Na depletion in modern adakites via melt / rock reaction within the sub-arc mantle

Interaction between slab-derived melt and mantle peridotite and the role of slab melt as a metasomatizing agent in the sub-arc mantle is being increasingly recognized. Adakite, the slab melt erupted on the surface, usually exhibits anomalously high MgO, CaO, Cr and Ni contents that indicate interaction with mantle peridotitite. Here we note that Cenozoic adakites have Na₂O contents below 5.8 wt.% with ∼95% samples lower than 5.0 wt.%, and are generally depleted in this component relative to experimental basalt partial melts (mostly beyond 5.0 wt.% and up to 9.0 wt.% Na₂O) produced under 1.5-3.0 GPa conditions that are most relevant to adakite production. We interpret the adakite Na depletion to be also a consequence of the melt / rock reaction that takes place within the hot mantle wedge. During ascent and reaction with mantle peridotite, primary adakite melts gain mantle components MgO, CaO, Cr and Ni but lose Na₂O, SiO₂ and perhaps K₂O to the mantle, leading to Na-rich mantle metasomatism. Selective assimilation of predominately mantle clinopyroxene, some spinel and minor olivine at high T/P has been considered to be an important process in producing high-Mg adakites from primary low-Mg slab melts [Killian, R., Stern, C. R., 2002. Constraints on the interaction between slab melts and the mantle wedge from adakitic glass in peridotite xenoliths. Eur. J. Mineral. 14, 25-36]. In such a process, Na depletion in the assimilated melt is the result of dilution due to the increase in melt mass. Phase relationships in the reaction system siliceous melt + peridotite and quantitative calculation suggest that assimilation of mantle clinopyroxene, olivine and spinel and fractional crystallization of sodic amphibole and orthopyroxene, under conditions of moderate T/P and increasing melt mass, is also an important process that modifies the composition of adakites and causes the Na depletion.     

Quaternary tectonic faulting in the Eastern United States

Paleoseismological study of geologic features thought to result from Quaternary tectonic faulting can characterize the frequencies and sizes of large prehistoric and historical earthquakes, thereby improving the accuracy and precision of seismic-hazard assessments. Greater accuracy and precision can reduce the likelihood of both underprotection and unnecessary design and construction costs. Published studies proposed Quaternary tectonic faulting at 31 faults, folds, seismic zones, and fields of earthquake-induced liquefaction phenomena in the Appalachian Mountains and Coastal Plain. Of the 31 features, seven are of known origin. Four of the seven have nontectonic origins and the other three features are liquefaction fields caused by moderate to large historical and Holocene earthquakes in coastal South Carolina, including Charleston; the Central Virginia Seismic Zone; and the Newbury, Massachusetts, area. However, the causal faults of the three liquefaction fields remain unclear. Charleston has the highest hazard because of large Holocene earthquakes in that area, but the hazard is highly uncertain because the earthquakes are uncertainly located.Of the 31 features, the remaining 24 are of uncertain origin. They require additional work before they can be clearly attributed either to Quaternary tectonic faulting or to nontectonic causes. Of these 24, 14 features, most of them faults, have little or no published geologic evidence of Quaternary tectonic faulting that could indicate the likely occurrence of earthquakes larger than those observed historically. Three more features of the 24 were suggested to have had Quaternary tectonic faulting, but paleoseismological and other studies of them found no evidence of large prehistoric earthquakes. The final seven features of uncertain origin require further examination because all seven are in or near urban areas. They are the Moodus Seismic Zone (Hartford, Connecticut), Dobbs Ferry fault zone and Mosholu fault (New York City), Lancaster Seismic Zone and the epicenter of the shallow Cacoosing Valley earthquake (Lancaster and Reading, Pennsylvania), Kingston fault (central New Jersey between New York and Philadelphia), and Everona fault-Mountain Run fault zone (Washington, D.C., and Arlington and Alexandria, Virginia).     

Vapor pressures and evaporation coefficients for melts of ferromagnesian chondrule-like compositions

To determine evaporation coefficients for the major gaseous species that evaporate from silicate melts, the Hertz-Knudsen equation was used to model the compositions of residues of chondrule analogs produced by evaporation in vacuum by Hashimoto [Hashimoto A. (1983) Evaporation metamorphism in the early solar nebula-evaporation experiments on the melt FeO-MgO-SiO₂-CaO-Al₂O₃ and chemical fractionations of primitive materials. Geochem. J. 17, 111-145] and Wang et al. [Wang J., Davis A. M., Clayton R. N., Mayeda T. K., Hashimoto A. (2001) Chemical and isotopic fractionation during the evaporation of the FeO-MgO-SiO₂-CaO-Al₂O₃-TiO₂ rare earth element melt system. Geochim. Cosmochim. Acta 65, 479-494], in vacuum and in H₂ by Yu et al. [Yu Y., Hewins R. H., Alexander C. M. O’D., Wang J. (2003) Experimental study of evaporation and isotopic mass fractionation of potassium in silicate melts. Geochim. Cosmochim. Acta 67, 773-786], and in H₂ by Cohen et al. [Cohen B. A., Hewins R. H., Alexander C. M. O’D. (2004) The formation of chondrules by open-system melting of nebular condensates. Geochim. Cosmochim. Acta 68, 1661-1675]. Vapor pressures were calculated using the thermodynamic model of Ghiorso and Sack [Ghiorso M. S., Sack R. O. (1995) Chemical mass transfer in magmatic processes IV. A revised and internally consistent thermodynamic model for the interpolation and extrapolation of liquid-solid equilibria in magmatic systems at elevated temperatures and pressures. Contrib. Mineral. Petrol. 119, 197-212], except for the late, FeO-free stages of the Wang et al. (2001) and Cohen et al. (2004) experiments, where the CMAS activity model of Berman [Berman R. G. (1983) A thermodynamic model for multicomponent melts, with application to the system CaO-MgO-Al₂O₃-SiO₂. Ph.D. thesis, University of British Columbia] was used. From these vapor pressures, evaporation coefficients (α) were obtained that give the best fits to the time variation of the residue compositions. Evaporation coefficients derived for Fe_(g), Mg_(g), and SiO_(g) from the Hashimoto (1983) experiments are similar to those found by Alexander [Alexander C. M. O’D. (2004) Erratum. Meteoritics Planet. Sci. 39, 163] in his EQR treatment of the same data and also adequately describe the FeO-bearing stages of the Wang et al. (2001) experiments. From the Yu et al. (2003) experiments at 1723 K, α_Na = 0.26 ± 0.05, and α_K = 0.13 ± 0.02 in vacuum, and α_Na = 0.042 ± 0.020, andα_K = 0.017 ± 0.002 in 9 × 10⁻⁵ bar H₂. In the FeO-free stages of the Wang et al. (2001) experiments, α_Mg and α_SiO are significantly different from their respective values in the FeO-bearing portions of the same experiments and from the vacuum values obtained at the same temperature by Richter [Richter F. M., Davis A. M., Ebel D. S., Hashimoto A. (2002) Elemental and isotopic fractionation of Type B calcium-, aluminum-rich inclusions: experiments, theoretical considerations, and constraints on their thermal evolution. Geochim. Cosmochim. Acta 66, 521-540] for CMAS compositions much lower in MgO. When corrected for temperature, the values of α_Mg and α_SiO that best describe the FeO-free stages of the Wang et al. (2001) experiments also adequately describe the FeO-free stage of the Cohen et al. (2004) H₂ experiments, but α_Fe that best describes the FeO-bearing stage of the latter experiment differs significantly from the temperature-corrected value derived from the Hashimoto (1983) vacuum data.     

The mechanisms of reduction of hexavalent chromium by green rust sodium sulphate: Formation of Cr-goethite

The molecular-level processes that control green rust sodium sulphate (GR_Na,SO4) reaction with chromate were studied using high-resolution techniques. Changes in solid morphology, structure and composition were observed with atomic force microscopy, transmission electron microscopy and X-ray diffraction. The results suggest the following mechanisms: Chromate replaces sulphate in the GR interlayer and is reduced by Fe(II). Formation of sparingly soluble Cr(III)-solid blocks further chromate entry, but Cr(VI) reduction continues at the GR solid/solution interface. Electron transfer from the centre of the GR crystals to the surface facilitates rapid reaction. Less stable zones of the reacted GR_Na,SO4 dissolve and amorphous Cr(III),Fe(III)-solid forms. During equilibration, Cr-substituted goethite evolves in association with remaining GR_Na,SO4, fed by material from the amorphous phase and dissolving oxidised GR. In contrast, previous Cr(VI) experiments with the carbonate form of GR, GR_CO3, have suggested only reaction and deposition at the surface. From the perspective of environmental protection, these results have important implications. Goethite is sparingly soluble and the inclusion of Cr(III) as a solid-solution makes it even less soluble. Compared to Cr adsorbed at the surface of an Fe(III)-phase, Cr(III) incorporated in goethite is much less likely to be released back to groundwater.     

Tracing nitrogen in volcanic and geothermal volatiles from the Nicaraguan volcanic front

We report new chemical and isotopic data from 26 volcanic and geothermal gases, vapor condensates, and thermal water samples, collected along the Nicaraguan volcanic front. The samples were analyzed for chemical abundances and stable isotope compositions, with a focus on nitrogen abundances and isotope ratios. These data are used to evaluate samples for volatile contributions from magma, air, air-saturated water, and the crust. Samples devoid of crustal contamination (based upon He isotope composition) but slightly contaminated by air or air-saturated water are corrected using N₂/Ar ratios in order to obtain primary magmatic values, composed of contributions from upper mantle and subducted hemipelagic sediment on the down-going plate. Using a mantle endmember with δ¹⁵N = −5‰ and N₂/He = 100 and a subducted sediment component with δ¹⁵N = +7‰ and N₂/He = 10,500, the average sediment contribution to Nicaraguan volcanic and geothermal gases was determined to be 71%. Most of the gases were dominated by sediment-derived nitrogen, but gas from Volcán Mombacho, the southernmost sampling location, had a mantle signature (46% from subducted sediment, or 54% from the mantle) and an affinity with mantle-dominated gases discharging from Costa Rica localities to the south. High CO₂/N_{2 exc.} ratios (N_{2 exc.} is the N₂ abundance corrected for contributions from air) in the south are similar to those in Costa Rica, and reflect the predominant mantle wedge input, whereas low ratios in the north indicate contribution by altered oceanic crust and/or preferential release of nitrogen over carbon from the subducting slab. Sediment-derived nitrogen fluxes at the Nicaraguan volcanic front, estimated by three methods, are 7.8 × 10⁸ mol N/a from ³He flux, 6.9 × 10⁸ mol/a from SO₂ flux, and 2.1 × 10⁸ and 1.3 × 10⁹ mol/a from CO₂ fluxes calculated from ³He and SO₂, respectively. These flux results are higher than previous estimates for Central America, reflecting the high sediment-derived volatile contribution and the high nitrogen content of geothermal and volcanic gases in Nicaragua. The fluxes are also similar to but higher than estimated hemipelagic nitrogen inputs at the trench, suggesting addition of N from altered oceanic basement is needed to satisfy these flux estimates. The similarity of the calculated input of N via the trench to our calculated outputs suggests that little or none of the subducted nitrogen is being recycled into the deeper mantle, and that it is, instead, returned to the surface via arc volcanism.     

Acid leaching of ash and coal: Time dependence and trace element occurrences

The leaching of coal and coal/asphaltite/wood-ashes in sulfuric acid (pH 1.0, 25 °C, S/L, 1:10) was studied as a function of time; acid consumption and extracted metal concentrations are presented. Whole coals consumed acid rapidly during the first few minutes, followed by slow acid consumption. Wood-, lignite-, and asphaltite-ashes consumed acid in two stages, the rapid phase extending < 30 min and the slow phase extended up to 10 days. The rapid phase was dominated by the dissolution of Ca, K and Mg ions for wood-ash, by Ca, Al and Mg ions for lignite-ash and Ca and Mg ions for asphaltite-ash. The sulfur concentration in solution and the concentrations of Ca, Fe, K, Mg, Na, P, Al and Mn in the aqueous phase verified the neutralizing capacity of the untreated ashes as well as the formation of insoluble sulfates in the residues. The slow phase kinetics differed for different fuels and exhibited leaching of several abundant elements—Fe, Al, K, Na and Mn. Trace elements (Ba, Cd, Co, Cr, Cu, Mo, Ni, Pb, Th, U, V, Zn) sometimes required up to 32 h for maximal extraction from ashes. Suggestions are presented regarding the chemical nature of trace elements in the untreated coals and ashes and suitable residence times for economical industrial processes. We think it possible to combine bacteriological oxidation of sulfidic concentrates of acid leaching from ash of various qualities or even whole coals.     

Effects of enhanced zinc and copper in drinking water on spatial memory and fear conditioning

Ingestion of enhanced zinc can cause memory impairments and copper deficiencies. This study examined the effect of zinc supplementation, with and without copper, on two types of memory. Rats raised pre- and post-natally on 10 mg/kg ZnCO₃ or ZnSO₄ in the drinking water were tested in a fear-conditioning experiment at 11 months of age. Both zinc groups showed a maladaptive retention of fearful memories compared to controls raised on tap water. Rats raised on 10 mg/kg ZnCO₃, 10 mg/kg ZnCO₃ + 0.25 mg/kg CuCl₂, or tap water, were tested for spatial memory ability at 3 months of age. Significant improvements in performance were found in the ZnCO₃ + CuCl₂ group compared to the ZnCO₃ group, suggesting that some of the cognitive deficits associated with zinc supplementation may be remediated by addition of copper.     

Geochemical evolution of the Capim River kaolin, Northern Brazil

The Capim River kaolin, located in the eastern Brazilian Amazon, constitutes one of the most important kaolin deposits in the world. Known for its high whiteness, its noble application is in the paper industry. Studies were carried out on samples from the six facies of the deposit (sand kaolin, soft kaolin, lower transition facies, ferruginous crust, upper transition facies and flint kaolin) in order to trace its geochemical evolution. The kaolin developed at the expense of Cretaceous sandy–clayey sediments of the Ipixuna Formation. Intense lateritic processes characterized by ferruginization and deferruginization mechanisms led to the distinction of the different facies.