Kinetics of zinc and arsenate co-sorption at the goethite-water interface

Little or no information is available in the literature about reaction processes of co-sorbing metals and arsenate [As(V)] on variable-charged surfaces or factors influencing these reactions. Arsenic and metal contamination are, however, a common co-occurrence in many contaminated environments. In this study, we investigated the co-sorption kinetics of 250 μM As(V) and zinc [Zn(II)] in 10, 100, and 1000 mg goethite L⁻¹ 0.01 M NaCl solution at pH 7, collected complementary As and Zn K-edge extended X-ray absorption fine structure (EXAFS) data after various aging times, and performed a replenishment desorption/dissolution study at pH 4 and 5.5 after 6 months of aging time. Arsenate and Zn(II) formed adamite-like and koritnigite-like precipitates on goethite in 100- and 10-ppm goethite suspensions, respectively, whereas in 1000-ppm goethite suspensions, As(V) formed mostly double-corner sharing complexes and Zn(II) formed a solid solution on goethite according to EXAFS spectroscopic analyses. In all goethite suspension densities, surface adsorption reactions were part of the initial reaction processes. In 10- and 100-ppm goethite suspensions, a heterogeneous nucleation reaction occurred in which adamite-like precipitates began to form 48 h earlier than koritnigite-like surface precipitates. Arsenate and Zn(II) uptake from solution decreased after 4 weeks. Replenishment desorption studies showed that the precipitates and surface adsorbed complexes on goethite were susceptible to proton-promoted dissolution resulting in many cases in more than 80% loss of Zn(II) and ∼ 60% to 70% loss of arsenate. The molar Zn:As dissolution ratio was dependent on the structure of the precipitate and was cyclic for the adamite and koritnigite-like surface precipitates, reflecting the concentric and plane-layered structures of adamite and koritnigite, respectively.     

Thermodynamics and fluid dynamics of effusive subglacial eruptions

We consider the thermodynamic and fluid dynamic processes that occur during subglacial effusive eruptions. Subglacial eruptions typically generate catastrophic floods (jökulhlaups) due to melting of ice by lava and generation of a large water cavity. We consider the heat transfer from basaltic and rhyolitic lava eruptions to the ice for typical ranges of magma discharge and geometry of subglacial lavas in Iceland. Our analysis shows that the heat flux out of cooling lava is large enough to sustain vigorous natural convection in the surrounding meltwater. In subglacial eruptions the temperature difference driving convection is in the range 10–100??°C. Average temperature of the meltwater must exceed 4??°C and is usually substantially greater. We calculate melting rates of the walls of the ice cavity in the range 1–40?m/day, indicating that large subglacial lakes can form rapidly as observed in the 1918 eruption of Katla and the 1996 eruption of Gjálp fissure in Vatnajökull. The volume changes associated with subglacial eruptions can cause large pressure changes in the developing ice cavity. These pressure changes can be much larger than those associated with variation of bedrock and glacier surface topography. Previous models of water-cavity stability based on hydrostatic and equilibrium conditions may not be applicable to water cavities produced rapidly in volcanic eruptions. Energy released by cooling of basaltic lava at the temperature of 1200??°C results in a volume deficiency due to volume difference between ice and water, provided that heat exchange efficiency is greater than approximately 80%. A negative pressure change inhibits escape of water, allowing large cavities to build up. Rhyolitic eruptions and basaltic eruptions, with less than approximately 80% heat exchange efficiency, cause positive pressure changes promoting continual escape of meltwater. The pressure changes in the water cavity can cause surface deformation of the ice. Laboratory experiments were carried out to investigate the development of a water cavity by melting ice from a finite source area at its base. The results confirm that the water cavity develops by convective heat transfer.     

The differentiation of the Skaergaard intrusion

Conclusions We find no support for the claim that the Skaergaard magma followed the trend of common tholeiitic volcanic magmas, such as those of Iceland and the Scottish Tertiary. The end product of differentiation was not a large mass of rhyolite but an iron-rich, silica-poor liquid not unlike that deduced by Wager in 1960.The proposal that a large mass of rhyolitic liquid occupied the upper levels of the intrusion finds no support in the field. The thick series of ferrogabbos, which became richer in iron and poorer in silica until they reached a field of immiscibility cannot be reconciled with crystallization of a large mass of felsic magma. Mass-balance calculations that indicate otherwise are invalid, because they fail to take into account large volumes of rocks that differ in composition from those assumed in the calculations.While ignoring the existence of major units of the intrusion, Hunter and Sparks propose that lavas in Scotland and Iceland are more relevant to the liquid compositions than rocks that are intimately associated with the intrusion. Their argument that the Skaergaard Intrusion followed a trend of silica enrichment that is universal to tholeiitic magmas is based on an incomplete knowledge of the rocks and faulty calculations of mass-balance relations.We agree that much remains to be learned about the Skaergaard Intrusion and the basic mechanisms of magmatic differentiation. In this case, however, we are ready to hang our case on well-established field relations and a mass of laboratory data for what must be the most intensely studied body of rock on Earth.     

Chemical and physical studies of type 3 chondrites—III. Chondrules from the Dhajala H3.8 chondrite

Fifty-eight chondrules were separated from the Dhajala H3.8 chondrite and their thermoluminescence properties were measured. Chips from 30 of the chondrules were examined petrographically and with electron-microprobe techniques; the bulk compositions of 30 chondrules were determined by the fused bead technique. Porphyritic chondrules, especially 5 which have particularly high contents of mesostasis, tend to have higher TL (mass-normalized) than non-porphyritic chondrules. Significant correlations between log(TL) and the bulk CaO, Al₂O₃ and MnO content of the chondrules, and between log(TL) and the CaO, Al₂O₃, SiO₂ and normative anorthite content of the chondrule glass, indicate an association between TL and the abundance and composition of mesostasis. Unequilibrated chondrules ( i.e. those whose olivine is compositionally heterogeneous and high in Ca) have low TL, whereas equilibrated chondrules have a wide range of TL, depending on their chemical and petrographic properties.We suggest that the TL level in a given chondrule is governed by its bulk composition (which largely determined the abundance and composition of constituent glass) and by metamorphism (which devitrfied the glass in those chondrules with high Ca glass to produce the TL phosphor). We also suggest that one reason why certain chondrules in type 3 ordinary chondrites are unequilibrated, while others are equilibrated, is that the mesostasis of the unequilibrated chondrules resisted the devitrification. This devitrification is necessary for the diffusive communication between chondrule grains and matrix that enables equilibration.     

火山通道岩浆流动动力学模型在天池火山喷发过程中的应用

在圆柱形火山通道的下部,岩浆上升速度与岩浆粘度、密度及压力有关。这时的流体动力学过程可以应用一般的牛顿流体模型。火山通道中部气泡化岩浆上升时,液相和气相的转化符合质量守恒方程,混合相总体符合动量守恒方程。其中气泡形成与生长过程符合达西定律与数密度方程。在火山通道靠上部的碎屑化带里,不同组分符合质量守恒方程,混合相总体符合动量守恒方程。天池火山千年大喷发时,通道直径是62m。岩浆房内的岩浆含有约3%体积百分数的气泡,气泡体积在65%时岩浆破碎,颗粒离开通道时的速度是145ms~(-1),而气体离开通道时的速度是170ms~(-1)。气体颗粒分散相出口压力是12.2MPa。在破火山口塌陷之前,岩浆房内气泡体积可高达30%～40%。与此同时,碎屑化发生时岩浆的孔隙度也增加到70%～75%左右。这时的出口压力降低至7～8MPa,出口气体速度增加到180ms~(-1)。气象站碱流质寄生火山喷发对应的喷发通道直径是40m,喷发以气体出口速度15～25ms~(-1)的弱爆破性喷发和侵出式喷发为特征。这时浮岩的孔隙度比千年大喷发的孔隙度低,为48%～61%,而浮岩密度高,为1.01～1.35gcm~(-3)。在侵出相喷发时最高释放率可以达到42m~3s~(-1)(致密岩石当量 DRE),孔隙度变化范围是70%～80%。     

Nudging the Impasse? Lessons From the Nationwide Online Wolf Management Forum in Finland

During the early 2010s, Finnish wolf (Canis lupus) policy reached an impasse. Unfavorable conservation status, intensifying wolf–human conflict, civil disobedience, legislative confusion, and administrative frustration characterized the situation. As part of a participatory updating process for the Finnish national wolf management plan in 2014, we organized a nationwide wolf management forum to explore how e-participation could be used to nurture deliberation for improved wolf policy. We present our interactive method and the resulting wolf territory-based solutions to the wolf problems that the participants of a nationwide online forum identified. The theoretical and practical significance of our work is that we ascribe value to the functional features of these solutions as modifications to the action environment, shared by people and wolves. In this vein, we discuss the role of e-deliberation on the path toward an institutional fit, and we consider how local decision making could help to implement promising wolf territory-level policy interventions.     

Shallow-level decompression crystallisation and deep magma supply at Shiveluch Volcano

Recent petrological studies indicate that some crustal magma chambers may be built up slowly by the intermittent ascent and amalgamation of small packets of magma generated in a deep-seated source region. Despite having little effect on whole-rock compositions, this process should be detectable as variable melt trace element composition, preserved as melt inclusions trapped in phenocrysts. We studied trace element and H₂O contents of plagioclase- and hornblende-hosted melt inclusions from andesite lavas and pumices of Shiveluch Volcano, Kamchatka. Melt inclusions are significantly more evolved than the whole rocks, indicating that the whole rocks contain a significant proportion of recycled foreign material. H₂O concentrations indicate trapping at a wide range of pressures, consistent with shallow decompression-driven crystallisation. The variation of trace element concentrations indicates up to ∼30% decompression crystallisation, which accounts for crystallisation of the groundmass and rims on phenocrysts. Trace element scatter could be explained by episodic stalling during shallow magma ascent, allowing incompatible element concentrations to increase during isobaric crystallisation. Enrichment of Li at intermediate pH₂O reflects influx and condensation of metal-rich vapours. A set of “exotic melts”, identified by their anomalous incompatible trace element characteristics, indicate variable source chemistry. This is consistent with evolution of individual magma batches with small differences in trace element chemistry, and intermittent ascent of magma pulses. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Periodic density functional theory calculations of bulk and the (010) surface of goethite

Background  

Goethite is a common and reactive mineral in the environment. The transport of contaminants and anaerobic respiration of microbes are significantly affected by adsorption and reduction reactions involving goethite. An understanding of the mineral-water interface of goethite is critical for determining the molecular-scale mechanisms of adsorption and reduction reactions. In this study, periodic density functional theory (DFT) calculations were performed on the mineral goethite and its (010) surface, using the Vienna Ab Initio Simulation Package (VASP).     

0422−476: a shell galaxy with azimuthally distributed shells

A morphological and two-colour charge-coupled device photometry study of the shell galaxy 0422−476, one of the richest known azimuthally distributed shell galaxies, is presented. Taking this galaxy as a prototype, a general method for reducing observational data of these objects is defined and quantitative parameters for use in further theoretical studies are derived.
According to some recent models (e.g. that of Thomson and Wright in 1990), the shells in such a galaxy could be density waves induced in a thick disc population of dynamically cold stars by a weak interaction with another galaxy. In 0422−476 there is no evidence of either a conventional exponential disc or a thick disc. Although it is not possible to rule out the weak interaction model, the observations continue to favour the merger model (e.g. that of Quinn from 1984).