Stable isotope evidence for regional-scale fluid migration in a Barrovian metamorphic terrane,Vermont, USA

We measured the C- and O-isotopic composition of carbonate minerals in the Waits River Formation, eastern Vermont, to determine the extent of fluid infiltration during regional metamorphism over an approx. 2000 km² area in a deep-seated (>25 km) Barrovian terrane. From a petrologic study of this terrane, Ferry proposed the existence of a large regional metamorphic hydrothermal system with two first-order features: (1) on the scale of the entire terrane fluid flow was focused into the axes of two major antiforms of regional extent; (2) on a smaller scale (about 100 km²) flow was further focused around synmetamorphic granitic plutons that intruded along the axes of the antiforms. We find isotopic evidence for both the regional hydrothermal activity along the antiforms and the more intense fluid flow around synmetamorphic plutons. The evidence for hydrothermal activity around the plutons is large heavy isotope depletions, up to 6–9 in ¹⁸O_carb and ¹³C_carb, in diopside zone rocks adjacent to the plutons. These isotopic shifts are greater than can be explained solely by prograde metamorphic reactions. We find two lines of evidence for the more diffuse regional flow that was focused into axes of the antiforms. First, ¹⁸O_carb and ¹³C_carb, within individual outcrops become increasingly homogeneous with increasing grade towards antiform axes, indicating that the rocks equilibrated with a permeating fluid. Second, there are depletions in ¹⁸O near the margins of the Waits River Formation which can be interpreted as a dispersed, advective infiltration front displaced toward the antiform axes. These fronts were modelled using Eq. 13 of Bickle and Baker and imply time-integrated fluid of 10⁵–10⁶ cm³/cm², which are consistent with values derived by Ferry from measured progress of prograde devolatilization reactions.     

Scientific CMOS Pixels

High performance CMOS pixels are introduced; and their development is discussed. 3T (3-transistor) photodiode, 5T pinned diode, 6T photogate and 6T photogate back illuminated CMOS pixels are examined in detail, and the latter three are considered as scientific pixels. The advantages and disadvantages of these options for scientific CMOS pixels are examined. Pixel characterization, which is used to gain a better understanding of CMOS pixels themselves, is also discussed. This revised version was published online in July 2006 with corrections to the Cover Date.     

Estimates of surface drifter trajectories in the equatorial Atlantic: a multi-model ensemble approach

We compared the estimates of surface drifter trajectories from 1 to 7?days in the equatorial Atlantic over an 18-month period with five eddying ocean general circulation model (OGCM) reanalyses and one observational product. The cumulative distribution of trajectory error was estimated using over 7,000?days of drifter trajectories. The observational product had smaller errors than any of the individual OGCM reanalyses. Three strategies for improving trajectory estimates using the ensemble of five operational ocean analysis and forecasting products were explored: two methods using a multi-model ensemble estimate and also spatial low-pass filtering. The results were insensitive to the method used to create the ensemble estimates, and by most measures, the results were better than the observational product. Comparison of relative skill of the various OGCM reanalyses suggested promising avenues for exploration for further improvements: forcing with higher frequency wind stress and quality control of input data. One of the lowest horizontal resolution OGCMs, with 1/4° longitude horizontal resolution, made the best trajectory estimates. The individual OGCMs were dominated by errors at spatial scales smaller than about 100 to 200?km, i.e., less than the local deformation radius. But buried in those errors were valuable signals that could be retrieved by combining all the OGCM velocity fields to produce a multi-model ensemble-based estimate. This estimate had skill down to spatial scales about 75?km. Results from this study are consistent with previous work showing that ensemble-mean forecast skill is superior to individual forecasts.     

Prograde and retrograde fluid flow during contact metamorphism of siliceous carbonate rocks from the Ballachulish aureole,Scotland

 Siliceous dolomites and limestones contain abundant retrograde minerals produced by hydration-carbonation reactions as the aureole cooled. Marbles that contained periclase at the peak of metamorphism bear secondary brucite, dolomite, and serpentine; forsterite-dolomite marbles have retrograde tremolite and serpentine; wollastonite limestones contain secondary calcite and quartz; and wollastonite-free limestones have retrograde tremolite. Secondary tremolite never appears in marbles where brucite has replaced periclase or in wollastonite-bearing limestones. A model for infiltration of siliceous carbonates by CO₂-H₂O fluid that assumes (a) vertical upwardly-directed flow, (b) fluid flux proportional to cooling rate, and (c) flow and reaction under conditions of local equilibrium between peak temperatures and ≈400 °C, reproduces the modes of altered carbonate rocks, observed reaction textures, and the incompatibility between tremolite and brucite and between tremolite and wollastonite. Except for samples from a dolomite xenolith, retrograde time-integrated flux recorded by reaction progress is on the order of 1000 mol fluid/cm² rock. Local focusing of flow near the contact is indicated by samples from the xenolith that record values an order of magnitude greater. Formation of periclase, forsterite, and wollastonite at the peak of metamorphism also required infiltration with prograde time-integrated flux approximately 100–1000 mol/cm². The comparatively small values of prograde and retrograde time-integrated flux are consistent with lack of stable isotope alteration of the carbonates and with the success of conductive thermal models in reproducing peak metamorphic temperatures recorded by mineral equilibria. Although isobaric univariant assemblages are ubiquitous in the carbonates, most formed during retrograde metamorphism. Isobaric univariant assemblages observed in metacarbonates from contact aureoles may not record physical conditions at the peak of metamorphism as is commonly assumed. Received: 19 September 1995 / Accepted: 14 March 1996     

Experimental calibration of the partitioning of Fe and Mg between biotite and garnet

The cation exchange reaction Fe₃Al₂Si₃O₁₂ +KMg₃AlSi₃O₁₀(OH)₂ = Mg₃Al₂Si₃O₁₂+KFe₃-AlSi₃ O₁₀(OH)₂ has been investigated by determining the partitioning of Fe and Mg between synthetic garnet, (Fe, Mg)₃Al₂Si₃O₁₂, and synthetic biotite, K(Fe, Mg)₃AlSi₃O₁₀(OH)₂. Experimental results at 2.07 kbar and 550 °–800 ° C are consistent with In [(Mg/Fe) garnet/(Mg/Fe) biotite] = -2109/T(°K) +0.782. The preferred estimates for ¯H and ¯S of the exchange reaction are 12,454 cal and 4.662 e.u., respectively. Mixtures of garnet and biotite in which the ratio garnet/biotite=49/1 were used in the cation exchange experiments. Consequently the composition of garnet-biotite pairs could approach equilibrium values in the experiments with minimal change in garnet composition (few tenths of a mole percent). Equilibrium was demonstrated at each temperature by reversal of the exchange reaction. Numerical analysis of the experimental data yields a geothermometer for rocks containing biotite and garnet that are close to binary Fe-Mg compounds.     

La plate-forme carbonatée oxfordienne de Lorraine : arguments pour une ouverture vers la mer Germanique

The study of sedimentary facies in the quarry of Dompcevrin (Middle Oxfordian) located northwestward of St-Mihiel (Meuse department) provides evidences of high-energy depositional conditions. The occurrence of beaches associated with hurricane coral breccias containing megaclasts is characteristic of platform edge environments. The open sea was located northeastward, in the direction of Germany, as it is indicated by the direction of progradation of beaches. It is concluded that the Oxfordian carbonate platform of Lorraine was opened to the northeast toward the Germanic Sea during the Middle Oxfordian. To cite this article: C. Carpentier et al., C. R. Geoscience 336 (2004).     

Formation and destruction of periclase by fluid flow in two contact aureoles

Periclase formed in steeply dipping marbles from the Beinn an Dubhaich aureole, Scotland, and the Silver Star aureole, Montana, by the reaction dolomite = periclase + calcite + CO₂. Equilibrium between rock and fluids with X _{CO 2} < 1 requires that reaction was infiltration-driven. Brucite pseudomorphs after periclase occur in the Beinn an Dubhaich aureole either as bed-by-bed replacement of dolomite or in a lens along the contact between dolomite and a pre-metamorphic dike. Transport theory predicts that infiltration drove both periclase reaction and ¹⁸O-depletion fronts which moved at significantly different velocities along the flow path. The distributions of brucite and ¹⁸O-depleted rocks are identical in surface exposures, thus indicating upward flow. Time-integrated flux (q) was <500 mol/cm² and the fluid source was magmatic. Because periclase and its hydrated equivalent brucite are unaltered to dolomite by retrograde reactions, the exposure of brucite marbles accurately images the flow paths of peak metamorphic fluids. In the Silver Star aureole brucite pseudomorphs after periclase exclusively occur in tabular bodies that are beds with elevated Mg/Ca. The spatial pattern of ¹⁸O-depletion requires upward vertical fluid flow. Estimated prograde q ≈ 10³–10⁴ mol/cm² and the fluid source was magmatic. Low Mg/Ca, ¹⁸O-depleted, brucite-free rocks pose a dilemma because the periclase reaction front should have traveled ≈18 times further through them than the isotope alteration front. The dilemma is resolved by reaction textures that indicate periclase and brucite were destroyed in low Mg/Ca rocks by infiltration-driven retrograde carbonation reactions. Values of retrograde q were ≈10³–10⁴ mol/cm². Brucite (after periclase) was preserved only in high Mg/Ca layers where periclase developed in greater abundance. The geometry of brucite marbles at Silver Star thus reflects the location of high Mg/Ca beds rather than the geometry of fluid flow. Retrograde reactions must be considered before the mineralogical record of prograde fluid flow can correctly be interpreted. In both aureoles fluid flow, mineral reaction, and isotope depletion were structurally controlled by bedding and lithologic contacts. Received: 30 July 1996 / Accepted: 21 March 1997     

Constraints on the thermodynamic mixing properties of plagioclase feldspars

Taking account of the Cˉ1/Iˉ1 (Al/Si order/disorder) transformation at high temperatures in the albite-anorthite solid solution leads to a simple model for the mixing properties of the high structural state plagioclase feldspars. The disordered (Cˉ1) solid solution can be treated as ideal (constant activity coefficient) and, for anorthite-rich compositions, deviations from ideality can be ascribed to cation ordering. Values of the activity coefficient for anorthite in the Cˉ1 solid solution (γ _An ^Cˉ1 ) are then controlled by the free energy difference between Cˉ1 and Iˉ1 anorthite at the temperature (T) of interest according to the relation: ΔˉG _ord ^Iˉ1 ⇌Cˉ1 =RT ln γ _An ^Cˉ1 . If the Iˉ1⇌Cˉ1 transformation in pure anorthite is treated, to a first approximation, as first order and the enthalpy and entropy of ordering are taken as 3.7±0.6 kcal/mole (extrapolated from calorimetric data) and 1.4–2.2 cal/mole (using an equilibrium order/disorder temperature for An₁₀₀ of 2,000–2,250 K), a crude estimate of γ _An ^Cˉ1 for all temperatures can be made. The activity coefficient of albite in the Cˉ1 solid solution (γ _Ab ^Cˉ1 ) can be taken as 1.0. The possible importance of this model lies in its identification of the principal constraints on the mixing properties rather than in the actual values of γ _An ^Cˉ1 and γ _Ab ^Cˉ1 obtained. In particular it is recognised that γ _An ^Cˉ1 depends critically on ordering in anorthite as well as, at lower temperatures, any ordering in the Cˉ1 solid solution. A brief review of activity-composition data, from published experiments involving ranges of plagioclase compositions and from the combined heats of mixing plus Al-avoidance entropy model (Newton et al. 1980), reveals some inconsistencies. The values of γ _An ^Cˉ1 calculated using the approach of Newton et al. (1980), although consistent with Orville's (1972) ion exchange data, are slightly lower than values derived from experiments by Windom and Boettcher (1976) and Goldsmith (1982) or from ion-exchange experiments of Kotel'nikov et al. (1981). Based on the Cˉ1/Iˉ1 transformation model, values of γ _An ^Cˉ1 <1.0 are unlikely. Discrepancies between the experimental data sets are attributed to incomplete (non-equilibrium) Al/Si order attained during the experiments. It is suggested that the choice of activity coefficients remains somewhat subjective. The development of accurate mixing models would be greatly assisted by better thermodynamic data for ordering in pure anorthite and by more thorough characterisation of the state of order in plagioclase crystals used for phase equilibrium experiments.     

Prograde destruction and formation of monazite and allanite during contact and regional metamorphism of pelites: petrology and geochronology

The conditions at which monazite and allanite were produced and destroyed during prograde metamorphism of pelitic rocks were determined in a Buchan and a Barrovian regional terrain and in a contact aureole, all from northern New England, USA. Pelites from the chlorite zone of each area contain monazite that has an inclusion-free core surrounded by a highly irregular, inclusion-rich rim. Textures and ²⁰⁸Pb/²³²Th dates of these monazites in the Buchan terrain, obtained by ion microprobe, suggest that they are composite grains with detrital cores and very low-grade metamorphic overgrowths. At exactly the biotite isograd in the regional terrains, composite monazite disappears from most rocks and is replaced by euhedral metamorphic allanite. At precisely the andalusite or kyanite isograd in all three areas, allanite, in turn, disappears from most rocks and is replaced by subhedral, chemically unzoned monazite neoblasts. Allanite failed to develop at the biotite isograd in pelites with lower than normal Ca and/or Al contents, and composite monazite survived at higher grades in these rocks with modified texture, chemical composition, and Th-Pb age. Pelites with elevated Ca and/or Al contents retained allanite in the andalusite or kyanite zone. The best estimate of the time of peak metamorphism at the andalusite or kyanite isograd is the mean Th-Pb age of metamorphic monazite neoblasts that have not been affected by retrograde metamorphism: 364.3Dž.5 Ma in the Buchan terrain, 352.9NJ.9 Ma in the Barrovian terrain, and 403.4LJ.9 Ma in the contact aureole. Some metamorphic monazites from the Buchan terrain have ages partially to completely reset during an episode of retrograde metamorphism at 343.1Nj.1 Ma. Interpretation of Th-Pb ages of individual composite monazite grains is complicated by the occurrence of subgrain domains of detrital material intergrown with domains of material formed or recrystallized during prograde and retrograde metamorphism.     

Organic geochemistry in a sequence stratigraphic framework. The siliciclastic shelf environment of Cretaceous series, SE France

For a better understanding of siliciclastic shelf environments, correlation between sequence stratigraphy and organic geochemistry is used. Our study is focused on the Cretaceous deposits of Marcoule (Gard, France), particularly on a close-packed siltites layer (200–400 m thick), which is well characterized as a marine flooding facies of a single trangressive–regressive cycle. During the Uppermost Albian and the Lower Cenomanian, the stratigraphic data indicate a change in the depositional environment from offshore to shoreface. Organic geochemistry is used in order to characterize origin and variability of the organic matter in relation to the stratigraphic data. The study is carried out on core samples from 2 drill holes (MAR 203 and MAR 501). Analyses of the aliphatic and aromatic hydrocarbons were performed using GC–MS and focused on biomarker distributions. The biomarkers indicate a contribution of mixed terrestrial and marine organic matter. The changes in molecular signatures are related to variations in the source of organic matter (marine versus terrestrial), preservation conditions (largely influenced by clay and early diagenesis), environmental oxidation-reduction and acidic conditions as well as bioturbation. Various environmental zones, characterized by different molecular signatures, can be distinguished. Resin derived biomarkers can be assigned to higher plant material input and may reflect the evolution and diversity of Gymnospermae versus Angiospermae during the transgressive/regressive cycle. The relative sea-level variations are clearly correlated with the nature and the preservation of the organic matter. For example, the Pr/Ph and Pr/n-C₁₇ ratios as well as the regular steranes distributions underline the maximum flooding surface evidenced by other studies. We observe a good correlation between the organic data and sequence stratigraphy: changes in geochemical signatures reflect the 3rd order depositional cycles.