Titanium in subduction zone fluids: First insights from abinitio molecular metadynamics simulations

The preferential incorporation of High-Field-Strength Elements (HFSE) in rutile (TiO₂), combined with its supposed stability in subduction zone settings, make it an ideal candidate to explain the low HFSE concentrations in subduction-derived magmas. The solubility behaviour of rutile is key to these arguments, but at present experimental and field-based evidence are contradictory.We have used abinitio molecular (meta)dynamics to investigate the coordination environment of Ti(IV) in pure water at 300 and 1000 K and densities ranging from 900-1260 kg m⁻³ (approximate pressures 0.9-3.6 GPa). In all high temperature simulations, the long-range structure of the solvent indicates a breakdown of the hydrogen bonding network as expected for supercritical water. The five-fold coordination of titanium to water is energetically most favourable in aqueous fluids at room temperature and pressure, separated from four and six-fold configurations by ∼175 and ∼200 kJ mol⁻¹, respectively. The average first shell Ti-O distance is 2.00 Å, in excellent agreement with bond lengths obtained from experiments. At similar densities and 1000 K, titanium is on average six-fold coordinate with water, and shows some degree of water dissociation in the first hydration shell. This coordination environment is remarkably persistent with increasing density from 1021 to 1260 kg m⁻³ at constant temperature (1000 K). At lower densities, however, (900 kg m⁻³ at 1000 K), the coordination with first shell water molecules is less than five. The observed coordination changes could promote association of titanium with peralkaline or peraluminous domains in the aqueous fluid, and thereby explain field-and laboratory based evidence of enhanced HFSE concentrations.This study demonstrates that abinitio molecular dynamics has considerable potential to access details of element behaviour in aqueous fluids at geologically relevant conditions that are impossible to examine otherwise. Changes in the solvent structure due to density variations lead to differences in solvent behaviour allowing access to new domains for fluid-solid interaction. Moreover, changes in the solvent structure are strongly linked to the effectiveness of element solvation.     

Temperature effects on the calcite skeletal composition of deep-water gorgonians (Isididae)

We test for and calibrate a proxy for ocean temperature based on the skeletal composition of the widely distributed, deep-sea gorgonians in the family Isididae (bamboo corals), through use of three complementary methods: a short-term comparison of element/Ca ratios to a four-year temperature record, a long-term comparison with oceanographic records spanning forty years, and a geographic comparison of Isidids collected at sites ranging from the tropics to Antarctica. The assays consistently support a temperature-dependency for Mg/Ca ratios and suggest S/Ca is indirectly affected by temperature, but indicate little or no effect of temperature on P/Ca and Sr/Ca. The consensus relationship between Mg/Ca and temperature for Isidid calcite from the comparisons with the temperature time-series is T = −0.505 + 0.048 Mg/Ca, where T is in °C, Mg/Ca is in mmol/mol, and the applicable range is 3-6 °C. The results of the geographic assay, though imprecise, suggest the applicable range extends to temperatures below freezing. The scatter of data points around the regression of temperature and Mg/Ca is wide in all assays. This could reflect the effect of factors other than temperature on Mg/Ca ratios, but is also likely to reflect limitations of the field data, the effects of assumed constant growth rates in the corals and instrumental analytical error. The combined effects of micro-scale variability in growth rates and wide confidence intervals for each data point suggests that environmental reconstruction from Isidid internode calcite from sparse data or at time scales less than decades be done with caution. Comparisons within and among colonies do not indicate strong vital effects on ontogenetic variability in the corals, other than possibly close to the central pore of the coral. However, similar Mg/Ca ratios for Isidids from Antarctic and more temperate regions suggest adaptation to local conditions and hence a role for physiology at higher taxonomic levels, at least. Taxonomically higher level vital effects are also suggested by large differences between gorgonian families in their regressions between Mg/Ca and temperature, by Mg/Ca ratios that overlap over a wide temperature and habitat range, and for a non-linear relationship between temperature and the slope of the Mg/Ca-temperature relationship across the order.     

Decadal-Timescale Estuarine Geomorphic Change Under Future Scenarios of Climate and Sediment Supply

Future estuarine geomorphic change, in response to climate change, sea-level rise, and watershed sediment supply, may govern ecological function, navigation, and water quality. We estimated geomorphic changes in Suisun Bay, CA, under four scenarios using a tidal-timescale hydrodynamic/sediment transport model. Computational expense and data needs were reduced using the morphological hydrograph concept and the morphological acceleration factor. The four scenarios included (1) present-day conditions; (2) sea-level rise and freshwater flow changes of 2030; (3) sea-level rise and decreased watershed sediment supply of 2030; and (4) sea-level rise, freshwater flow changes, and decreased watershed sediment supply of 2030. Sea-level rise increased water levels thereby reducing wave-induced bottom shear stress and sediment redistribution during the wind-wave season. Decreased watershed sediment supply reduced net deposition within the estuary, while minor changes in freshwater flow timing and magnitude induced the smallest overall effect. In all future scenarios, net deposition in the entire estuary and in the shallowest areas did not keep pace with sea-level rise, suggesting that intertidal and wetland areas may struggle to maintain elevation. Tidal-timescale simulations using future conditions were also used to infer changes in optical depth: though sea-level rise acts to decrease mean light irradiance, decreased suspended-sediment concentrations increase irradiance, yielding small changes in optical depth. The modeling results also assisted with the development of a dimensionless estuarine geomorphic number representing the ratio of potential sediment import forces to sediment export forces; we found the number to be linearly related to relative geomorphic change in Suisun Bay. The methods implemented here are widely applicable to evaluating future scenarios of estuarine change over decadal timescales.     

10Be and 26Al exposure‐age dating of bedrock surfaces on the Aran ridge,Wales: evidence for a thick Welsh Ice Cap at the Last Glacial Maximum

This paper presents results of the analysis of paired cosmogenic isotopes (¹⁰Be and ²⁶Al) from eight quartz‐rich samples collected from ice‐moulded bedrock on the Aran ridge, the highest land in the British Isles south of Snowdon. On the Aran ridge, comprising the summits of Aran Fawddwy (905 m a.s.l.) and Aran Benllyn (885 m a.s.l.), ²⁶Al and ¹⁰Be ages indicate complete ice coverage and glacial erosion at the global Last Glacial Maximum (LGM). Six samples from the summit ridge above 750–800 m a.s.l. yielded paired ¹⁰Be and ²⁶Al ages ranging from 17.2 to 34.4 ka, respectively. Four of these samples are very close in age (¹⁰Be ages of 17.5 ± 0.6, 17.5 ± 0.7, 19.7 ± 0.8 and 20.0 ± 0.7 ka) and are interpreted as representing the exposure age of the summit ridge. Two other summit samples are much older (¹⁰Be ages of 27.5 ± 1.0 and 33.9 ± 1.2 ka) and these results may indicate nuclide inheritance. The ²⁶Al/¹⁰Be ratios for all samples are indistinguishable within one‐sigma uncertainty from the production rate ratio line, indicating that there is no evidence for a complex exposure history. These results indicate that the last Welsh Ice Cap was thick enough to completely cover the Aran ridge and achieve glacial erosion at the LGM. However, between c. 20 and 17 ka ridge summits were exposed as nunataks at a time when glacial erosion at lower elevations (below 750–800 m a.s.l.) was achieved by large outlet glaciers in the valleys surrounding the mountains. Copyright © 2011 John Wiley & Sons, Ltd.     

Tropical glacier fluctuations in the Cordillera Blanca,Peru between 12.5 and 7.6 ka from cosmogenic 10Be dating

We report cosmogenic surface exposure ¹⁰Be ages of 21 boulders on moraines in the Jeullesh and Tuco Valleys, Cordillera Blanca, Peru (～10°S at altitudes above 4200 m). Ages are based on the sea-level at high-latitude reference production rate and scaling system of Lifton et al. (2005. Addressing solar modulation and long-term uncertainties in scaling secondary cosmic rays for in situ cosmogenic nuclide applications. Earth and Planetary Science Letters 239, 140–161) in the CRONUS-Earth online calculator of Balco et al. (2008. A complete and easily accessible means of calculating surface exposure ages or erosion rates from ¹⁰Be and ²⁶Al measurements. Quaternary Geochronology 3, 174–195). Using the Lifton system, large outer lateral moraines in the Jeullesh Valley have a ¹⁰Be exposure age of 12.4 ka, inside of which are smaller moraine systems dated to 10.8, 9.7 and 7.6 ka. Large outer lateral moraines in the Tuco Valley have a ¹⁰Be exposure age of 12.5 ka, with inner moraines dated to 11.3 and 10.7 ka. Collectively, these data indicate that glacier recession from the Last Glacial Maximum (LGM) in the Cordillera Blanca was punctuated by three to four stillstands or minor advances during the period 12.5–7.6 ka, spanning the Younger Dryas Chronozone (YDC; ～12.9–11.6 ka) and the cold event identified in Greenland ice cores and many other parts of the world at 8.2 ka. The inferred fluctuations of tropical glaciers at these times, well after their withdrawal from the LGM, indicate an increase in precipitation or a decrease in temperature in this region. Although palaeoenvironmental records show regional and temporal variability, comparison with proxy records (lacustrine sediments and ice cores) indicate that regionally this was a cold, dry period so we ascribe these glacier advances to reduced atmospheric temperature rather than increased precipitation.     

Tidal and wind-induced circulation within the Southeastern limit of the Bay of Biscay: Pasaia Bay,Basque Coast

The Basque coastal area, in the southeastern Bay of Biscay, can be characterised as being more influenced by land climate and inputs, than other typically ‘open sea’ areas. The influence of coastal processes, together with the presence of irregular and steep topography, complicate greatly the water circulation patterns. Water movement along the Basque coastal area is not well understood; observations are scarce and long-term current records are lacking. The knowledge available is confined to the surface currents: the surface water circulation is controlled mainly by wind forcing, with tidal and density currents being weak. However, there is a lack of knowledge available on currents within the lower levels of the water column; likewise, on the main time-scales involved in the water circulation. This study quantifies the contribution of the tidal and wind-induced currents, to the overall water circulation; it identifies the main time-scales involved within the tidal and wind-induced flows, investigating difference in such currents, throughout the water column, within Pasaia Bay (Basque coast). Within this context, extensive oceanographic and meteorological data have been obtained, in order to describe the circulation. The present investigation reveals that the circulation, within the surface and the sub-surface waters, is controlled mainly by wind forcing fluctuations, over a wide range of meteorological frequencies: third-diurnal, semidiurnal and diurnal land–sea breezes; synoptic variability; frequencies, near fortnightly periods; and seasonal. At the lower levels of the water column, the main contribution to the water circulation arises from residual currents, followed by wind-induced currents on synoptic time-scales. In contrast, tidal currents contribute minimally to the overall circulation throughout the water column.     

Paragenetic relations in gedrite — cordierite — staurolite — biotite sillimanite — kyanite gneisses at Ajitpura,Rajasthan, India

Aluminous parageneses containing gedrite, cordierite, garnet, staurolite, biotite, sillimanite, kyanite, quartz or spinel plus corundum are found as dark colored lenses in the polymetamorphic, multideformed Archean complex at Ajitpura in northwest peninsular India. Staurolite, like kyanite, is a relict phase of earlier metamorphism and is excluded as a paragenetic mineral in view of its incompatibility with quartz and gedrite and its lower X _Mg values than for garnet of the assemblage. Its stability here is attributed to zinc content of up to 3 wt%. The XMg in other ferromagnesian minerals decreases in the order: cordierite, biotite, gedrite, garnet, as found elsewhere in high grade rocks.The textural criteria and systematic partitioning of Fe and Mg in the ferromagnesian phases, excluding staurolite, indicate attainment of equilibrium during the second metamorphism. From tie line configurations in the phase diagrams, X _Mg ratios in the constituent minerals, and other petrographic criteria, it is suggested that gedrite — cordierite-garnet — sillimanite — biotite assemblage has been produced by the reactions: Biotite+Sillimanite+Quartz = Cordierite+Garnet+K-feldspar+Vapor (1) and Biotite+Sillimanite+Quartz = Cordierite +Gedrite+K-feldspar+Vapor (2) which occurred during partial melting of the rocks at fixed P and T conditions.By isothermal P-X(Fe-Mg) sections it has been demonstrated that release of FeO, SiO₂ and other components modified the composition of the reactant biotite presumably by the substitution FeSi2 Al, whereby reaction 1 was replaced by reaction 2. Cordierite with higher X _Mg was produced with gedrite instead of with garnet, whose X _Mg is less than X _Mg of gedrite. Reaction 2 has been tentatively located in T-P space from the intersection of some continuous loops in the P-X(Fe-Mg) diagram at 700°C and also by other constraints. The discontinuous reaction 2 is located about 1–2 kilobars higher than reaction 1, which implies that it is difficult to distinguish between effects of pressure and those of melting on the X _Mg ratios of the reaction phases.The P-T calibrations of garnet — cordierite, garnet — biotite and garnet — plagioclase equilibria and the calibrations from other dehydration curves give temperatures near 700°C and pressure (assuming ) about 6 kilobars.