Emilie Janots

Metamorphic rates in collisional orogeny from in situ allanite and monazite dating

The prograde sequence of rare earth minerals recorded in metapelites during regional metamorphism reveals a series of irreversible reactions among silicates and phosphates. In individual samples from the northern Lepontine (Central Alps), allanite is partly replaced by monazite at 560–580 °C. Relic allanite retains its characteristic growth zoning acquired at greenschist facies conditions (430–450 °C). Coexisting monazite and allanite were dated in situ to delimit in time successive stages of the Barrovian metamorphism. In situ sensitive high-resolution ion microprobe (SHRIMP) U-Th-Pb dating of allanite (31.5 ± 1.3 and 29.2 ± 1.0 Ma) and monazite (18.0 ± 0.3 and 19.1 ± 0.3 Ma) constrains the time elapsed between 430–450 °C and 560–580 °C, which implies an average heating rate of 8–15 °C/m.y. Combined with new fission track ages (zircon, 10–9 Ma; apatite, 7.5–6.5 Ma), metamorphic rates of the entire orogenic cycle, from prograde to final cooling, can be reconstructed.

Evidence for Mio-Pliocene retrograde monazite in the Lesser Himalaya, far western Nepal

A multichronometric study involving 40Ar/39Ar and 208Pb/232Th ion-microprobe dating was performed on the two northernmost windows of Lesser Himalayan rocks in far western Nepal. Both regions were sampled for their monazite-rich series. Metamorphic peak temperatures range from 540°C to 370°C. In the highest-grade rocks (Tmax ∼ 540°C), 40Ar/39Ar chronology on hornblende, biotite and muscovite gives ages of 12.9 ± 1.9 Ma, 8.9–11.7 Ma and 4.8 ± 0.4 Ma, respectively. Monazite grains yield two different 208Pb/232Th age populations of 9.3–11.4 Ma and 3.3–5.8 Ma range, respectively. The oldest monazites are found in garnet-rich samples whereas the youngest monazite grains texturally replace allanite in sample retrogressed under greenschist-facies conditions. The lowest-grade sample (Tmax ∼ 370°C) bears also young monazites at 9.0 ± 1.0 Ma, as replacement products of allanite. The chronological results as well as the clear textural relationships between allanite and monazite (which furthermore show identical REE patterns) indicate a monazite growth at the expense of allanite at low temperature (< 370°C) during exhumation. This study shows that young Mio-Pliocene Himalayan monazite should not be considered systematically as a prograde or metamorphic-peak mineral.

Partial resetting of the U-Th-Pb systems in experimentally altered monazite: Nanoscale evidence of incomplete replacement

Alteration experiments on natural monazite crystals (Manangotry standard, Madagascar) under alkali conditions at 300, 400, 500 and 600 °C and 200 MPa were conducted to clarify mechanisms behind incomplete resetting of U-Th-Pb geochronological systems in monazite replaced by dissolution and precipitation processes. Above 400 °C, experimental products show typical replacement textures: a compositionally distinct monazite rim, referred as altered rim, surrounds the primary monazite (Mnz1). Isotopic and electron microprobe U-Th-Pb in situ dating of the altered rim yields intermediate ages between pristine monazite (555 Ma) and complete experimental resetting (0 Ma). Lead is systematically detected in altered rims, with concentration decreasing from 400 °C to 600 °C. The origin of incomplete resetting is elucidated with transmission electron microscope images that reveal an incomplete replacement of Mnz1 by a secondary monazite (Mnz2) within the altered rim. With increasing temperature, the size and volume of the Mnz2 within the altered rim become more important. Because no structural Pb or Pb nanoinclusions were observed, Pb in the altered rim is attributed to the Mnz1 component. Partial resetting of U-Th-Pb systems depends on the nanomixture of different Mnz1 proportions in the analyzed volume, and explains the higher rejuvenation at 600 °C than at lower temperatures. Although microanalytical techniques have the spatial resolution to date micrometer-sized rims, they are unable to resolve a nanoscale mixture of pristine and secondary monazite that could occur in altered rims formed by fluid-driven replacement, especially at low temperatures. Porosity and/or inclusions and complex age scattering in zoned monazite are significant markers that can indicate a possible nano-sized partial replacement.

Nucleation and Growth of Chrysotile Nanotubes in H2SiO3/MgCl2/NaOH Medium at 90 to 300 °C

Herein, we report new insights into the nucleation and growth processes of chrysotile nanotubes by using batch and semi-continuous experiments. For the synthesis of this highly carcinogenic material, the influences of temperature (90, 200, and 300 °C), Si/Mg molar ratio, and reaction time were investigated. From the semi-continuous experiments (i.e., sampling of the reacting suspension over time) and solid-state characterization of the collected samples by XRPD, TGA, FTIR spectroscopy, and FESEM, three main reaction steps were identified for chrysotile nucleation and growth at 300 °C: 1) formation of the proto-serpentine precursor within the first 2 h of the reaction, accompanied by the formation of brucite and residual silica gel; 2) spontaneous nucleation and growth of chrysotile between about 3 and 8 h reaction time, through a progressive dissolution of the proto-serpentine, brucite, and residual silica gel; and 3) Ostwald ripening growth of chrysotile from 8 to 30 h reaction time, as attested to by BET and FESEM measurements. Complementary results from batch experiments confirmed a significant influence of the reaction temperature on the kinetics of chrysotile formation. However, FESEM observations revealed some formation of chrysotile nanotubes at low temperatures (90 °C) after 14 days of reaction. Finally, doubling the Si/Mg molar ratio promoted the precipitation of pure smectite (stevensite-type) under the same P (8.2 MPa)/T (300 °C)/pH (13.5) conditions.

Thermochemical characterization of Ca4La6(SiO4)6(OH)2 a synthetic La- and OH-analogous of britholite: implication for monazite and LREE apatites stability

Thermochemical characterization of Ca4La6(SiO4)6(OH)2 a synthetic La- and OH-analogous of britholite: implication for monazite and LREE apatites stability In this contribution, monazite (LREEPO4) solubility is addressed in a chemical system involving REE-bearing hydroxylapatite, (Ca, LREE)10(PO4,SiO4)6(OH)2. For this purpose, a synthetic (La)- and (OH)-analogous of britholite, Ca4La6(SiO4)6(OH)2, was synthesised and its thermodynamic properties were measured. Formation enthalpy of -14,618.4±31.0 kJ·mol-1 was obtained by high-temperature drop-solution calorimetry using a Tian-calvet twin calorimeter (Bochum, Germany) at 975 K using lead borate as solvent. Heat capacities (Cp) were measured in the 143-323 K and 341-623 K ranges with an automated Perkin-Elmer DSC 7. For calculations of solubility diagrams at 298 K, the GEMS program was used because it takes into account solid solutions. In conditions representative of those expected in nuclear waste disposal, calculations show that La-monazite is stable from pH = 4 to 9 with a minimum of solubility at pH = 7. La-bearing hydroxylapatite precipitates at pH > 7 with a nearly constant composition of 99% hydroxylapatite and 1% La-britholite. Each mineral buffers solution at extremely low lanthanum concentrations (log{La} = 10-10-10-15 mol·kg-1 for pH = 4 to 13). In terms of chemical durability, both La-monazite and La-rich apatite present low solubility, a requisite property for nuclear-waste forms.

Th-Pb ion probe dating of zoned hydrothermal monazite and its implications for repeated shear zone activity: An example from the Central Alps, Switzerland: Dating Hydrothermal Monazite, Shear Zones

Th-Pb age dating of zoned hydrothermal monazite from alpine-type fissures/clefts is a powerful tool for constraining polyphase deformation at temperatures below 350°C and presents an alternative to K/Ar and 40Ar/39Ar dating techniques for dating brittle tectonics. This study considers the relationship between cleft orientations in ductile shear zones and cleft mineral crystallization during subsequent brittle overprinting. In the Grimsel area, located in the Aar Massif of the Central Alps, horizontal clefts formed during a primary thrust dominated deformation, while younger and vertically oriented clefts developed during secondary strike-slip movements. The change is due to a switch in orientation between the principal stress axes σ2 and σ3. The transition is associated with monazite crystallization and chloritization of biotite at around 11.5 Ma. Quartz fluid inclusion data allow a link between deformation stages and temperatures to be established and indicate that primary monazite crystallization occurred in both cleft systems at 300–350°C. While cleft monazite crystallization ceases at ~11 Ma in inactive shear zones, monazite growth, and/or dissolution-reprecipitation continues under brittle deformation conditions in vertical clefts during later deformation until ~7 Ma. This younger shear zone activity occurs in association with dextral strike-slip movement of the Rhone-Simplon fault system. With the exception of varying Th/U values correlated with the degree of oxidation, there is only limited compositional variation in the studied cleft monazites.