Crystal chemistry of titanite-structured compounds: the CaTi1-x Zr x OSiO4 (x≤0.5) series

Inhomogeneous aggregates of late-stage titanite enriched in Zr have been described recently from post-magmatic parageneses in silica-undersaturated rocks. In the natural samples, simple isovalent substitution of the large Zr (^[vi]R⁴⁺=0.72 Å) for Ti (^[vi]R⁴⁺=0.605 Å) is limited to an empirical maximum of 0.25 afu (15.3 wt.% ZrO₂). As the natural material is not suitable for crystallographic study, a series of CaTi_1-xZr_xOSiO₄ titanite samples have been synthesized by standard ceramic methods at ambient pressure in air, and their crystal structure determined by Rietveld refinement of laboratory powder X-ray diffraction patterns. All of the synthetic Zr-doped titanite varieties adopt space group A2/a and consist of distorted CaO₇ polyhedra together with less distorted (Ti_1-xZr_x)O₆ octahedra and SiO₄ tetrahedra. Cell dimensions and atomic coordinates together with volumes and distortion indices are given for all polyhedra. The empirical limit for Zr substitution in synthetic (F,OH)-free titanite is 0.5 afu (29.6 wt.% ZrO₂). The existence of a Zr analogue of titanite in nature is considered to be unlikely.     

Variation in nitrate and calcium as indicators of recharge pathways in Nolte Spring, PA

This study documents variations in calcium and nitrate concentrations that suggest changes in recharge pathways in a karst spring. The nitrate concentrations increased at the end of the growing season, showing the importance of the soil zone in the recharge pathway. The increase occurred over just a few days, which may be indicative of a change in contribution of baseflow in different seasons from deep to shallow groundwater. The calcium concentrations decreased several days after storm events. A change in the carbonate equilibrium is hypothesized because chloride was not diluted during these events. The decrease in calcium could be due to outgassing and calcite precipitation in the recharge area when older, higher ionic strength matrix water mixes with stormwater in open conduits. The use of geochemical indicators to better understand recharge pathways benefited from long-term monitoring and periods of daily sampling.     

Gas hydrate systems at Hydrate Ridge offshore Oregon inferred from molecular and isotopic properties of hydrate-bound and void gases

We report and discuss molecular and isotopic properties of hydrate-bound gases from 55 samples and void gases from 494 samples collected during Ocean Drilling Program (ODP) Leg 204 at Hydrate Ridge offshore Oregon. Gas hydrates appear to crystallize in sediments from two end-member gas sources (deep allochthonous and in situ) as mixtures of different proportions. In an area of high gas flux at the Southern Summit of the ridge (Sites 1248-1250), shallow (0-40 m below the seafloor [mbsf]) gas hydrates are composed of mainly allochthonous mixed microbial and thermogenic methane and a small portion of thermogenic C₂₊ gases, which migrated vertically and laterally from as deep as 2- to 2.5-km depths. In contrast, deep (50-105 mbsf) gas hydrates at the Southern Summit (Sites 1248 and 1250) and on the flanks of the ridge (Sites 1244-1247) crystallize mainly from microbial methane and ethane generated dominantly in situ. A small contribution of allochthonous gas may also be present at sites where geologic and tectonic settings favor focused vertical gas migration from greater depth (e.g., Sites 1244 and 1245). Non-hydrocarbon gases such as CO₂ and H₂S are not abundant in sampled hydrates. The new gas geochemical data are inconsistent with earlier models suggesting that seafloor gas hydrates at Hydrate Ridge formed from gas derived from decomposition of deeper and older gas hydrates. Gas hydrate formation at the Southern Summit is explained by a model in which gas migrated from deep sediments, and perhaps was trapped by a gas hydrate seal at the base of the gas hydrate stability zone (GHSZ). Free gas migrated into the GHSZ when the overpressure in gas column exceeded sealing capacity of overlaying sediments, and precipitated as gas hydrate mainly within shallow sediments. The mushroom-like 3D shape of gas hydrate accumulation at the summit is possibly defined by the gas diffusion aureole surrounding the main migration conduit, the decrease of gas solubility in shallow sediment, and refocusing of gas by carbonate and gas hydrate seals near the seafloor to the crest of the local anticline structure.     

Glacial flood pulse effects on benthic fauna in equatorial high‐Andean streams

Equatorial glacier‐fed streams present unique hydraulic patterns when compared to glacier‐fed observed in temperate regions as the main variability in discharge occurs on a daily basis. To assess how benthic fauna respond to these specific hydraulic conditions, we investigated the relationships between flow regime, hydraulic conditions (boundary Reynolds number, Re*), and macroinvertebrate communities (taxon richness and abundance) in a tropical glacier‐fed stream located in the high Ecuadorian Andes (> 4000 m). Both physical and biotic variables were measured under four discharge conditions (base‐flow and glacial flood pulses of various intensities), at 30 random points, in two sites whose hydraulic conditions were representative to those found in other streams of the study catchment. While daily glacial flood pulses significantly increased hydraulic stress in the benthic habitats (appearance of Re* > 2000), low stress areas still persisted even during extreme flood events (Re* < 500). In contrast to previous research in temperate glacier‐fed streams, taxon richness and abundance were not significantly affected by changes in hydraulic conditions induced by daily glacial flood pulses. However, we found that a few rare taxa, in particular rare ones, preferentially occurred in highly stressed hydraulic habitats. Monte‐Carlo simulations of benthic communities under glacial flood reduction scenarios predicted that taxon richness would be significantly reduced by the loss of high hydraulic stress habitats following glacier shrinking. This pioneer study on the relationship between hydraulic conditions and benthic diversity in an equatorial glacial stream evidenced unknown effects of climate change on singular yet endangered aquatic systems. Copyright © 2013 John Wiley & Sons, Ltd.     

High‐grade metamorphism and partial melting in Archean composite grey gneiss complexes

Much of the exposed Archean crust is composed of composite gneiss which includes a large proportion of intermediate to tonalitic material. These gneiss terranes were typically metamorphosed to amphibolite to granulite facies conditions, with evidence for substantial partial melting at higher grade. Recently published activity–composition (a?x) models for partial melting of metabasic to intermediate compositions allows calculation of the stable metamorphic minerals, melt production and melt composition in such rocks for the first time. Calculated P?T pseudosections are presented for six bulk rock compositions taken from the literature, comprising two metabasic compositions, two intermediate/dioritic compositions and two tonalitic compositions. This range of bulk compositions captures much of the diversity of rock types found in Archean banded gneiss terranes, enabling us to present an overview of metamorphism and partial melting in such terranes. If such rocks are fluid saturated at the solidus, they first begin to melt in the upper amphibolite facies. However, at such conditions, very little (< 5%) melt is produced and this melt is granitic in composition for all rocks. The production of greater proportions of melt requires temperatures ～800–850 °C and is associated with the first appearance of orthopyroxene at pressures below 8–9 kbar or with the appearance and growth of garnet at higher pressures. The temperature at which orthopyroxene appears varies little with composition providing a robust estimate of the amphibolite–granulite facies boundary. Across this boundary, melt production is coincident with the breakdown of hornblende and/or biotite. Melts produced at granulite facies range from tonalite–trondhjemite–granodiorite for the metabasic protoliths, granodiorite to granite for the intermediate protoliths and granite for the tonalitic protoliths. Under fluid‐absent conditions the melt fertility of the different protoliths is largely controlled by the relative proportions of hornblende and quartz at high grade, with the intermediate compositions being the most fertile. The least fertile rocks are the most leucocratic tonalites due to their relatively small proportions of hydrous mafic phases such as hornblende or biotite. In the metabasic rocks, melt production becomes limited by the complete consumption of quartz to higher temperatures. The use of phase equilibrium forward‐modelling provides a thermodynamic framework for understanding melt production, melt loss and intracrustal differentiation during the Archean.     

Anisotropic damage of rock joints during cyclic loading: constitutive framework and numerical integration

This work describes a constitutive framework for modeling the behavior of rough joints under cyclic loading. Particular attention is paid to the intrinsic links between dilatancy, surface degradation, and mobilized shear strength. The framework also accounts for the important effect of shear‐induced anisotropy. The resulting approach is fully three‐dimensional and is not restricted to plane‐displacement kinematics. Both the governing formulation and an algorithm for implicit numerical integration are presented. While the proposed methods are general, we also postulate a specific model that is compared with experimental data. It employs relatively few free parameters but shows good agreement with laboratory tests. Copyright © 2013 John Wiley & Sons, Ltd.     

New mineral activity–composition relations for thermodynamic calculations in metapelitic systems

New activity–composition (a–x) relations for minerals commonly occurring in metapelites are presented for use with the internally consistent thermodynamic dataset of Holland & Powell ( 2011 , Journal of Metamorphic Geology, 29 , 333–383). The a–x relations include a broader consideration of Fe₂O₃ in minerals, changes to the formalism of several phases and order–disorder in all ferromagnesian minerals where Fe–Mg mixing occurs on multiple sites. The a–x relations for chlorite, biotite, garnet, chloritoid, staurolite, cordierite, orthopyroxene, muscovite, paragonite and margarite have been substantially reparameterized using the approach outlined in the companion paper in this issue. For the first time, the entire set of a–x relations for the common ferromagnesian minerals in metapelitic rocks is parameterized simultaneously, with attention paid to ensuring that they can be used together to calculate phase diagrams of geologically appropriate topology. The a–x relations developed are for use in the Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–O₂ (NCKFMASHTO) system for both subsolidus and suprasolidus conditions. Petrogenetic grids in KFMASH and KFMASHTO are similar in topology to those produced with earlier end‐member datasets and a–x relations, but with some notable differences. In particular, in subsolidus equilibria, the FeO/(FeO + MgO) of garnet is now greater than in coexisting staurolite, bringing a number of key staurolite‐bearing equilibria into better agreement with inferences from field and petrographic observations. Furthermore, the addition of Fe³⁺ and Ti to a number of silicate phases allows more plausible equilibria to be calculated in relevant systems. Pseudosections calculated with the new a–x relations are also topologically similar to equivalent diagrams using earlier a–x relations, although with many low variance fields shifting in P–T space to somewhat lower pressure conditions.     

Fluvial archives as a framework for the Lower and Middle Palaeolithic: patterns of British artefact distribution and potential chronological implications

With the adoption of an ‘expanded chronology’ for the Middle Pleistocene, based on the greater number of warm and cold episodes evident in the marine oxygen isotope record from deep ocean cores, has come the recognition of a meaningful progression of artefact types, something that could not be achieved with reference to the previous ‘compressed chronology’. In Britain, at least, it has been established that Levallois knapping techniques appeared in MIS 9–8, that bout coupé handaxes are indicative of MIS 3 and, rather more tentatively, that assemblages with twisted ovate handaxes in significant numbers represent MIS 11 occupation. Added to these key markers, it is now possible to suggest that further tool types occur preferentially in deposits of particular age: assemblages with significant proportions of cleavers and ‘ficron’ handaxes appear to be correlated with deposits formed at around the time of the MIS 9 interglacial. This newly recognized patterning within the Lower and Middle Palaeolithic record differs markedly from the previous use, in the mid‐20th century, of archaeological typology as a means of dating Pleistocene sequences, which was based on a relative refinement of tool making that is now recognized to be unrelated to age. Indeed, the authors would wish to emphasize that, even with reference to the new scheme presented here, the archaeological record should only be seen as dating evidence ‘of last resort’.