Isotopic and Petrologic Investigation, and a Thermomechanical Model of Genesis of Large-Volume Rhyolites in Arc Environments: Karymshina Volcanic Complex, Kamchatka, Russia

The Kamchatka Peninsula of eastern Russia is currently one of the most volcanically active areas on Earth where a combination of > 8 cm/yr subduction convergence rate and thick continental crust generates large silicic magma chambers, reflected by abundant large calderas and caldera complexes. This study examines the largest center of silicic 4-0.5 Ma Karymshina Volcanic Complex, which includes the 25 × 15 km Karymshina caldera, the largest in Kamchatka. A series of rhyolitic tuff eruptions at 4 Ma were followed by the main eruption at 1.78 Ma and produced an estimated 800 km3 of rhyolitic ignimbrites followed by high-silica rhyolitic post-caldera extrusions. The postcaldera domes trace the 1.78 Ma right fracture and form a continuous compositional series with ignimbrites. We here present results of a geologic, petrologic, and isotopic study of the Karymshina eruptive complex, and present new Ar-Ar ages, and isotopic values of rocks for the oldest pre- 1.78 Ma caldera ignimbrites and intrusions, which include a diversity of compositions from basalts to rhyolites. Temporal trends in δ18O, 87Sr/86Sr, and 144Nd/143Nd indicate values comparable to neighboring volcanoes, increase in homogeneity, and temporal increase in mantle-derived Sr and Nd with increasing differentiation over the last 4 million years. Data are consistent with a batholithic scale magma chamber formed by primarily fractional crystallization of mantle derived composition and assimilation of Cretaceous and younger crust, driven by basaltic volcanism and mantle delaminations. All rocks have 35–45% quartz, plagioclase, biotite, and amphibole phenocrysts. Rhyolite-MELTS crystallization models favor shallow (2 kbar) differentiation conditions and varying quantities of assimilated amphibolite partial melt and hydrothermally-altered silicic rock. Thermomechanical modeling with a typical 0.001 km3/yr eruption rate of hydrous basalt into a 38 km Kamchatkan arc crust produces two magma bodies, one near the Moho and the other engulfing the entire section of upper crust. Rising basalts are trapped in the lower portion of an upper crustal magma body, which exists in a partially molten to solid state. Differentiation products of basalt periodically mix with the resident magma diluting its crustal isotopic signatures. At the end of the magmatism crust is thickened by 8 km. Thermomechanical modeling show that the most likely way to generate large spikes of rhyolitic magmatism is through delamination of cumulates and mantle lithosphere after many millions of years of crustal thickening. The paper also presents a chemical dataset for Pacific ashes from ODDP 882 and 883 and compares them to Karymshina ignimbrites and two other Pleistocene calderas studied by us in earlier works

Large-volume silicic volcanism in Kamchatka: Ar–Ar and U–Pb ages, isotopic, and geochemical characteristics of major pre-Holocene caldera-forming eruptions

The Kamchatka Peninsula in far eastern Russia represents the most volcanically active arc in the world in terms of magma production and the number of explosive eruptions. We investigate large-scale silicic volcanism in the past several million years and present new geochronologic results from major ignimbrite sheets exposed in Kamchatka. These ignimbrites are found in the vicinity of morphologically-preserved rims of partially eroded source calderas with diameters from ∼ 2 to ∼ 30 km and with estimated volumes of eruptions ranging from 10 to several hundred cubic kilometers of magma. We also identify and date two of the largest ignimbrites: Golygin Ignimbrite in southern Kamchatka (0.45 Ma), and Karymshina River Ignimbrites (1.78 Ma) in south-central Kamchatka. We present whole-rock geochemical analyses that can be used to correlate ignimbrites laterally. These large-volume ignimbrites sample a significant proportion of remelted Kamchatkan crust as constrained by the oxygen isotopes. Oxygen isotope analyses of minerals and matrix span a 3‰ range with a significant proportion of moderately low-δ18O values. This suggests that the source for these ignimbrites involved a hydrothermally-altered shallow crust, while participation of the Cretaceous siliceous basement is also evidenced by moderately elevated δ18O and Sr isotopes and xenocryst contamination in two volcanoes. The majority of dates obtained for caldera-forming eruptions coincide with glacial stages in accordance with the sediment record in the NW Pacific, suggesting an increase in explosive volcanic activity since the onset of the last glaciation 2.6 Ma. Rapid changes in ice volume during glacial times and the resulting fluctuation of glacial loading/unloading could have caused volatile saturation in shallow magma chambers and, in combination with availability of low-δ18O glacial meltwaters, increased the proportion of explosive vs effusive eruptions. The presented results provide new constraints on Pliocene–Pleistocene volcanic activity in Kamchatka, and thus constrain an important component of the Pacific Ring of Fire

Hydrogen and oxygen isotope behaviors during variable degrees of upper mantle melting: Example from the basaltic glasses from Macquarie Island

We present measurements of hydrogen and oxygen isotopes in MORB glasses from Macquarie Island (SW. Pacific Ocean) coupled with determination of bulk H2O content by two independent techniques: total dehydration and FTIR. The incompatible trace elements in these glasses vary by a factor of 12 to 17, with K2O varying from 0.1 to 1.7 wt.%; these ranges reflect a variable degree of closed-system mantle melting, estimated from 1 to 15%. Water concentrations determined by the two techniques match well, yielding a range from 0.25 to 1.49 wt.% which correlates positively with all of the measured incompatible trace elements, suggesting that water is un-degassed, and behaves conservatively during mantle melting. Also, the agreement between the FTIR-determined and extracted water contents gives us confidence that the measured isotopic values of hydrogen reflect that of the mantle. Comparison of the range of water content with that of other incompatible trace elements allows estimation of the water partition coefficient in lherzolite, 0.0208 (ranging from 0.017 to 0.023), and the water content in the source, 386 ppm (ranging from 370 to 440 ppm). We observe a fairly narrow range in delta D and delta O-18 values of -75.5 +/- 4.5 parts per thousand and 5.50 +/- 0 .05 parts per thousand respectively, that can be explained by partial melting of normal lherzolitic mantle. The measured delta D and delta O-18 values of Macquarie Island glasses that range from nepheline- to hypersthene-normative, and from MORB to EMORB in composition, are identical to those in average global MORB. The observed lack of variation of delta D and delta O-18 with 1 to 15% degree of mantle melting is consistent with a bulk melting model of delta D and delta O-18 fractionation, in which water is rapidly scavenged into the first partial melt. The narrow ranges of delta D and delta O-18 in normal mantle are mostly due to the buffering effect of clino- and orthopyroxenes in the residual assemblage; additionally, fast ``wet'' diffusion of oxygen and hydrogen isotopes through the melting regions may further smooth isotopic differences. (C) 2012 Elsevier B.V. All rights reserved

Influence of high marine Ca/SO4 ratio on alteration of submarine basalts at 2.41 Ga documented by triple O and Sr isotopes of epidote

Over the course of Earth’s history, marine sulfate concentrations have been increasing in response to long-term atmospheric oxygenation. In contrast to modern oceans, where abundant sulfate precipitates in hot oceanic crust as anhydrite, Precambrian oceans contained much less (~0–10 mM) sulfate, so that submarine hydrothermal systems were comparatively poor in anhydrite. As a step towards exploring the role of chemical evolution of seawater solutes, we investigate the reaction between basalt and seawater that took place at the ca. 2.43–2.41 Ga Vetreny Belt (Karelia craton, NW Russia) using fluid inclusion and multi-isotope measurements complemented by reactive transport and static aqueous-mineral equilibrium calculations. Using fluid inclusion measurements by LA-ICP-MS, we constrain the Sr concentration in the least modified seawater-derived fluids and address the effect of phase separation. Then, we complement the previous δ18O – Δ′17O datasets with new 87Sr/86Sr measurements performed on 2.41 Ga epidote from the Vetreny Belt, and recent (0–6 Ma) oceanic epidote from Reykjanes, Iceland and the drilling site 504B in the eastern Pacific Ocean. The 2.41 Ga epidote with 87Sr/86Srinitial of 0.7029–0.7042 and Δ′17O of –0.06 to 0.00‰ is best explained by a relatively high fraction (~90%) of marine Sr that was delivered from contemporaneous seawater with 87Sr/86Sr ≈ 0.7045, and without significant removal by early anhydrite. Using Monte-Carlo simulation of a dual-porosity model, we constrain the range of possible exchange trajectories based on the variability of physical parameters (porosity, fluid flow velocity, fracture spacing, recrystallization rates). Further, we use a series of static equilibrium seawater-basalt reaction calculations with emphasis on the possible range of marine Ca/SO4 values at 2.41 Ga. Our calculations demonstrate that co-existing quartz and epidote in absence of feldspars represent equilibrium with less-evolved hydrothermal fluids. Consequently, equilibrium assemblage of quartz and epidote provide an insightful archive for marine Sr. Based on our modeling and assumptions about marine 87Sr/86Sr and Sr/Ca ratios, the 2.41 Ga epidotes document a seawater-basalt reaction where the initial fluid contained between 30 and 40 mM of Ca and 0–10 mM SO4, representing a high marine input and the possible effect of phase separation. Based on our data, we suggest that high Ca/SO4 ratio of seawater (≫1) and low concentration of anhydrite in submarine systems of the contemporaneous oceans promote a higher fraction of seawater Sr to be permanently stored in silicates of altered oceanic crust. In contrast, modern altered oceanic crust is depleted in radiogenic Sr due to partitioning into anhydrite, which partly returns into the ocean upon cooling