Extent and chronology of Quaternary glaciation

In a recent INQUA project the extent of Pleistocene glaciations has been digitally mapped and the chronology of events reviewed. The onset of the present Ice Age in both hemispheres dates back to the Palaeogene. In Greenland, Iceland, North America and southernmost South America sizeable ice sheets formed well before 2.6 ka BP. In Alaska and on Tierra del Fuego the ice advanced further than in any later glaciations. Evidence for Early Pleistocene glaciation （2.6-0. 78 Ma） has been reported from many parts of the world, but in most cases dating remains problematic, and the size of the glaciers and ice sheets is unknown.     

A new method to estimate the oxidation state of basaltic series from microprobe analyses

The oxygen fugacity and therefore the iron redox state of a melt is known to have a strong influence on the liquid line of descent of magmas and thus on the composition of the coexisting melts and crystals. We present a new method to estimate this critical parameter from electron probe microanalyses of two of the most common minerals of basaltic series, plagioclase and clinopyroxene. This method is not based on stoichiometric calculations, but on the different partitioning behaviour of Fe³⁺ and Fe²⁺ between both minerals and a melt phase: plagioclase can incorporate more Fe³⁺ than Fe²⁺, while clinopyroxene can incorporate more Fe²⁺ than Fe³⁺. For example, the effect of oxidizing a partly molten basaltic system (Fe³⁺ is stabilized with respect to Fe²⁺) results in an increase of FeO_total in plagioclase, but a decrease in the associated clinopyroxene. We propose an equation, based on published partition coefficients, that allows estimating the redox state of a melt from these considerations. An application to a set of experimental and natural data attests the validity of the proposed model. The associated error can be calculated and is on average < 1 log unit of the prevailing oxygen fugacity.In order to reduce the number of different variables influencing the Fe²⁺/Fe³⁺ mineral/melt equilibrium, our model is restricted to basaltic series with SiO₂ < 60% that have crystallized at intermediate to low pressure (< 0.5 GPa) and under relatively oxidizing conditions (?FMQ > 0; where FMQ is the fayalite–magnetite–quartz oxygen buffer equilibrium), but it may be parameterized for other conditions. A spreadsheet is provided to assist the use of equations, and to perform the error propagation analysis.     

Effect of oxygen fugacity and water on phase equilibria of a hydrous tholeiitic basalt

The influence of oxygen fugacity and water on phase equilibria and the link between redox conditions and water activity were investigated experimentally using a primitive tholeiitic basalt composition relevant to the ocean crust. The crystallization experiments were performed in internally heated pressure vessels at 200 MPa in the temperature range 940–1,220°C. The oxygen fugacity was measured using the H₂-membrane technique. To study the effect of oxygen fugacity, three sets of experiments with different hydrogen fugacities were performed, showing systematic effects on the phase relations and compositions. In each experimental series, the water content of the system was varied from nominally dry to water-saturated conditions, causing a range of oxygen fugacities varying by ~3 log units per series. The range in oxygen fugacity investigated spans ~7 log units. Systematic effects of oxygen fugacity on the stability and composition of the mafic silicate phases, Cr–spinel and Fe–Ti oxides, under varying water contents were recorded. The Mg# of the melt, and therefore also the Mg# of olivine and clinopyroxene, changed systematically as a function of oxygen fugacity. An example of the link between oxygen fugacity and water activity under hydrogen-buffered conditions is the change in the crystallization sequence (olivine and Cr–spinel) due to a change in the oxygen fugacity caused by an increase in the water activity. The stability of magnetite is restricted to highly oxidizing conditions. The absence of magnetite in most of the experiments allows the determination of differentiation trends as a function of oxygen fugacity and water content, demonstrating that in an oxide-free crystallization sequence, water systematically affects the differentiation trend, while oxygen fugacity seems to have a negligible effect.     

Microbial Dynamics During and After In Situ Chemical Oxidation of Chlorinated Solvents

In situ chemical oxidation (ISCO) followed by a bioremediation step is increasingly being considered as an effective biphasic technology. Information on the impact of chemical oxidants on organohalide respiring bacteria (OHRB), however, is largely lacking. Therefore, we used quantitative PCR (qPCR) to monitor the abundance of OHRB (Dehalococcoides mccartyi, Dehalobacter, Geobacter, and Desulfitobacterium) and reductive dehalogenase genes (rdh; tceA, vcrA, and bvcA) at a field location contaminated with chlorinated solvents prior to and following treatment with sodium persulfate. Natural attenuation of the contaminants tetrachloroethene (PCE) and trichloroethene (TCE) observed prior to ISCO was confirmed by the distribution of OHRB and rdh genes. In wells impacted by persulfate treatment, a 1 to 3 order of magnitude reduction in the abundances of OHRB and complete absence of rdh genes was observed 21 days after ISCO. Groundwater acidification (pH<3) and increase in the oxidation reduction potential (>500 mV) due to persulfate treatment were significant and contributed to disruption of the microbial community. In wells only mildly impacted by persulfate, a slight stimulation of the microbial community was observed, with more than 1 order of magnitude increase in the abundance of Geobacter and Desulfitobacterium 36 days after ISCO. After six months, regeneration of the OHRB community occurred, however, neither D. mccartyi nor any rdh genes were observed, indicating extended disruption of biological natural attenuation (NA) capacity following persulfate treatment. For full restoration of biological NA activity, additional time may prove sufficient; otherwise addition electron donor amendment or bioaugmentation may be required.     

Zircon record of fractionation,hydrous partial melting and thermal gradients at different depths in oceanic crust (ODP Site 735B,South-West Indian Ocean)

Felsic veins (plagiogranites) are distributed throughout the whole oceanic crust section and offer insight into late-magmatic/high temperature hydrothermal processes within the oceanic crust. Despite constituting only 0.5% of the oceanic crust section drilled in IODP Site 735B, they carry a significant budget of incompatible elements, which they redistribute within the crust. Such melts are saturated in accessory minerals, such as zircon, titanite and apatite, and often zircon is the only remaining phase that preserves magmatic composition and records processes of felsic melt formation and evolution. In this study, we analysed zircon from four depths in IODP Site 735B; they come from the oxide gabbro (depth approximately 250 m below sea floor) and plagiogranite (depths c. 500, 860, 940 m below sea floor). All zircons have similar εHf composition of c. 15 units indicating an isotopically homogenous source for the mafic magmas forming IODP Site 735B gabbro. Zircons from oxide gabbro are scarce and variable in composition consistent with their crystallization from melts formed by both fractionation of mafic magmas and hydrous remelting of gabbro cumulate. On the other hand, zircon from plagiogranite is abundant and each sample is characterized by compositional trends consistent with crystallization of zircon in an evolving melt. However, the trends are different between the plagiogranite at 500 m bsf and the deeper sections, which are interpreted as the record of plagiogranite formation by two processes: remelting of gabbro cumulate at 500 m bsf and fractionation at deeper sections. Zircon from both oxide gabbro and plagiogranite has δ¹⁸O from 3.5 to 6.0‰. Values of δ¹⁸O are best explained by redistribution of δ¹⁸O in a thermal gradient and not by remelting of hydrothermally altered crust. Tentatively, it is suggested that fractionation could be an older episode contemporaneous with gabbro crystallization and remelting could be a younger one, triggered by deformation and uplift of the crustal pile.     

Effect of water on tholeiitic basalt phase equilibria: an experimental study under oxidizing conditions

To investigate the effect of water on phase relations and compositions in a basaltic system, we performed crystallization experiments at pressures of 100, 200 and 500 MPa in a temperature range of 940 to 1,220°C using four different water contents. Depending on the water activity, the oxygen fugacity varied between 1 and 4 log units above the quartz-magnetite-fayalite buffer. Addition of water to the dry system shifts the solidus > 250°C to lower temperatures and increases the amount of melt drastically. For instance, at 1,100°C and 200 MPa, the melt fraction increases from 12.5 wt% at a water content of 1.6 wt% to 96.3% at a water content of 5 wt% in the melt. The compositions of the experimental phases also show a strong effect of water. Plagioclase is shifted to higher anorthite contents by the addition of water. Olivine and clinopyroxene show generally higher MgO/FeO ratios with added water, which could also be related to the increasing oxygen fugacity with water. Moreover, water affects the partitioning of certain elements between minerals and melts, e.g., the Ca partitioning between olivine and melt. Plagioclase shows a characteristic change in the order of crystallization with water that may help to explain the formation of wehrlites intruding the lower oceanic crust (e.g., in Oman, Macquarie Island). At 100 MPa, plagioclase crystallizes before clinopyroxene at all water contents. At pressures > 100 MPa, plagioclase crystallizes before clinopyroxene at low water contents (e.g. < 3 wt%), but after clinopyroxene at H₂O in the melt > 3 wt%. This change in crystallization order indicates that a paragenesis typical for wehrlites (olivine–clinopyroxene–without plagioclase) is stabilized at low pressures typical of the oceanic crust only at high water contents. This opens the possibility that typical wehrlites in the oceanic crust can be formed by the fractionation and accumulation of olivine and clinopyroxene at 1,060°C and > 100 MPa in a primitive tholeiitic basaltic system containing more than 3 wt% water. The comparison of the experimental results with evolution trends calculated by the thermodynamic models “MELTS” and “Comagmat” shows that neither model predicts the experimental phase relations with sufficient accuracy.Electronic Supplementary Material Supplementary material is available for this article at and is accessible for authorized users.     

Dating Holocene lavas on Stromboli,Italy using cosmogenic He

In-situ cosmogenic ³He exposure ages of pyroxene phenocrysts from basalts from the Upper Neostromboli formation in southwest Stromboli date its eruption at 7.0 ± 0.3 ka (1σ, n = 3, Ginostra site) and 6.8 ± 0.2 ka (1σ, n = 10, Timpone del Fuoco site) respectively. Correlation of our new data to previous K/Ar and palaeomagnetic ages from the northwestern Neostromboli phase suggests that it erupted within a confined period between roughly 6 and 14 ka. The low uncertainty on the ³He_cos ages as well as on individual exposure ages (4.4–8.7%) demonstrates that ³He_cos exposure dating is a viable tool for dating Holocene basalt lavas. The ages compare favourably to uncertainties obtained for radiocarbon dating of similar rocks.     

Cosmogenic 3He exposure dating of the Quaternary basalts from Fogo,Cape Verdes: Implications for rift zone and magmatic reorganisation

We have used cosmogenic ³He to date pre- and post-collapse lava flows from southwestern Fogo, Cape Verdes, in order to date rift zone magmatic reorganisation following the lateral collapse of the flank of the Monte Amarelo volcano. The post-collapse flows have exposure ages ranging from 62 to 11 ka. The analysis of multiple flow tops on each lava flows, often at different elevations, provides an internal check for age consistency and the exposures ages conform with stratigraphic level. The exposure ages suggest that volcanic activity along the western branch of the triple-armed rift zone was more or less continuous from before 62 ka to approximately 11 ka. The absence of magmatic activity for the last 11 kyr reflects a structural reconfiguration of the volcano and may be related to renewed flank instability. This volcanic hiatus is similar in duration to that observed in the Canary Islands. Replicate ³He exposure ages of a pre-collapse flow (123.0 ± 5.2 ka) brackets the time of the Monte Amarelo collapse between 62 ka and 123 ka. Reproducible cosmogenic ³He exposure ages of less than 123 ka from flows away from major erosion features demonstrates that the technique is a viable alternative to the radiocarbon, K/Ar and ⁴⁰Ar/³⁹Ar chronometers for dating recent volcanism in arid climate zones.     

Geochemical nature and age of the plagiogranite-gabbronorite association of the oceanic core complex of the Mid-Atlantic ridge at 5°10′S

Our newly obtained data on the geochemistry and age of plagiogranite-gabbronorite association in the oceanic core complex of the Mid-Atlantic Ridge (MAR) at 5°10′S suggest close genetic relations between these rocks in this segment of the ridge. The U/Pb zircon age of an oceanic plagiogranite (OPG) sample is 1.059 ± 0.055 Ma and is in good agreement with the zircon age of plutonic rocks in the oceanic core complex of northern MAR. A distinctive geochemical feature of the rocks is their unusually depleted ⁸⁷Sr/⁸⁶Sr and ¹⁴³Nd/¹⁴⁴Nd ratios, which suggest that the plutonic rocks of the gabbronorite-plagiogranite association in MAR at 5°10′S could be derived from the most strongly depleted mantle reservoir of all known to occur beneath the axial MAR zone. The COMAGMAT-5.2 numerical thermodynamic simulation of the possible crystallization links between the plagiogranite and gabbronorite from the MAR segment at 5°10′S led us to conclude that the leading role in the origin of the plagiogranite was played by a two-stage process: the partial melting of the gabbronorite and the subsequent fractionation of the newly generated melt. The regional differences between the isotopic-geochemical parameters of MAR plagiogranites can, perhaps, reflect local specifics of so-called hydrothermal anatexis, such as the geochemical features of the rocks involved in this process and the parameters of the hydrothermal process, for example, variations in the W/R ratio.     

Incomplete reaction of plagioclase in experimental dehydration melting of amphibolite

Dehydration melting of a hornblende‐plagioclase mixture of amphibolitic composition was investigated at 1000°C and at 800 MPa and 1200 MPa. At 1200 MPa the reaction products are garnet, clinopyroxene, melt and relatively Ab‐rich plagioclase (An₄₇). At 800 MPa the products are orthopyroxene, clinopyroxene, magnetite, amphibole (pargasite) and An‐rich plagioclase (An₇₅). The melts are rich in plagioclase components (especially in Ab) and, when compared to tonalites, relatively poor in silica. The grainsize of the starting materials was ≤?5 μm in the 800 MPa and ≤?10 μm in the 1200 MPa runs. All run products show unchanged plagioclase cores, which are the remnants of a very sluggish reaction assumed to be controlled by dissolution/precipitation processes at the plagioclase grain boundaries. The results indicate that only local equilibrium could have been obtained in recent investigations on dehydration melting experiments in plagioclase‐bearing systems. The results also suggest that plagioclase compositions once formed may persist for a very long time, even in hot magma chambers, if the prevailing water activity is low.