The double solid reactant method: II. An application to the shallow groundwaters of the Porto Plain,Vulcano Island (Italy)

This paper presents an example of application of the double solid reactant method (DSRM) of Accornero and Marini (Environmental Geology, 2007a), an effective way for modeling the fate of several dissolved trace elements during water–rock interaction. The EQ3/6 software package was used for simulating the irreversible water–rock mass transfer accompanying the generation of the groundwaters of the Porto Plain shallow aquifer, starting from a degassed diluted crateric steam condensate. Reaction path modeling was performed in reaction progress mode and under closed-system conditions. The simulations assumed: (1) bulk dissolution (i.e., without any constraint on the kinetics of dissolution/precipitation reactions) of a single solid phase, a leucite-latitic glass, and (2) precipitation of amorphous silica, barite, alunite, jarosite, anhydrite, kaolinite, a solid mixture of smectites, fluorite, a solid mixture of hydroxides, illite-K, a solid mixture of saponites, a solid mixture of trigonal carbonates and a solid mixture of orthorhombic carbonates. Analytical concentrations of major chemical elements and several trace elements (Cr, Mn, Fe, Ni, Cu, Zn, As, Sr and Ba) in groundwaters were satisfactorily reproduced. In addition to these simulations, similar runs for a rhyolite, a latite and a trachyte permitted to calculate major oxide contents for the authigenic paragenesis which are comparable, to a first approximation, with the corresponding data measured for local altered rocks belonging to the silicic, advanced argillic and intermediate argillic alteration facies. The important role played by both the solid mixture of trigonal carbonates as sequestrator of Mn, Zn, Cu and Ni and the solid mixture of orthorhombic carbonates as scavenger of Sr and Ba is emphasized.

Experimental constraints on the effects of pressure and H2O on the fractional crystallization of high-Mg island arc basalt

H₂O-undersaturated melting experiments of synthesized basalt (SiO₂ = 50.7 wt.%, MgO = 8.3 wt.%, Mg# = 60) were conducted at fO₂ corresponding to NNO+1 and NNO−1 to clarify the effects of pressure (2–7 kbar) and H₂O on fractional crystallization in island arcs. H₂O content was ranged from nominally anhydrous to 4.4 wt.%. Differentiation trends, namely the liquid lines of descent, change sensitively according to pressure-H₂O relations. Tholeiitic differentiation trends are reproduced with H₂O ≤ ∼2 wt.% in primary magma. With such quantities of H₂O, fractional crystallization is controlled by olivine + plagioclase at 2 kbar. Increasing the pressure from 2 to ≥4 kbar induces early crystallization of orthopyroxene instead of olivine and therefore SiO₂ enrichment in the residual melts is suppressed. Increasing H₂O (≥ ∼2 wt.% in primary magma) stabilizes clinopyroxene relative to orthopyroxene and/or magnetite. Although the phase relations and proportions strongly depend on fO₂ and H₂O content, differentiation trends are always calc-alkaline.     

Low-pressure,water-assisted anatexis of basic dykes in a contact metamorphic aureole,Fuerteventura (Canary Islands): oxygen isotope evidence for a meteoric fluid origin

Migmatites produced by low-pressure anatexis of basic dykes are found in a contact metamorphic aureole around a pyroxenite–gabbro intrusion (PX2), on Fuerteventura. Dykes outside and inside the aureole record interaction with meteoric water, with low or negative δ¹⁸O whole-rock values (+0.2 to −3.4‰), decreasing towards the contact. Recrystallised plagioclase, diopside, biotite and oxides, from within the aureole, show a similar evolution with lowest δ¹⁸O values (−2.8, −4.2, −4.4 and −7.6‰, respectively) in the migmatite zone, close to the intrusion. Relict clinopyroxene phenocrysts preserved in all dykes, retain typically magmatic δ¹⁸O values up to the anatectic zone, where the values are lower and more heterogeneous. Low δ¹⁸O values, decreasing towards the intrusion, can be ascribed to the advection of meteoric water during magma emplacement, with increasing fluid/rock ratios (higher dyke intensities towards the intrusion acting as fluid-pathways) and higher temperatures promoting increasing exchange during recrystallisation. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Magma Ascent and Crustal Accretion at Ultraslow-Spreading Ridges: Constraints from Plagioclase Ultraphyric Basalts from the Arctic Mid-Ocean Ridge

Plagioclase ultraphyric basalts (PUBs) with up to 54% plagioclasephenocrysts were dredged in the rift valley and adjacent flanksof the ultraslow-spreading Mohns and Knipovich ridges. The PUBsshow large variations in crystal morphologies and zoning. Thelarge variations suggest that single basalt samples containa mixture of plagioclase crystals that aggregated at differentlevels in the magma conduits. Resorbed crystals and repeatedreverse zones suggest that the magma reservoirs were replenishedand heated several times. Thin concentric zones with melt inclusions,and sharp reductions in the anorthite content of 3–7%,are common between the reverse zones. These zones, and skeletalcrystals with distinctly lower anorthite contents than massivecrystals, are interpreted to be the result of rapid crystalliztionduring strong undercooling. The changes between short periodsof cooling and longer periods with reheating are explained bymultiple advances of crystal-rich magma into cool regions followedby longer periods of gradual magma inflow and temperature increase.The porphyritic basalts are characterizd by more depleted andmore fractionated compositions than the aphyric basalts, withlower (La/Sm)_N, K₂O and Mg-numbers. This relationship, and theobservation that PUBs are sampled only close to segment centresalong these ridges, suggests that the PUBs formed by higherdegrees of melting and evolved in more long-lived magma reservoirs.We propose that the zoning patterns of plagioclase crystalsand crystal morphologies of these PUBs reflect the developmentand flow of magma through a stacked sill complex-like conduitsystem, whereas the aphyric equivalents represent later flowof magma through the conduit. The formation of voluminous higher-degreemelts may trigger the development of the magma conduits andexplain the generally depleted compositions of PUB magmas. KEY WORDS: basalt; mineral chemistry; MORB; magma mixing; magma chamber; major element     

Depths of Partial Crystallization of H2O-bearing MORB: Phase Equilibria Simulations of Basalts at the MAR near Ascension Island (7 11{degrees}S)

Phase equilibria simulations were performed on naturally quenchedbasaltic glasses to determine crystallization conditions priorto eruption of magmas at the Mid-Atlantic Ridge (MAR) east ofAscension Island (7–11°S). The results indicate thatmid-ocean ridge basalt (MORB) magmas beneath different segmentsof the MAR have crystallized over a wide range of pressures(100–900 MPa). However, each segment seems to have a specificcrystallization history. Nearly isobaric crystallization conditions(100–300 MPa) were obtained for the geochemically enrichedMORB magmas of the central segments, whereas normal (N)-MORBmagmas of the bounding segments are characterized by polybariccrystallization conditions (200–900 MPa). In addition,our results demonstrate close to anhydrous crystallization conditionsof N-MORBs, whereas geochemically enriched MORBs were successfullymodeled in the presence of 0·4–1 wt% H₂O in theparental melts. These estimates are in agreement with direct(Fourier transform IR) measurements of H₂O abundances in basalticglasses and melt inclusions for selected samples. Water contentsdetermined in the parental melts are in the range 0·04–0·09and 0·30–0·55 wt% H₂O for depleted and enrichedMORBs, respectively. Our results are in general agreement (within±200 MPa) with previous approaches used to evaluate pressureestimates in MORB. However, the determination of pre-eruptiveconditions of MORBs, including temperature and water contentin addition to pressure, requires the improvement of magma crystallizationmodels to simulate liquid lines of descent in the presence ofsmall amounts of water. KEY WORDS: MORB; Mid-Atlantic Ridge; depth of crystallization; water abundances; phase equilibria calculations; cotectic crystallization; pressure estimates; polybaric fractionation     

Geobarometry for Peridotites: Experiments in Simple and Natural Systems from 6 to 10 GPa

Experiments with peridotite minerals in simple (MgO–Al₂O₃–SiO₂,CaO–MgO–SiO₂ and CaO–MgO–Al₂O₃–SiO₂)and natural systems were conducted at 1300–1500°Cand 6–10 GPa using a multi-anvil apparatus. The experimentsin simple systems demonstrated consistency with previous lowerpressure experiments in belt and piston–cylinder set-ups.The analysis of spatial variations in pyroxene compositionswithin experimental samples was used to demonstrate that pressureand temperature variations within the samples were less than0·4 GPa and 50°C. Olivine capsules were used in natural-systemexperiments with two mineral mixtures: SC1 (olivine + high-Alorthopyroxene + high-Al clinopyroxene + spinel) and J4 (olivine+ low-Al orthopyroxene + low-Al clinopyroxene + garnet). Theexperiments produced olivine + orthopyroxene + garnet ±clinopyroxene assemblages, occasionally with magnesite and carbonate-richmelt. Equilibrium compositions were derived by the analysisof grain rims and evaluation of mineral zoning. They were comparedwith our previous experiments with the same starting mixturesat 2·8–6·0 GPa and the results from simplesystems. The compositions of minerals from experiments withnatural mixtures show smooth pressure and temperature dependencesup to a pressure of 8 GPa. The experiments at 9 and 10 GPa producedandradite-rich garnets and pyroxene compositions deviating fromthe trends defined by the lower pressure experiments (e.g. higherAl in orthopyroxene and Ca in clinopyroxene). This discrepancyis attributed to a higher degree of oxidation in the high-pressureexperiments and an orthopyroxene–high-P clinopyroxenephase transition at 9 GPa. Based on new and previous resultsin simple and natural systems, a new version of the Al-in-orthopyroxenebarometer is presented. The new barometer adequately reproducesexperimental pressures up to 8 GPa. KEY WORDS: garnet; mineral equilibrium; multi-anvil apparatus; orthopyroxene; geobarometry     

Room-temperature equation of state of Li<Subscript>2</Subscript>VOSiO<Subscript>4</Subscript> up to 8.5 GPa

High-pressure single-crystal X-ray diffraction measurements of lattice parameters of the compound Li₂VOSiO₄, which crystallises with a natisite-type structure, has been carried out to a pressure of 8.54(5) GPa at room temperature. Unit-cell volume data were fitted with a second-order Birch-Murnaghan EoS (BM-EoS), simultaneously refining V ₀ and K ₀ using the data weighted by the uncertainties in V. The bulk modulus is K ₀ = 99(1) GPa, with K′ fixed to 4. Refinements of third order equations-of-state yielded values of K′ that did not differ significantly from 4. The compressibility of the unit-cell is strongly anisotropic with the c axis (K ₀(c) = 49.7 ± 0.5 GPa) approximately four times more compressible than the a axis (K ₀(a) = 195 ± 3 GPa).     

In situ strength measurements on natural upper-mantle minerals

Using in situ strength measurements at pressures up to 10 GPa and at room temperature, 400, 600, and 700°C, we examined rheological properties of olivine, orthopyroxene, and chromian-spinel contained in a mantle-derived xenolith. Mineral strengths were estimated using widths of X-ray diffraction peaks as a function of pressure, temperature, and time. Differential stresses of all minerals increase with increasing pressure, but they decrease with increasing temperature because of elastic strain on compression and stress relaxation during heating. During compression at room temperature, all minerals deform plastically at differential stress of 4–6 GPa. During subsequent heating, thermally induced yielding is observed in olivine at 600°C. Neither orthopyroxene nor spinel shows complete stress relaxation, but both retain some stress even at 700°C. The strength of the minerals decreases in the order of chromian-spinel ≈ orthopyroxene > olivine for these conditions. This order of strength is consistent with the residual pressure of fluid inclusions in mantle xenoliths.     

EPR investigation of the methyl radical,the hydrogen atom and carbon oxide radicals in Maxixe-type beryl

The EPR spectra of Maxixe-type beryl contain a large number of overlapping signals. The angular dependence of the 1:3:3:1 signal typical for the CH₃ radical shows that this radical is located at the center of the channel cavity with its symmetry axis parallel to the crystal c-axis and is rotating around this axis. Its EPR spectrum is axially symmetric with g _// = 2.00263, g _⊥ = 2.00249 and A_// = 2.288 mT, A_⊥ = 2.256 mT. These anisotropies have the opposite signs of those found for surface-adsorbed methyl radicals. Hydrogen atoms are located at position 2a at the center of the beryl cavity and the EPR parameters of the narrow doublet signal are A ₀ = 1,407 MHz and g = 2.00230. Another doublet signal, which is broader and has axial symmetry with g _// = 2.00265, g _⊥ = 2.00625 and A_// = 0.895 mT, A_⊥ = 0.885 mT, could come from a HCO₃ radical. One narrow and easily saturated signal with g _// = 2.00227 and g _⊥ = 2.00386 is interpreted to arise from a carbon monoxide radical in the beryl channel, oriented with its axis parallel to the crystal c-axis. Additional weak doublet lines, which have similar g values as the carbon monoxide radical, are created by nearby hydrogens. A powder spectrum with g _// = 2.0017 and g _⊥ = 2.0004 appears upon UV irradiation of the single crystal and is easily saturated. This spectrum is interpreted to arise from a carbon dioxide radical, which rotates around its symmetry axis.     

引水工程秦巴段隧洞地应力模拟及工程地质问题

利用Ansys有限元软件对三峡引水工程秦巴段线路不同深度、不同截面形态隧洞围岩的应力重分布情况进行模拟计算,得到圆形隧洞、城门形隧洞和马蹄形隧洞围岩的应力数值和等值线图.利用库仑一纳维尔强度准则,对花岗岩区及灰岩区隧洞围岩的剪切破坏进行分析;利用三种岩爆应力判别指标,对岩爆进行初步预测;进而对不同深度、不同截面形态的隧洞围岩的稳定性进行分析;最后对引水工程隧洞设计中截面形态的选择给出了初步建议.