The solubility of fluorite in hydrothermal solutions,an experimental study

The solubility of fluorite in NaCl solutions increases with increasing temperature at all ionic strengths up to about 100°C. Above this temperature, the solubility passes through a maximum and possibly a minimum with increasing temperature at NaCl concentrations of 1.0M or less, and increases continuously with increasing temperature at NaCl concentrations above 1.0M. At any given temperature, the solubility of fluorite increases with increasing salt concentration in NaCl, KCl and CaCl₂ solutions. The solubility follows Debye-Hückel theory for KCl solutions. In NaCl and CaCl₂ solutions, the solubility of fluorite increases more rapidly than predicted by Debye-Hückel theory: the excess solubility is due to the presence of NaF^c, CaF⁺, and possibly of Na₂F⁺. The solubility of fluorite in NaCl-CaCl₂ and in NaCl-CaCl₂-MgCl₂ solutions is controlled by the common ion effect and by the presence of NaF^c, CaF⁺, and MgF⁺. The solubility of fluorite in NaCl-HCl solutions increases rapidly with increasing initial HCl concentration; the large solubility increase is due to the presence of HF^c. It seems likely that complexes other than those identified in this study rarely play a major role in fluoride transport and fluorite deposition at temperatures below 300°C.     

Fluorite deposition in hydrothermal systems

During the formation of fluorite deposits fluorite is precipitated either as a consequence of changes in temperature and pressure along the flow path of hydrothermal solutions or due to fluid mixing, or as the result of the interaction of hydrothermal solutions with wall rocks.A decrease in temperature in the flow direction is the most appealing, though still unproven, mechanism of fluorite deposition in Mississippi Valley fluorite deposits.Mixing can produce solutions which are either undersaturated or supersaturated with respect to fluorite. The most important parameters are the temperature, the salinity, and the calcium and fluoride concentration of the fluids prior to mixing.A variety of wall rock reactions can lead to fluorite precipitation. Among these reactions which increase the pH of initially rather acid (pH ≤ 3) hydrothermal solutions are apt to be particularly important.     

Confronted by Insurmountable Opportunities: Geography in Society at the AAG's Centennial*

Geographers at the AAG's centennial are challenged with exceptional opportunities to create a more central place for geography in society and in the university. Realizing these opportunities requires identifying and leveraging key emerging trends in the formation and uses of geographic knowledge. Better integration of geography's profound technological innovations with its core traditions also is necessary to strengthen the discipline's research capacity, and to more effectively engage with and contribute to the needs of society. Trends toward multidisciplinary research and integrative science, and the heightened need for geographic understanding in today's world, hold further promise for advancing the discipline while sustaining its historic strengths and diversity.     

Evidence from kimberlitic zircon for a decreasing mantle Th/U since the Archean

A decoupling in MORB of measured Th/U (κ = 2.5) from that calculated by Pb isotopes (κ = 3.8) for the depleted asthenosphere is well established, and has been referred to as the second Pb paradox (Kramers, J.D., and Tolstikhin, I.N., 1997. Two terrestrial lead isotope paradoxes, forward transport modelling, core formation and the history of the continental crust. Chem. Geol., 139, 75–110.) or the kappa conundrum (Elliott, T., Zindler, A., and Bourdon, B., 1999. Exploring the kappa conundrum: the role of recycling in the lead isotope evolution of the mantle. Earth Planet. Sci. Lett., 169, 129–145.). More controversial has been the cause and timing of this phenomenon, although a higher return flux of U⁶⁺ relative to Th⁴⁺ and(or) the recycling of crustal Pb into the mantle have become the preferred explanations of most workers. Such a combined mechanism effectively operating over the past 2.5 Ga was modelled in plumbotectonics (Zartman, R.E., and Haines, S., 1988. The plumbotectonics model for Pb isotopic systematics among major terrestrial reservoirs—a case for bi–directional transport. Geochim. Cosmochim. Acta, 52, 1327–1339. 709.33.), and found to be quantitatively feasible.A large TIMS, SIMS and LA-ICPMS database of Th and U concentrations for kimberlite-hosted zircon, particularly from Cr-poor megacrystic suites, now exists (Kinny et al., 1989, Berryman et al., 1999, Griffin et al., 2000 and Spetsius et al., 2002; Appendix A and Appendix B, this work). Six suites comprising 10 or more zircon grains with ages between 90 and 2550 Ma reveal consistent patterns when plotted on Th/U vs. U diagrams. We interpret these patterns as resulting from fractional crystallization of a melt with kimberlite affinity presumably derived from the asthenosphere, permitting the extrapolation to an initial Th/U at the time zircon crystallization began. A two-fold decrease is seen in this ratio over the past 2.5 Ga, suggesting that during this time a similar change has occurred in the parent silicate melt. Estimates of Th and U distribution coefficients between zircon and coexisting melt permit calculation of Th/U in the melt, which, for these highly incompatible elements, presumably is the same as for its mantle source rock. Kimberlitic zircon may thus indeed give evidence of a reduction in κ, tentatively calculated as from 4 to 2, since the Archean for the depleted asthenosphere.     

Manganese oxidation in pH and O2 microenvironments produced by phytoplankton

Pure cultures of Chlorella sp. catalyzed the oxidation of soluble Mn(II) to particulate, extracellular, manganic oxides. Manganese oxidation was dependent on photosynthetic activity: no oxidation was observed in the dark when cells were grown heterotrophically on glucose, or in the light when photosystem II was inhibited by the addition of DCMU. Manganates were not formed when media were buffered below pH 8.0, suggesting that an important driving force for manganese oxidation was the high pH resulting from photosynthesis. Field studies with minielectrodes in Oneida Lake, New York, demonstrated steep gradients of O2 and pH and the presence of particulate manganic oxides associated with pelagic aggregates of the cyanobacterium Microcystis sp. The manganese oxidation reaction apparently occurs only when photosynthesizing algae are present as dense populations that can generate microenvironments of high (>9.0) pH, either as aggregates in the pelagic zone or concentrated cell cultures in the laboratory. A large-scale transition from soluble to particulate manganese was measured in the surface waters of Oneida Lake throughout summer 1986. Removal of Mn(II) was correlated with the presence of aggregate-forming cyanobacteria that oxidize Mn(II) by the mechanism described above.     

Chemistry of rainfall,throughfall and stemflow in a eucalypt forest and a pine plantation in south-eastern Australia: 1. Rainfall

Rainfall samples were collected from several hundred rainfall events. Up to nine samples per event were collected from sites 3–500 m apart. They differed substantially in both concentration and composition, even though great care was taken to wash all collectors beforehand. Dryfall, storage and analytical procedures could not explain the variation. When data for rainfall events of similar size (but very different cation inputs) were examined, the major differences were associated with the prevailing wind direction. Events leading to high concentrations were associated with easterly winds and showed the influence of a marine source. Chemical concentration and composition were not altered by the occurrence of a drought year followed by a very wet year. The mean pH was 5·3 and ranged from 4·6 to 5·8. For a given event, a difference of 0·5 often occurred between collection sites. Regular seasonal variations in the concentration of NO₃-N and the NO₃/NH₄ ratio occurred, with the ratio being higher in summer due primarily to bush fires. Organic nitrogen comprised 14% of total nitrogen.     

1500 years of lake sedimentation due to fire,earthquakes, floods and land clearance in the Oregon Coast Range: geomorphic sensitivity to floods during timber harvest period

Sediment cores retrieved from landslide‐dammed Loon Lake recorded events back to the 5th century AD in a forested, mountainous catchment, thereby providing an opportunity to compare the impacts of known recent perturbations, including floods and timber harvesting with those of an early period in the cores, floods, fires, and earthquakes. High‐resolution multi‐parameter (grain size, %TC, %TN, and magnetic susceptibility) data allowed the core stratigraphy to be classified as background sedimentation and events. ¹³⁷Cs and radiocarbon dating, as well as a varved record in the last 75 years provided age control. Mean mass accumulation rate from 1939 to 1978 AD, the time of peak timber harvest and a cool wet phase of the Pacific Decadal Oscillation, was 0.79 (0.74–0.92, 95% C.L.) g cm^‐2 y^‐1, significantly higher than mean rates of both the more recent contemporary period (coincident with the passing of the legislation that regulated harvesting practices in the region), 1979–2012 AD, at 0.58 (0.48‐0.70) and the entire early period, 0.44 (0.41–0.46). Several event deposits are coeval with independently estimated ages of eight Cascadia subduction zone earthquakes in the early period, including the 1700 AD Mw 9.0 event. These deposits are predominantly formed by hyperpycnal flows, as are the known event deposits in the contemporary period. The high mass accumulation rate and greater frequency of thick event deposits during the early contemporary period point to the extraordinary role of timber harvesting in priming the landscape for subsequent sedimentary delivery during floods. Copyright © 2017 John Wiley & Sons, Ltd.     

Sailfish (Istiophorus platypterus) spawning and larval environment in a Florida Current frontal eddy

Fronts and eddies are widely hypothesized to be critical spawning habitat for large pelagic fishes, due to increased larval and/or adult feeding opportunities at these features. We examined sailfish (Istiophorus platypterus) spawning around a cyclonic, submesoscale (∼13 × 7 km) Florida Current frontal eddy. The temporal progression of eddy dynamics over a 65 h period was determined using ocean color satellite imagery, continuous surface measurements along the cruise track, and non-linear least-squares fitting of the positions of three drifters deployed within the eddy. A peak in larval sailfish densities (n = 2435, stations = 49), composed primarily of yolk-sac and first-feeding larvae, occurred at the eddy frontal zone. A majority of these larvae were estimated to have been spawned during the formation of the eddy. A comparison between the distribution of similar-age sailfish and scombrid larvae indicated that the peak in larval sailfish density likely resulted from spawning directly at the front, rather than transport by convergent flow. The first-feeding prey items of larval sailfish (Farranula and Corycaeus copepods) were most abundant at the frontal zone and to a lesser extent inside the eddy. Egg distributions were used to indirectly assess the distribution of adult sailfish prey items. Euthynnus alleteratus and Auxis spp. eggs were in highest abundance outside the eddy, while the eggs of small carangids were in highest abundance at the eddy frontal zone. Overall, this study indicates that sailfish spawn at small-scale oceanographic features that provide a favorable feeding environment for their larvae and potentially also for the adults.