Chlorine concentrations and stable isotope ratios in Izu Bonin tephra

d37Cl values were determined for Izu Bonin arc magmas erupted 0-44 Ma in order to better understand the time-dependent processing of volatiles in subduction zones. Pristine ash-sized particles (glass, pumice, scoria, and rock fragments) were handpicked from tephra drilled at ODP Site 782. d37Cl values for these particles span a large range from -2.1 to +1.7 per mil (error = ± 0.3 per mil) vs. SMOC (Standard Mean Ocean Chloride, defined as 0 per mil). The temporal data extend the previously reported range of d37Cl values of -2.6 to 0.4 per mil (bulk ash) and -5.4 to -0.1 per mil (volcanic gases) from the Quaternary Izu Bonin-Mariana volcanic front to more positive values. Overall, the temporal data indicate a time-progressive evolution, from isotopically negative Eocene and Oligocene magmas (-0.7 ± 1.1 per mil, n = 10) to Neogene magmas that have higher ?37Cl values on average (+0.3 ± 1.1 per mil; n = 13). The increase is due to the emergence of positive d37Cl values in the Neogene, while minimum d37Cl values are similar through time. The range in d37Cl values cannot be attributed to fractionation during melt formation and differentiation, and must reflect the diversity of Cl present in the arc magma sources. Cl clearly derives from the slab (> 96% Cl in arc magmas), but d37Cl values do not correlate with isotope tracers (e.g. 207Pb/204Pb and 87Sr/86Sr) that are indicative of the flux from subducting sedimentary and igneous crust. Given the steady, high Cl flux since at least 42 Ma, the temporal variability of d37Cl values is best explained by a flux from subducting isotopically positive and negative serpentinite formed in the ocean basins that mingles with and possibly overprints the isotopically negative flux from sediment and igneous crust at arc front depths. The change in the d37Cl values before and after backarc spreading may reflect either a tectonically induced change in the mechanism of serpentinite formation on the oceanic plate, or possibly the integration of isotopically positive wedge serpentinite as arc fluid source during the Neogene. Our study suggests that serpentinites are important fluid sources at arc front depth, and implies the return of isotopically positive and negative Cl from the Earth surface to the mantle.

(Table 1) Li, B and Sr isotopic composition and concentration in ODP Leg 209 samples

Spinel harzburgites from ODP Leg 209 (Sites 1272A, 1274A) drilled at the Mid-Atlantic ridge between 14°N and 16°N are highly serpentinized (50-100%), but still preserve relics of primary phases (olivine >= orthopyroxene >> clinopyroxene). We determined whole-rock B and Li isotope compositions in order to constrain the effect of serpentinization on d11B and d7Li. Our data indicate that during serpentinization Li is leached from the rock, while B is added. The samples from ODP Leg 209 show the heaviest d11B (+29.6 to +40.52 per mil) and lightest d7Li (-28.46 to +7.17 per mil) found so far in oceanic mantle. High 87Sr/86Sr ratios (0.708536 to 0.709130) indicate moderate water/rock ratios (3 to 273, on the average 39), in line with the high degree of serpentinization observed. Applying the known fractionation factors for 11B/10B and 7Li/6Li between seawater and silicates, serpentinized peridotite in equilibrium with seawater at conditions corresponding to those of the studied drill holes (pH: 8.2; temperature: 200 °C) should have d11B of +21.52 per mil and d7Li of +9.7 per mil. As the data from ODP Leg 209 are clearly not in line with this, we modelled a process of seawater-rock interaction where d11B and d7Li of seawater evolve during penetration into the oceanic plate. Assuming chemical equilibrium between fluid and a rock with d11B and d7Li of ODP Leg 209 samples, we obtain d11B and d7Li values of +50 to +60 per mil, -2 to +12 per mil, respectively, for the coexisting fluid. In the oceanic domain, no hydrothermal fluids with such high d11B have yet been found, but are predicted by theoretical calculations. Combining the calculated water/rock ratios with the d7Li and d11B evolution in the fluid, shows that modification of d7Li during serpentinization requires higher water/rock ratios than modification of d11B. Extremely heavy d11B in serpentinized oceanic mantle can potentially be transported into subduction zones, as the B budget of the oceanic plate is dominated by serpentinites. Extremely light d7Li is unlikely to survive as the Li budget is dominated by the oceanic crust, even at small fractions.

Oceanographic data, oxygen and methane concentrations, and C-CH4 isotope ratios measured at Jaco Scar

Methane (CH4) concentrations and CH4 stable carbon isotopic composition (d13CCH4) were investigated in the water column within Jaco Scar. It is one of several scars formed by massive slides resulting from the subduction of seamounts offshore Costa Rica, a process that can open up structural and stratigraphical pathways for migrating CH4. The release of large amounts of CH4 into the adjacent water column was discovered at the outcropping lowermost sedimentary sequence of the hanging wall in the northwest corner of Jaco Scar, where concentrations reached up to 1,500 nmol L-1. There CH4-rich fluids seeping from the sedimentary sequence stimulate both growth and activity of a dense chemosynthetic community. Additional point sources supplying CH4 at lower concentrations were identified in density layers above and below the main plume from light carbon isotope ratios. The injected CH4 is most likely a mixture of microbial and thermogenic CH4 as suggested by d13CCH4 values between -50 and -62 per mil Vienna Pee Dee Belemnite. This CH4 spreads along isopycnal surfaces throughout the whole area of the scar, and the concentrations decrease due to mixing with ocean water and microbial oxidation. The supply of CH4 appears to be persistent as repeatedly high CH4 concentrations were found within the scar over 6 years. The maximum CH4 concentration and average excess CH4 concentration at Jaco Scar indicate that CH4 seepage from scars might be as significant as seepage from other tectonic structures in the marine realm. Hence, taking into account the global abundance of scars, such structures might constitute a substantial, hitherto unconsidered contribution to natural CH4 sources at the seafloor.

Tsunami characteristics along the Peru-Chile trench: analysis of the 2015 Mw8.3 Illapel, the 2014 Mw8.2 iquique and the 2010 Mw8.8 maule tsunamis in the near-field

Tsunamis occur quite frequently following large magnitude earthquakes along the Chilean coast. Most of these earthquakes occur along the Peru-Chile Trench, one of the most seismically active subduction zones of the world. This study aims to understand better the characteristics of the tsunamis triggered along the Peru-Chile Trench. We investigate the tsunamis induced by the Mw8.3 Illapel, the Mw8.2 Iquique and the Mw8.8 Maule Chilean earthquakes that happened on September 16th, 2015, April 1st, 2014 and February 27th, 2010, respectively. The study involves the relation between the co-seismic deformation and the tsunami generation, the near-field tsunami propagation, and the spectral analysis of the recorded tsunami signals in the near-field. We compare the tsunami characteristics to highlight the possible similarities between the three events and, therefore, attempt to distinguish the specific characteristics of the tsunamis occurring along the Peru-Chile Trench. We find that these three earthquakes present faults with important extensions beneath the continent which result in the generation of tsunamis with short wavelengths, relative to the fault widths involved, and with reduced initial potential energy. In addition, the presence of the Chilean continental margin, that includes the shelf of shallow bathymetry and the continental slope, constrains the tsunami propagation and the coastal impact. All these factors contribute to a concentrated local impact but can, on the other hand, reduce the far-field tsunami effects from earthquakes along Peru-Chile Trench.

Evolution of strength and physical properties of ultramafic and carbonate rocks under hydrothermal conditions

Interaction of rocks with fluids can significantly change mineral assemblage and structure. This so-called hydrothermal alteration is ubiquitous in the Earth’s crust. Though the behavior of hydrothermally altered rocks can have planet-scale consequences, such as facilitating oceanic spreading along slow ridge segments and recycling volatiles into the mantle at subduction zones, the mechanisms involved in the hydrothermal alteration are often microscopic. Fluid-rock interactions take place where the fluid and rock meet. Fluid distribution, flux rate and reactive surface area control the efficiency and extent of hydrothermal alteration. Fluid-rock interactions, such as dissolution, precipitation and fluid mediated fracture and frictional sliding lead to changes in porosity and pore structure that feed back into the hydraulic and mechanical behavior of the bulk rock. Examining the nature of this highly coupled system involves coordinating observations of the mineralogy and structure of naturally altered rocks and laboratory investigation of the fine scale mechanisms of transformation under controlled conditions. In this study, I focus on fluid-rock interactions involving two common lithologies, carbonates and ultramafics, in order to elucidate the coupling between mechanical, hydraulic and chemical processes in these rocks. I perform constant strain-rate triaxial deformation and constant-stress creep tests on several suites of samples while monitoring the evolution of sample strain, permeability and physical properties. Subsequent microstructures are analyzed using optical and scanning electron microscopy. This work yields laboratory-based constraints on the extent and mechanisms of water weakening in carbonates and carbonation reactions in ultramafic rocks. I find that inundation with pore fluid thereby reducing permeability. This effect is sensitive to pore fluid saturation with respect to calcium carbonate. Fluid inundation weakens dunites as well. The addition of carbon dioxide to pore fluid enhances compaction and partial recovery of strength compared to pure water samples. Enhanced compaction in CO2-rich fluid samples is not accompanied by enhanced permeability reduction. Analysis of sample microstructures indicates that precipitation of carbonates along fracture surfaces is responsible for the partial restrengthening and channelized dissolution of olivine is responsible for permeability maintenance.

Anisotropic seismic tomography with the reversible jump Markov chain Monte Carlo

The established isotropic tomographic models show the features of subduction zones in terms of seismic velocity anomalies, but they are generally subjected to the generation of artifacts due to the lack of anisotropy in forward modelling. There is evidence for the significant influence of seismic anisotropy in the mid-upper mantle, especially for boundary layers like subducting slabs. As consequence, in isotropic models artifacts may be misinterpreted as compositional or thermal heterogeneities. In this thesis project the application of a trans-dimensional Metropolis-Hastings method is investigated in the context of anisotropic seismic tomography. This choice arises as a response to the important limitations introduced by traditional inversion methods which use iterative procedures of optimization of a function object of the inversion. On the basis of a first implementation of the Bayesian sampling algorithm, the code is tested with some cartesian two-dimensional models, and then extended to polar coordinates and dimensions typical of subduction zones, the main focus proposed for this method. Synthetic experiments with increasing complexity are realized to test the performance of the method and the precautions for multiple contexts, taking into account also the possibility to apply seismic ray-tracing iteratively. The code developed is tested mainly for 2D inversions, future extensions will allow the anisotropic inversion of seismological data to provide more realistic imaging of real subduction zones, less subjected to generation of artifacts.

Subduction of the Nazca Ridge and the Inca Plateau: Insights into the formation of ore deposits in Peru

A large number of ore deposits that formed in the Peruvian Andes during the Miocene (15-5 Ma) are related to the subduction of the Nazea plate beneath the South American plate. Here we show that the spatial and temporal distribution of these deposits correspond with the arrival of relatively buoyant topographic anomalies, namely the Nazca Ridge in central Peru and the now-consumed Inca Plateau in northern Peru, at the subduction zone. Plate reconstruction shows a rapid metallogenic response to the arrival of the topographic anomalies at the subduction trench. This is indicated by clusters of ore deposits situated within the proximity of the laterally migrating zones of ridge subduction. It is accordingly suggested that tectonic changes associated with impingement of the aseismic ridge into the subduction zone may trigger the formation of ore deposits in metallogenically fertile suprasubduction environments. (c) 2005 Elsevier B.V All rights reserved.

Unraveling an antique subduction process from metamorphic basement around Medellin city, Central Cordillera of Colombian Andes

In the surroundings of Caldas and El Retiro cities (Colombia) metamorphic rocks derived from basic and pelitic protoliths comprise the Caldas amphibole schist and the Ancon schist respectively. Subordinated metamorphosed granite bodies (La Miel gneiss) are associated to these units, and The El Retiro amphibolites, migmatites and granulites crops out eastwards of these units, separated by shear zones. The Caldas amphibole schist and the Ancon schist protoliths could have been formed in a distal marine reduced environment and amalgamated to the South American continent in an apparent Triassic subduction event. The El Retiro rocks are akin to a continental basement and possible include impure metasediments of continental margin, whose metamorphism originated granulite facies rocks and migmatites as a result of the anatexis of quartz-feldspathic rocks. The metamorphism was accompanied by intense deformation, which has juxtaposed both migmatites and granulite blocks. Afterward, heat and fluid circulation associated with the emplacement of minor igneous intrusions resulted in intense fluid-rock interaction, variations in the grain size of the minerals and, especially, intense retrograde metamorphic re-equilibrium. Thermobarometric estimations for the Caldas amphibole schist indicate metamorphism in the Barrovian amphibolite fades. The metamorphic path is counter-clockwise, but retrograde evolution could not be precisely defined. The pressures of the metamorphism in these rocks range from 6.3 to 13.5 kbar, with narrow temperature ranging from 550 to 630 degrees C. For the Ancon schist metapelites the P-T path is also counter-clockwise, with a temperature increase evidenced by the occurrence of sillimanite and the cooling by later kyanite. The progressive metamorphism event occurred at pressures of 7.6-7.2 kbar and temperatures of 645-635 degrees C for one sample and temperature between 500 and 600 degrees C under constant pressure of 6 kbar. The temperature estimated for these rocks varies between 400 and 555 degrees C at pressures of 5-6 kbar in the retrograde metamorphic path. The El Retiro rocks evidence strong decompression with narrow variation in temperature, showing pressure values between 8.7 and 2.7 kbar at temperatures of 740-633 degrees C. These metamorphic fragments of the basement in the Central Cordillera of the Colombian Andes could represent a close relationship with an antique subduction zone. (C) 2011 Elsevier Ltd. All rights reserved.

Deformational evolution of a Cretaceous subduction complex: Elephant Island, South Shetland Islands, Antarctica

New structural data from Elephant Island and adjacent islands are presented with the objective to improve the understanding of subduction kinematics in the area northeast of the Antarctic Peninsula. on the island, a first deformation phase, D-1, produced a strong SL fabric with steep stretching and mineral lineations, partly defined by relatively high pressure minerals, such as crossite and glaucophane. D-1 is interpreted to record southward subduction along an E-W trench with respect to the present position of the island. A second phase, D-2, led to intense folding with steep E-W-trending axial surfaces. The local presence of sinistral C'-type sheer bands related to this phase and the oblique inclination of the L-2 stretching lineations are the main arguments to interpret this phase as representing oblique sinistral transpressive shear along steep, approximately E-W-trending shear zones, with the northern (Pacific) block going down with respect to the southern (Antarctic Peninsula) block. The sinistral strike-slip component may represent a trench-linked strike-slip movement as a consequence of oblique subduction. Lithostatic pressure decreased and temperature increased to peak values during D-2, interpreted to represent the collision of thickened oceanic crust with the active continental margin. The last deformation phase, D-3, is characterised by post-metamorphic kink bands, partially forming conjugate sets consistent with E-W shortening and N-S extension. The rock units that underlie the island probably rotated during D-3, in Cenozoic times, together with the trench, from an NE-SW to the present ENE-WSW position, during the progressive opening of the Scotia Sea. The similarity between the strain orientation of D-3 and that of the sinistral NE-SW Shackleton Fracture Zone is consistent with this interpretation. (C) 2000 Elsevier B.V. B.V. All rights reserved.

Metamorphic evolution of a subduction complex, South Shetland Islands, Antarctica

A subduction complex composed of ocean floor material mixed with arc-derived metasediments crops out in the Elephant Island group and at Smith Island, South Shetland Islands, Antarctica, with metamorphic ages of 120-80 Ma and 58-47 Ma? respectively. Seven metamorphic zones (I-VII) mapped on Elephant Island delineate a gradual increase in metamorphic grade from the pumpellyite-actinolite facies, through the crossite-epidote blueschist facies, to the lower amphibolite facies. Geothermometry in garnet-amphibole and garnet-biotite pairs yields temperatures of about 350 degrees C in zone III to about 525 degrees C in zone VII. Pressures were estimated on the basis of Si content in white mica, Al2O3 content in alkali amphibole, Na-M4/Al-IV in sodic-calcic and calcic amphibole, Al-VI/Si in calcic amphibole, and jadeite content in clinopyroxene. Mean values vary from about 6-7.5 kbar in zone II to about 5 kbar in zone VII. Results from the other islands of the Elephant Island group are comparable to those from the main island; Smith Island yielded slightly higher pressures, up to 8 kbar, with temperatures estimated between 300 and 350 degrees C. Zoned minerals and other textural indications locally enable inference of P-T-t trajectories, all with a clockwise evolution. A reconstruction in space and time of these P-T-t paths allows an estimate of the thermal structure in the upper crust during the two ductile deformation phases (D-1 & D-2) that affected the area. This thermal structure is in good agreement with the one expected for a subduction zone. The arrival and collision of thickened oceanic crust may have caused the accretion and preservation of the subduction complex. In this model, D-1 represents the subduction movements expressed by the first vector of the clockwise P-T-t path, D-2 reflects the collision corresponding to the second vector with increasing temperature and decreasing pressure, and D-3 corresponds to isostatic uplift accompanied by erosion, under circumstances of decreasing temperature and pressure.

Understanding block rotation of strike-slip fault zones: Paleomagnetic and structural approach

This thesis is focused on the paleomagnetic rotation pattern inside the deforming zone of strike-slip faults, and the kinematics and geodynamics describing it. The paleomagnetic investigation carried out along both the LOFZ and the fore-arc sliver (38º-42ºS, southern Chile) revealed an asymmetric rotation pattern. East of the LOFZ and adjacent to it, rotations are up to 170° clockwise (CW) and fade out ~10 km east of fault. West of the LOFZ at 42ºS (Chiloé Island) and around 39°S (Villarrica domain) systematic CCW rotations have been observed, while at 40°-41°S (Ranco-Osorno domain) and adjacent to the LOFZ CW rotations reach up to 136° before evolving to CCW rotations at ~30 km from the fault. These data suggest a directed relation with subduction interface plate coupling. Zones of high coupling yield to a wide deforming zone (~30 km) west of the LOFZ characterized by CW rotations. Low coupling implies a weak LOFZ and a fore-arc dominated by CCW rotations related to NW-sinistral fault kinematics. The rotation pattern is consistent with a quasi-continuous crust kinematics. However, it seems unlikely that the lower crust flux can control block rotation in the upper crust, considering the cold and thick fore-arc crust. I suggest that rotations are consequence of forces applied directly on both the block edges and along the main fault, within the upper crust. Farther south, at the Austral Andes (54°S) I measured the anisotropy of magnetic susceptibility (AMS) of 22 Upper Cretaceous to Upper Eocene sites from the Magallanes fold-thrust belt internal domains. The data document continuous compression from the Early Cretaceous until the Late Oligocene. AMS data also show that the tectonic inversion of Jurassic extensional faults during the Late Cretaceous compressive phase may have controlled the Cenozoic kinematic evolution of the Magallanes fold-thrust belt, yielding slip partitioning.

Partitioning of deformation within a subduction channel during exhumation of high-pressure rocks: a case study from the Western Alps

The metamorphic belt of the Western Alps was subjected to widespread extensional tectonism at the end of the Eocene (ca. 45-35 Ma). Extension was accommodated by hinterland-directed movements along gently inclined extensional shear zones, which facilitated rapid exhumation of high-pressure and ultra-high-pressure rocks. This deformation resulted in a normal metamorphic sequence. Extension in the inner parts of the Western Alps was coeval with shortening at the front of the belt (foreland-directed thrusts), which took place during decompression, and emplaced higher grade metamorphic units over lower grade metamorphic rocks, thus forming an inverse metamorphic sequence. Two mechanisms for this extensional episode are discussed: (1) collapse of an overthickened lithosphere, and (2) internal readjustments within the orogenic wedge due to subduction channel dynamics. We favour the latter mechanism because it can account for the development of the observed inverse and normal metamorphic sequences along foreland-directed thrusts and hinterland-directed detachments, respectively. This hypothesis is supported by published structural, metamorphic and geochronological data from four geological transects through the Western Alps. This study also emphasizes the importance of post-shearing deformation (e.g. horizontal buckling versus vertical flattening), which can modify the distribution of hinterland- and foreland-directed shear zones in orogenic belts. (c) 2006 Elsevier Ltd. All rights reserved.

Geodynamic evolution of the SW Variscides: Orogenic collapse shown by new tectonometamorphic and isotopic data from western Ossa-Morena Zone, SW Iberia

The pre-Mesozoic geodynamic evolution of SW Iberia has been investigated on the basis of detailed structural analysis, isotope dating, and petrologic study of high-pressure (HP) rocks, revealing the superposition of several tectonometamorphic events: (1) An HP event older than circa 358 Ma is recorded in basic rocks preserved inside marbles, which suggests subduction of a continental margin. The deformation associated with this stage is recorded by a refractory graphite fabric and noncoaxial mesoscopic structures found within the host metasediments. The sense of shear is top to south, revealing thrusting synthetic with subduction (underthrusting) to the north. (2) Recrystallization before circa 358 Ma is due to a regional-scale thermal episode and magmatism. (3) Noncoaxial deformation with top to north sense of shear in northward dipping large-scale shear zones is associated with pervasive hydration and metamorphic retrogression under mostly greenschist facies. This indicates exhumation by normal faulting in a detachment zone confined to the top to north and north dipping shear zones during postorogenic collapse soon after 358 Ma ago (inversion of earlier top to south thrusts). (4) Static recrystallization at circa 318 Ma is due to regional-scale granitic intrusions. Citation: Rosas, F. M., F. O. Marques, M. Ballevre, and C. Tassinari (2008), Geodynamic evolution of the SW Variscides: Orogenic collapse shown by new tectonometamorphic and isotopic data from western Ossa-Morena Zone, SW Iberia, Tectonics, 27, TC6008, doi:10.1029/2008TC002333.

Zone trapping/merging zones in flow analysis: A novel approach for rapid assays involving relatively slow chemical reactions

A novel strategy for accomplishing zone trapping in flow analysis is proposed. The sample and the reagent solutions are simultaneously inserted into convergent carrier streams and the established zones merge together before reaching the detector, where the most concentrated portion of the entire sample zone is trapped. The main characteristics, potentialities and limitations of the strategy were critically evaluated in relation to an analogous flow system with zone stopping. When applied to the spectrophotometric determination of nitrite in river waters, the main figures of merit were maintained, exception made for the sampling frequency which was calculated as 189h(-1), about 32% higher relatively to the analogous system with zone stopping. The sample inserted volume can be increased up to 1.0 mL without affecting sampling frequency and no problems with pump heating or malfunctions were noted after 8-h operation of the system. In contrast to zone stopping, only a small portion of the sample zone is halted with zone trapping, leading to these beneficial effects. (C) 2011 Elsevier B.V. All rights reserved.

Discoloration and fungal growth on three fiber cement formulations exposed in urban, rural and coastal zones

Three formulations of fiber cement were evaluated for fungal colonization and color change after five years of exposure in aging stations located in urban (Sao Paulo), rural (Pirassununga) and coastal (Rio Grande) zones in Brazil. The lowest color change and fungal colonization were registered in Rio Grande, which has a temperate climate, as opposed to Sao Paulo and Pirassununga, which are tropical. The highest fungal colonization was recorded in Sao Paulo, one of the most air polluted cities in Brazil. Pirassununga samples had an intermediate fungal colonization, in spite of showing the highest color change with visible dark spots on the surfaces. These spots were identified as cyanobacteria, which significantly contributed to the darkening of the specimens. The fiber cement formulation, varying in proportion of organic fibers such as poly (vinyl alcohol) and cellulose, was less significant for fungal bioreceptivity than the characteristics of the exposure site. The most frequent fungal genus found in the tropical climate, in both urban and rural zones, and the main one responsible for the higher records in Sao Paulo, was Scytalidiurn sp. which was registered for the first time on this building material in Brazil. (C) 2010 Elsevier Ltd. All rights reserved.