Characterization of water in synthetic rhyolitic glasses and natural melt inclusions by Raman spectroscopy

Raman spectroscopy was used to analyze quantitatively water in silicate glasses and melt inclusions and to monitor H₂O–OH speciation. Calibration is based on synthetic glasses with various water contents (0.02–7.67% H₂O); water determination and OH–H₂O differentiation on the area of the Si–O broad band at 468 cm^–1 and the asymmetric O–H band at 3,550 cm^–1. Each Raman spectrum has been decomposed into four Gaussian + Lorentzian components centered at 3,330, 3,458, 3,560, and 3,626 cm^–1 using the Levenberg–Marquardt algorithm. These components are interpreted to be two different types of H₂O molecule sites. The influence of the temperature on the loss of water is more important for molecular water than for the hydroxyl groups. The H₂O–OH partition confirms the typical evolution of water speciation in rhyolitic glasses as a function of the bulk water content. Method limitations have been studied for the application to natural melt inclusions.Editorial responsibility: T.L Grove     

Relationships between field-aligned currents and convection observed by EISCAT and implications concerning the mechanism that produces region-2 currents: Statistical study

Fluid theories explain the origin of region-2 field-aligned currents as the closure of the ring current, driven itself by the azimuthal pressure gradients generated in the magnetospheric ring plasma by the sunward convection. Although the structure of pressure gradients appears experimentally complex, observations confirm that a close connection exists between the region-2 field-aligned currents and the ring current. The fluid linear theory of the adiabatic transport by convection of the ring plasma gives a first estimate of this process, and leads ultimately to phase quadrature (in terms of magnetic local time) between the region-2 field-aligned currents and the convection potential. When significant non-adiabatic processes are taken into account, such as precipitations at auroral latitudes, the theoretical phase difference rotates toward opposition. We determine experimentally the phase relationship between the region-2 field-aligned currents and the convection potential from recent statistics, depending on the magnetic activity index K_p, and performed from the EISCAT data base. For geometrical reasons of sufficient probing of region 2, it is only computed in the case of a moderate magnetic activity corresponding to 2\leqK_p<4. Region-2 field-aligned currents are found to be in phase opposition with the convection electrostatic potential at auroral latitudes. This confirms the importance of non adiabatic processes, especially ion losses, in the generation of region-2 field-aligned currents, as theoretically suggested.     

A multimodel comparison for assessing water temperatures under changing climate conditions via the equilibrium temperature concept: case study of the Middle Loire River,France

This paper investigates three categories of models that are derived from the equilibrium temperature concept to estimate water temperatures in the Loire River in France and the sensitivity to changes in hydrology and climate. We test the models' individual performances for simulating water temperatures and assess the variability of the thermal responses under the extreme changing climate scenarios that are projected for 2081–2100. We attempt to identify the most reliable models for studying the impact of climate change on river temperature (T_w). Six models are based on a linear relationship between air temperatures (T_a) and equilibrium temperatures (T_e), six depend on a logistic relationship, and six rely on the closure of heat budgets. For each category, three approaches that account for the river's thermal exchange coefficient are tested. In addition to air temperatures, an index of day length is incorporated to compute equilibrium temperatures. Each model is analysed in terms of its ability to simulate the seasonal patterns of river temperatures and heat peaks. We found that including the day length as a covariate in regression‐based approaches improves the performance in comparison with classical approaches that use only T_a. Moreover, the regression‐based models that rely on the logistic relationship between T_e and T_a exhibit root mean square errors comparable (0.90 °C) with those obtained with a classical five‐term heat budget model (0.82 °C), despite a small number of required forcing variables. In contrast, the regressive models that are based on a linear relationship T_e = f(T_a) fail to simulate the heat peaks and are not advisable for climate change studies. The regression‐based approaches that are based on a logistic relationship and the heat balance approaches generate notably similar responses to the projected climate changes scenarios. This similarity suggests that sophisticated thermal models are not preferable to cruder ones, which are less time‐consuming and require fewer input data. Copyright © 2012 John Wiley & Sons, Ltd.     

伊犁北部博罗霍努岩体年代学和地球化学研究及其大地构造意义

博罗霍努岩体是发育在新疆伊犁北部的一个大型海西期花岗岩体,总体沿近SE-NW向分布,出露面积逾2000km^2。该岩体主要包括三类花岗岩：灰黑色辉石闪长岩、浅色黑云母花岗岩和紫红色黑云母钾长花岗岩。锆石U-Pb La-ICP-MS定年表明,辉石闪长岩的年龄为301±7Ma．黑云母花岗岩的年龄范围为294±7～285±7Ma,而黑云母钾长花岗岩则形成于280±5～266±6Ma。岩石地球化学分析显示,黑云母花岗岩和钾长花岗岩以准铝或弱过铝I型花岗岩为主,个别属于弱过铝S型花岗岩。在微量元素方面,这些花岗岩均富集轻稀土而亏损重稀土,但来自两个剖面的花岗岩具有不同的稀土元素配分模式,可能代表它们的岩浆源区有所不同,因此需要进一步对这些花岗岩进行同位素地质学研究。相对于洋脊花岗岩而言,博罗霍努岩体的花岗岩明显富集K,Rb,Ba和Th,同时,显著亏损Nb,Ta,Y和Yb。以上地球化学特征及微量元素判别图表明,这些花岗岩类形成于俯冲有关的火山岛弧环境。结合伊犁及邻区岩浆岩的特征及其时代,可以认为博罗霍努岩体的形成与天山北部洋壳向南的俯冲造山作用有关。西天山北部俯冲造山作用最终在中二叠世结束,并在中—晚二叠世进入陆内造山和伸展拉张阶段。     

Assimilation of preexisting Pleistocene intrusions at Long Valley by periodic magma recharge accelerates rhyolite generation: rethinking the remelting model

Rhyolite flows and tuffs from the Long Valley area of California, which were erupted over a two-million-year time period, exhibit systematic trends in Nd, Hf, and Pb isotopes, trace element composition, erupted volume, and inferred magma residence time that provide evidence for a new model for the production of large volumes of silica-rich magma. Key constraints come from geochronology of zircon crystal populations combined with a refined eruption chronology from Ar–Ar geochronology; together these data give better estimates of magma residence time that can be evaluated in the context of changing magma compositions. Here, we report Hf, Nd, and Sr isotopes, major and trace element compositions, ⁴⁰Ar/³⁹Ar ages, and U–Pb zircon ages that combined with existing data suggest that the chronology and geochemistry of Long Valley rhyolites can be explained by a dynamic interaction of crustal and mantle-derived magma. The large volume Bishop Tuff represents the culmination of a period of increased mantle-derived magma input to the Long Valley volcanic system; the effect of this input continued into earliest postcaldera time. As the postcaldera evolution of the system continued, new and less primitive crustal-derived magmas dominated the system. A mixture of varying amounts of more mafic mantle-derived and felsic crustal-derived magmas with recently crystallized granitic plutonic materials offers the best explanation for the observed chronology, secular shifts in Hf and Nd isotopes, and the apparently low zircon crystallization and saturation temperatures as compared to Fe–Ti oxide eruption temperatures. This scenario in which transient crustal magma bodies remained molten for varying time periods, fed eruptions before solidification, and were then remelted by fresh recharge provides a realistic conceptual framework that can explain the isotopic and geochemical evidence. General relationships between crustal residence times and magma sources are that: (1) precaldera rhyolites had long crustal magma residence times and high crustal affinity, (2) the caldera-related Bishop Tuff and early postcaldera rhyolites have lower crustal affinity and short magma residence times, and (3) later postcaldera rhyolites again have stronger crustal signatures and longer magma residence times.     

The Activity Rhythm of Blennius sanguinolentus Pallas*

Abstract. In the field, feeding activity of the algivorous Blennius sanguinolentus increased remarkably from morning to late afternoon. Swimming is evenly distributed; other behaviour does not fall into regular daily patterns. No association was found, save in extreme values, between the distribution of any activity and environmental factors measured simultaneously. We suggest that the feeding cycle is an adaptation to the metabolic properties of green algae, the staple diet of B. sanguinolentus. Activity distributions following predictable short-term fluctuations in food quality are expected to be found in other animals.     

The influence of extraction rate on the reduced sulphur content of Aix-les-Bains’ thermal spring waters: Consequences for resource-quality monitoring

Sulphurous thermal springs account for a few percent of all thermal springs. As each degree of oxidation of elemental S corresponds to a different S species, sulphurous spring waters may contain a variety of S species. Total S content is one of the parameters measured when analysis is carried out for issuing a spa’s operating licence. Under French law these parameters must be stable over time. The two spas in Aix-les-Bains are fed by a number of natural springs and boreholes, whose waters have total reduced S concentrations of between 30 and 800 mg L⁻¹. To ensure compliance with the requirements of the spas’ operating licences, particularly in terms of total reduced S content, official analysis of the waters is carried out every month at random dates and times. Monthly analyses have revealed seasonal variations in the S content of some of Aix-les-Bains’ springs; therefore, more frequent monitoring was carried out in order to investigate the extent and causes of these fluctuations. As well as seasonal variations, this monitoring has revealed daily and hourly fluctuations that appear to be related to extraction rates. For some of the springs and boreholes, S concentrations were correlated with extraction rates; for others, an increase in extraction rate led to a reduction in total S content. Concentrations of sulphide ions (one of the species included in the total sulphur analyses) were monitored at the same time as the total S content. Variations in sulphide ion concentrations and in sulphide concentration/total S ratios did not appear to be linked to variations in flow rate. These tests show that random monthly testing is not suitable for monitoring the stability of S contents, as this parameter can only be considered stable in terms of its yearly mean value.     

Tidal sands as biogeochemical reactors

Sandy sediments of continental shelves and most beaches are often thought of as geochemical deserts because they are usually poor in organic matter and other reactive substances. The present study focuses on analyses of dissolved biogenic compounds of surface seawater and pore waters of Aquitanian coastal beach sediments. To quantitatively assess the biogeochemical reactions, we collected pore waters at low tide on tidal cross-shore transects unaffected by freshwater inputs. We recorded temperature, salinity, oxygen saturation state, and nutrient concentrations. These parameters were compared to the values recorded in the seawater entering the interstitial environment during floods. Cross-shore topography and position of piezometric level at low tide were obtained from kinematics GPS records. Residence time of pore waters was estimated by a tracer approach, using dissolved silica concentration and kinetics estimate of quartz dissolution with seawater. Kinetics parameters were based on dissolved silica concentration monitoring during 20-day incubations of sediment with seawater. We found that seawater that entered the sediment during flood tides remained up to seven tidal cycles within the interstitial environment. Oxygen saturation of seawater was close to 100%, whereas it was as low as 80% in pore waters. Concentrations of dissolved nutrients were higher in pore waters than in seawater. These results suggest that aerobic respiration occurred in the sands. We propose that mineralised organic matter originated from planktonic material that infiltrated the sediment with water during flood tides. Therefore, the sandy tidal sediment of the Aquitanian coast is a biogeochemical reactor that promotes or accelerates remineralisation of coastal pelagic primary production. Mass balance calculations suggest that this single process supplies about 37 kmol of nitrate and 1.9 kmol of dissolved inorganic phosphorus (DIP) to the 250-km long Aquitanian coast during each semi-diurnal tidal cycle. It represents about 1.5% of nitrate and 5% of DIP supplied by the nearest estuary.     

Competitive binding of REE to humic acid and manganese oxide: Impact of reaction kinetics on development of cerium anomaly and REE adsorption

The competitive binding of rare earth elements (REE) to purified humic acid (HA) and MnO₂ was studied experimentally using various HA/MnO₂ ratios over a range of pH (3 to 8). MnO₂, humic acid and REE solutions were simultaneously mixed to investigate the kinetics of the competitive reactions. Aqueous REE–HA complex is the dominant species whatever the experiment time, pH and HA/MnO₂ ratio. The value of the distribution coefficients between MnO₂ and solution (log K_d^Ree/Mno₂) increases with the HA/MnO₂ ratio, indicating that part of the REE–HA complexes are adsorbed onto MnO₂. The development of a Ce anomaly appears strongly limited in comparison with inorganic experimental conditions. Throughout the experimental run time, for HA/MnO₂ ratios of less than 0.4, MnO₂ acts as a competitor leading to a partial dissociation of the REE–HA complex. The majority of the dissociated REE is readsorbed onto the MnO₂ surface. The readsorption of REE is expressed by an increased Ce anomaly on the log K_d^Ree/Mno₂ pattern as well as a change in shape of the coefficient distribution of REE between soluble HA and solution pattern (log K_d^Ree/HA decrease for the heavy rare earth elements — HREE). Thus, REE are not only bound to MnO₂ as a REE–HA complex, but also as REE(III). Moreover, the competition between HA and MnO₂ for REE binding is shown to be higher at low pH (< 6) and low DOC/Mn ratio. This study partially confirms previous work that demonstrated the control of REE adsorption by organic matter, while shedding more light on the impact of pH as well as complexation reaction competition on long-term REE partitioning between solid surface and organic solutions. The latter point is important as regards to REE speciation under conditions typical of rock and/or mineral alteration.