A field and theoretical analysis of garnet+chlorite+chloritoid+biotite assemblages from the tri-state (MA,CT, NY) area,USA

The prograde evolution of minerals in metapelites of a Barrovian sequence from the tri-state area (Massachusetts, Connecticut, New York) of the Taconic Range involves assemblages with garnet (Ga), chlorite (Ch), chloritoid (Ct), biotite (Bi) and staurolite (St). Detailed petrologic observations, mineral compositions and chemical zoning in garnet show: (1) garnet high in Mn and Fe but low in Mg is stable with chlorite at grades below those where chloritoid+biotite is found; (2) early formed garnet reacted partially to form Ct+Bi at intermediate grades; (3) at higher grades garnet (with low Mn)+chlorite is again produced, at the expense of chloritoid+biotite, suggesting a reversal in the continuous reaction involving the phases Ga, Ch, Ct and Bi. Thermodynamic modeling of the assemblage Ga+Ch+Ct+Bi±St in the MnKFMASH system reveals: (1) in the MnKFASH system the prograde reaction is Ga+Ch=Ct+Bi whereas in the KFMASH system the prograde reaction is the opposite: Ct+Bi=Ga+Ch; (2) the Ga–Ch–Ct–Bi–St invariant point in the KFMASH system occurs twice, at approximately 6.5 kbar, 545° C and 14.8 kbar, 580° C (although one of them may be metastable in a complex phase system); the appearance of the petrogenetic grid is markedly different from that of Albee, but similar to that of Spear and Cheney; (3) as a consequence, in the KFMASH system, chloritoid+biotite are stable over a wide range of P-T conditions whereas garnet+chlorite assemblages are restricted to a narrow band of P-T conditions; (4) MnO increases the stability field of Ga+Ch relative to both Ct+Bi at low temperatures, and St+Bi at high temperatures; (5) in natural samples the occurrence of Ct+Bi is controlled more by bulk Mg–Fe(-Mn) composition than P-T conditions. Specifically, Ct+Bi is restricted to bulk compositions with Fe/(Mg+Fe+Mn)>0.6. Rocks with Fe/(Mg+Fe+Mn)<0.5 are likely to display only chlorite+biotite at low grade. These observations are consistent with Wang and Spear and Spear and Cheney.     

Rigid unit modes in the molecular dynamics simulation of quartz and the incommensurate phase transition

A molecular dynamics simulation of quartz at different temperatures both in the a and in the phase has been conducted. The - phase transition could be observed. A phonon analysis of the -phase confirms and rounds out in a quantitative way the origin of the incommensurate (ic) modulated phase. In particular it traces the optic soft mode at becoming (to a good approximation) a so-called rigid unit mode (RUM) at q0, and elucidates its coupling to the transverse acoustic mode which precipitates the incommensurate transition. This success underpins and illuminates the concept of RUMs and their role in structural phase transitions.     

Variability in the power spectrum of solar five-minute oscillations

Two-dimensional power spectra of solar five-minute oscillations display prominent ridge structures in (k, ω) space, where k is the horizontal wavenumber and ω is the temporal frequency. The positions of these ridges in k and ω can be used to probe temperature and velocity structures in the subphotosphere. We have been carrying out a continuing program of observations of five-minute oscillations with the diode array instrument on the vacuum tower telescope at Sacramento Peak Observatory (SPO). We have sought to establish whether power spectra taken on separate days show shifts in ridge locations; these may arise from different velocity and temperature patterns having been brought into our sampling region by solar rotation. Power spectra have been obtained for six days of observations of Doppler velocities using the Mgi λ5173 and Fei λ5434 spectral lines. Each data set covers 8 to 11 hr in time and samples a region 256″ × 1024″ in spatial extent, with a spatial resolution of 2″ and temporal sampling of 65 s. We have detected shifts in ridge locations between certain data sets which are statistically significant. The character of these displacements when analyzed in terms of eastward and westward propagating waves implies that changes have occurred in both temperature and horizontal velocity fields underlying our observing window. We estimate the magnitude of the velocity changes to be on the order of 100 m s^-1; we may be detecting the effects of large-scale convection akin to giant cells.     

Melting of the subcontinental lithospheric mantle by the Emeishan mantle plume; evidence from the basal alkaline basalts in Dongchuan, Yunnan, Southwestern China

The Emeishan continental flood basalt (ECFB) sequence in Dongchuan, SW China comprises a basal tephrite unit overlain by an upper tholeiitic basalt unit. The upper basalts have high TiO₂ contents (3.2–5.2 wt.%), relatively high rare-earth element (REE) concentrations (40 to 60 ppm La, 12.5 to 16.5 ppm Sm, and 3 to 4 ppm Yb), moderate Zr/Nb and Nb/La ratios (9.3–10.2 and 0.6–0.9, respectively) and relatively high _{Nd (t)} values, ranging from − 0.94 to 2.3, and are comparable to the high-Ti ECFB elsewhere. The tephrites have relatively high P₂O₅ (1.3–2.0 wt.%), low REE concentrations (e.g., 17 to 23 ppm La, 4 to 5.3 ppm Sm, and 2 to 3 ppm Yb), high Nb/La (2.0–3.9) ratios, low Zr/Nb ratios (2.3–4.2), and extremely low _{Nd (t)} values (mostly ranging from − 10.6 to − 11.1). The distinct compositional differences between the tephrites and the overlying tholeiitic basalts cannot be explained by either fractional crystallization or crustal contamination of a common parental magma. The tholeiitic basalts formed by partial melting of the Emeishan plume head at a depth where garnet was stable, perhaps > 80 km. We propose that the tephrites were derived from magmas formed when the base of the previously metasomatized, volatile-mineral bearing subcontinental lithospheric mantle was heated by the upwelling mantle plume.     

Carbon biogeochemistry of the Betsiboka estuary (north-western Madagascar)

Madagascar’s largest estuary (Betsiboka) was sampled along the salinity gradient during the dry season to document the distribution and sources of particulate and dissolved organic carbon (POC, DOC) as well as dissolved inorganic carbon (DIC). The Betsiboka was characterized by a relatively high suspended matter load, and in line with this, low DOC/POC ratios (0.4–2.5). The partial pressure of CO₂ (pCO₂) was generally above atmospheric equilibrium (270–1530 ppm), but relatively low in comparison to other tropical and subtropical estuaries, resulting in low average CO₂ emission to the atmosphere (9.1 ± 14.2 mmol m⁻² d⁻¹). Despite the fact that C4 vegetation is reported to cover >80% of the catchment area, stable isotope data on DOC and POC suggest that C4 derived material comprises only 30% of both pools in the freshwater zone, increasing to 60–70% and 50–60%, respectively, in the oligohaline zone due to additional lateral inputs. Sediments from intertidal mangroves in the estuary showed low organic carbon concentrations (<1%) and δ¹³C values (average −19.8‰) consistent with important inputs of riverine imported C4 material. This contribution was reflected in δ¹³C signatures of bacterial phospholipid derived fatty acids (i + a15:0), suggesting the potential importance of terrestrial organic matter sources for mineralization and secondary production in coastal ecosystems.     

Sulfur isotope measurement of sulfate and sulfide by high-resolution MC-ICP-MS

We have developed a technique for the accurate and precise determination of ³⁴S/³²S isotope ratios (δ³⁴S) in sulfur-bearing minerals using solution and laser ablation multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). We have examined and determined rigorous corrections for analytical difficulties such as instrumental mass bias, unresolved isobaric interferences, blanks, and laser ablation- and matrix-induced isotopic fractionation. Use of high resolution sector-field mass spectrometry removes major isobaric interferences from O₂⁺. Standard-sample bracketing is used to correct for the instrumental mass bias of unknown samples. Background on sulfur masses arising from memory effects and residual oxygen-tailing are typically minor (< 0.2‰, within analytical error), and are mathematically removed by on-peak zero subtraction and by bracketing of samples with standards determined at the same signal intensity (within 20%). Matrix effects are significant (up to 0.7‰) for matrix compositions relevant to many natural sulfur-bearing minerals. For solution analysis, sulfur isotope compositions are best determined using purified (matrix-clean) sulfur standards and sample solutions using the chemical purification protocol we present. For in situ analysis, where the complex matrix cannot be removed prior to analysis, appropriately matrix-matching standards and samples removes matrix artifacts and yields sulfur isotope ratios consistent with conventional techniques using matrix-clean analytes. Our method enables solid samples to be calibrated against aqueous standards; a consideration that is important when certified, isotopically-homogeneous and appropriately matrix-matched solid standards do not exist. Further, bulk and in situ analyses can be performed interchangeably in a single analytical session because the instrumental setup is identical for both. We validated the robustness of our analytical method through multiple isotope analyses of a range of reference materials and have compared these with isotope ratios determined using independent techniques. Long-term reproducibility of S isotope compositions is typically 0.20‰ and 0.45‰ (2σ) for solution and laser analysis, respectively. Our method affords the opportunity to make accurate and relatively precise S isotope measurement for a wide range of sulfur-bearing materials, and is particularly appropriate for geologic samples with complex matrix and for which high-resolution in situ analysis is critical.     

Numerical modeling assessment of three-gate structures for capturing contaminated groundwater

This modeling study evaluated the capability of alternative funnel-and-gate structures with three gates for capturing contaminated groundwater in a hypothetical unconfined aquifer. Simulated interceptor structures were linear and 45 m wide, consisting of three gates and two funnels (walls). One gate occupied the center and two gates occupied the ends of the interceptor structures. The structures, positioned perpendicular to regional groundwater flow, traversed the entire thickness of the aquifer. A total of four structures were evaluated (numbers designate widths of end, center, and end gates, respectively, in meters): 3-3-3, 2-5-2, 1-7-1, and 4-1-4. Particle tracking and zonal water budgets identified shapes of capture zones and discharge patterns for each interceptor structure. A mass transport model, accounting for advection and hydrodynamic dispersion, tested the capability of each structure for capturing a contaminant plume. Results suggest that: time-dependent capture zones underestimate the amount of time to capture a contaminant plume, wide center gates facilitate plume capture, and wide end gates facilitate lateral containment of contaminants. Of the structures simulated, the 2-5-2 configuration was relatively efficient at processing and containing the simulated contaminant plume.     

Late Palaeozoic hydrocarbon migration through the Clair field, West of Shetland, UK Atlantic margin

Geochemical analysis of bitumen- and hydrocarbon-bearing fluid inclusions from the Devonian-Carboniferous Clair field indicates that the reservoirs contain a mixture of oils from different marine and lacustrine sources. Reconstruction of the Clair field oil-charge history using fluid inclusion petrography show that oil-charging occurred at times of K-feldspar, quartz and calcite cementation. Temperature–composition–time data yielded from the integration of fluid inclusion microthermometry with high-resolution Ar–Ar dating, date hydrocarbon-bearing K-feldspar overgrowths at 247 ± 3.3 Ma. These data show that in order for oil to be trapped within primary fluid inclusions in K-feldspar overgrowths, hydrocarbon migration throughout the UK Atlantic margin must have been taking place during the Late Palaeozoic and as such, current industry oil-play models based solely on oil charging from Jurassic-Cretaceous marine sources are clearly incomplete and need revision. Apatite fission track analysis and vitrinite reflectance data were used to reconstruct thermal burial histories and assess potential oil generation from Middle Devonian lacustrine source rocks. Thermal history data from wells along The Rona Ridge adjacent to the Clair field show that the Palaeozoic section was heated to greater than 100 °C at some time between 270 and 230 Ma, confirming that Devonian source rocks were mature and expelling oil during the Late Palaeozoic at the time that authigenic K-feldspar overgrowths were growing in the Clair field.     

An experimental study of the grain-scale processes of peridotite melting: implications for major and trace element distribution during equilibrium and disequilibrium melting

The grain-scale processes of peridotite melting were examined at 1,340°C and 1.5 GPa using reaction couples formed by juxtaposing pre-synthesized clinopyroxenite against pre-synthesized orthopyroxenite or harzburgite in graphite and platinum-lined molybdenum capsules. Reaction between the clinopyroxene and orthopyroxene-rich aggregates produces a melt-enriched, orthopyroxene-free, olivine + clinopyroxene reactive boundary layer. Major and trace element abundance in clinopyroxene vary systematically across the reactive boundary layer with compositional trends similar to the published clinopyroxene core-to-rim compositional variations in the bulk lherzolite partial melting studies conducted at similar P–T conditions. The growth of the reactive boundary layer takes place at the expense of the orthopyroxenite or harzburgite and is consistent with grain-scale processes that involve dissolution, precipitation, reprecipitation, and diffusive exchange between the interstitial melt and surrounding crystals. An important consequence of dissolution–reprecipitation during crystal-melt interaction is the dramatic decrease in diffusive reequilibration time between coexisting minerals and melt. This effect is especially important for high charged, slow diffusing cations during peridotite melting and melt-rock reaction. Apparent clinopyroxene-melt partition coefficients for REE, Sr, Y, Ti, and Zr, measured from reprecipitated clinopyroxene and coexisting melt in the reactive boundary layer, approach their equilibrium values reported in the literature. Disequilibrium melting models based on volume diffusion in solid limited mechanism are likely to significantly underestimate the rates at which major and trace elements in residual minerals reequilibrate with their surrounding melt. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.