemical analysis of the well-exposed Pine Creek, California tungsten skarn deposit has been undertaken to evaluate changes in chemical gradients across various lithologies. Thermodynamic calculations using available experimental and thermodynamic data allow limits to be assigned to the activities of important chemical components in the metasomatic environment. Quantifiable changes in “non-volatile” component activites (CaO, MgO, Al 2 O 3 , Fe 2 O 3 , WO 3 ) and in fugacities (O 2 , F 2 ) have been traced across the system. The activities of Al 2 O 3 , Fe 2 O 3 and WO 3 generally increase from the marble (<10 2 , <10 −6 , <10 −5 respectively), through the outer skarn zone and into the massive garnet skarn (10 −1.7±0.3 , 10 −3.4±0.4 , 10 −4.8±0.1 ) While CaO and MgO activities decrease for the same traverse from 10 −5 and 10 −2.1±1 respectively, to <10 −5.7 and <10 −3 . Calculated oxygen fugacities are 10 −23.5+1.0 at T =800 K (527° C), about one log unit below QFM, and more reducing than that required by Mt-Py-Po. The high variance of the garnet-pyroxene-quartz assemblages adds sufficient uncertainty to the calculated activities for individual specimens that only the large-scale trends survive the small-scale scatter. None of the chemical variables emerge as major independent or controlling factors for the mineralogy or phase compositions. Changes in the activity of one component may be offset by compensatory changes in another resulting in an environment that, while different from Pine Creek, could still host scheelite mineralization. Mass balance calculations indicate that the exposed endoskarn cannot have supplied the necessary chemical components to convert the country rock to skarn.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/47341/1/410_2004_Article_BF00381557.pd

Ptotal, {Mathematical expression} and the occurrence of cummingtonite in volcanic rocks

The phenocryst assemblage of cummingtonite, orthopyroxene, quartz, titanomagnetite and ilmenite in rhyolites of New Zealand has been used to calculate Ptotal and {Mathematical expression}. The values of Ptotal and {Mathematical expression} depend strongly upon whether an ideal mixing, or an ordered, model is used for the solid-solutions, but in both cases {Mathematical expression} ≈Ptotal. The rhyolite magma contained over 9 per cent water (by weight) when the cummingtonite phenocrysts precipitated, and possibly as much as 12 per cent, so that it is surprising that one of these rhyolites is a coherent lava. The calculated values of Ptotal and {Mathematical expression} are very sensitive to uncertainty in both the composition of the solid-solutions and temperature. Calculations show that {Mathematical expression}>0.7-0.8 Ptotal for cummingtonite to precipitate in rhyolites, and that iron-rich olivine and cummingtonite could only exist in rhyolites over a small temperature range at a pressure near 5 kilobars. Hornblende phenocrysts co-existing with fayalitic olivine in rhyolites accordingly have a very low activity of Mg7Si8O22(OH)2. © 1973 Springer-Verlag

Ptotal, {Mathematical expression} and the occurrence of cummingtonite in volcanic rocks

The phenocryst assemblage of cummingtonite, orthopyroxene, quartz, titanomagnetite and ilmenite in rhyolites of New Zealand has been used to calculate Ptotal and {Mathematical expression}. The values of Ptotal and {Mathematical expression} depend strongly upon whether an ideal mixing, or an ordered, model is used for the solid-solutions, but in both cases {Mathematical expression} ≈Ptotal. The rhyolite magma contained over 9 per cent water (by weight) when the cummingtonite phenocrysts precipitated, and possibly as much as 12 per cent, so that it is surprising that one of these rhyolites is a coherent lava. The calculated values of Ptotal and {Mathematical expression} are very sensitive to uncertainty in both the composition of the solid-solutions and temperature. Calculations show that {Mathematical expression}&gt;0.7-0.8 Ptotal for cummingtonite to precipitate in rhyolites, and that iron-rich olivine and cummingtonite could only exist in rhyolites over a small temperature range at a pressure near 5 kilobars. Hornblende phenocrysts co-existing with fayalitic olivine in rhyolites accordingly have a very low activity of Mg7Si8O22(OH)2. © 1973 Springer-Verlag