Abstract. Retrograde metamorphic rocks provide key insights into the pressure–temperature (P–T) evolution of exhumed material, and resultant P–T constraints have direct implications for the mechanical and thermal conditions of subduction interfaces. However, constraining P–T conditions of retrograde metamorphic rocks has historically been challenging and has resulted in debate about the conditions experienced by these rocks. In this work, we combine elastic thermobarometry with oxygen isotope thermometry to quantify the P–T evolution of retrograde metamorphic rocks of the Cycladic Blueschist Unit (CBU), an exhumed subduction complex exposed on Syros, Greece. We employ quartz-in-garnet and quartz-in-epidote barometry to constrain pressures of garnet and epidote growth near peak subduction conditions and during exhumation, respectively. Oxygen isotope thermometry of quartz and calcite within boudin necks was used to estimate temperatures during exhumation and to refine pressure estimates. Three distinct pressure groups are related to different metamorphic events and fabrics: high-pressure garnet growth at ∼1.4–1.7 GPa between 500–550 ∘C, retrograde epidote growth at ∼1.3–1.5 GPa between 400–500 ∘C, and a second stage of retrograde epidote growth at ∼1.0 GPa and 400 ∘C. These results are consistent with different stages of deformation inferred from field and microstructural observations, recording prograde subduction to blueschist–eclogite facies and subsequent retrogression under blueschist–greenschist facies conditions. Our new results indicate that the CBU experienced cooling during decompression after reaching maximum high-pressure–low-temperature conditions. These P–T conditions and structural observations are consistent with exhumation and cooling within the subduction channel in proximity to the refrigerating subducting plate, prior to Miocene core-complex formation. This study also illustrates the potential of using elastic thermobarometry in combination with structural and microstructural constraints, to better understand the P–T-deformation conditions of retrograde mineral growth in high-pressure–low-temperature (HP/LT) metamorphic terranes.
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Evaluation and application of the quartz-inclusions-in-epidote mineral barometer
Abstract We have examined the suitability of a quartz-inclusions-in-epidote (qtz-in-ep) mineral barometer to better constrain P-T histories of epidote-bearing lithologies. Theoretical calculations applying an isotropic elastic model suggest that the qtz-in-ep barometer exhibits minimal temperature dependence, and thus, offers the potential to constrain growth conditions of epidote in various geologic environments, including skarn deposits, epidote-bearing granitoids, and metamorphic rocks. To test if the applied equations of state and isotropic elastic model reasonably simulate the elastic evolution of two anisotropic minerals, we measured Raman shifts of the 464 cm–1 band of quartz inclusions relative to that of an unencapsulated quartz standard. We calculated a quartz inclusion pressure (Pincl464) at various temperatures and compared these values with temperature-dependent Pincl predicted by elastic modeling (Pinclmod) at elevated temperatures. Three epidote-bearing samples with reasonably well-constrained P-T histories were also examined: (1) sample HF14C from the Upper Schieferhuelle in the Western Tauern Window, Italy (Pincl464=0.01 GPa); (2) sample LdC-31C from Lago di Cignana, Italy (Pincl464≈0.16 GPa); and (3) sample FT1E from the Frosnitz Tal in the Western Tauern region, Austria (Pincl464=0.57 GPa). Entrapment pressures (Pent464) calculated from Pincl464 determined at various temperatures show nominal differences from Pent calculated from Pinclmod, suggesting that for qtz-in-ep pairs, the calculated Pent does not significantly vary with the temperature of measurement. Furthermore, our calculated Pent464 for a sample from the Upper Schieferhuelle is in agreement with petrographic context and previously established P conditions, and the Pent464 determined for the Frosnitz Tal sample closely approximate previously reported pressures. The Lago di Cignana sample is derived from an epidote vein that is encased in a high-P foliation, and the calculated Pent464 is consistent with early, low-P epidote vein formation that pre-dates high-P metamorphism, or alternatively, late vein formation during exhumation, and confirms that the epidote did not form at or near peak conditions (~2.0 GPa). The results of this study indicate that the qtz-in-ep barometer potentially provides another tool that geoscientists can employ to better constrain P-T conditions in some epidote-bearing environments, where conventional thermobarometric techniques cannot be applied.
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- Award ID(s):
- 1725110
- NSF-PAR ID:
- 10221055
- Date Published:
- Journal Name:
- American Mineralogist
- Volume:
- 105
- Issue:
- 8
- ISSN:
- 0003-004X
- Page Range / eLocation ID:
- 1140 to 1151
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract Mineral inclusions are ubiquitous in metamorphic rocks and elastic models for host‐inclusion pairs have become frequently used tools for investigating pressure–temperature (
P–T ) conditions of mineral entrapment. Inclusions can retain remnant pressures () that are relatable to their entrapment P–T conditions using an isotropic elastic model andP–T–V equations of state for host and inclusion minerals. Elastic models are used to constrainP–T curves, known as isomekes, which represent the possible inclusion entrapment conditions. However, isomekes require a temperature estimate for use as a thermobarometer. Previous studies obtained temperature estimates from thermometric methods external of the host‐inclusion system. In this study, we present the firstP–T estimates of quartz inclusion entrapment by integrating the quartz‐in‐garnet elastic model with titanium concentration measurements of inclusions and a Ti‐in‐quartz solubility model (QuiG‐TiQ). QuiG‐TiQ was used to determine entrapmentP–T conditions of quartz inclusions in garnet from a quartzofeldspathic gneiss from Goodenough Island, part of the (ultra)high‐pressure terrane of Papua New Guinea. Raman spectroscopic measurements of the 128, 206, and 464 cm−1bands of quartz were used to calculate inclusion pressures using hydrostatic pressure calibrations (), a volume strain calculation ( ), and elastic tensor calculation ( ), that account for deviatoric stress. values calculated from the 128, 206, and 464 cm−1bands’ hydrostatic calibrations are significantly different from one another with values of 1.8 ± 0.1, 2.0 ± 0.1, and 2.5 ± 0.1 kbar, respectively. We quantified elastic anisotropy using the 128, 206 and 464 cm−1Raman band frequencies of quartz inclusions and stRAinMAN software (Angel, Murri, Mihailova, & Alvaro, 2019, 234 :129–140). The amount of elastic anisotropy in quartz inclusions varied by ~230%. A subset of inclusions with nearly isotropic strains gives an averageand of 2.5 ± 0.2 and 2.6 ± 0.2 kbar, respectively. Depending on the sign and magnitude, inclusions with large anisotropic strains respectively overestimate or underestimate inclusion pressures and are significantly different (<3.8 kbar) from the inclusions that have nearly isotropic strains. Titanium concentrations were measured in quartz inclusions exposed at the surface of the garnet. The average Ti‐in‐quartz isopleth (19 ± 1 ppm [2 σ ]) intersects the average QuiG isomeke at 10.2 ± 0.3 kbar and 601 ± 6°C, which are interpreted as theP–T conditions of quartzofeldspathic gneiss garnet growth and entrapment of quartz inclusions. TheP–T intersection point of QuiG and Ti‐in‐quartz univariant curves represents mechanical and chemical equilibrium during crystallization of garnet, quartz, and rutile. These three minerals are common in many bulk rock compositions that crystallize over a wide range ofP–T conditions thus permitting application of QuiG‐TiQ to many metamorphic rocks. -
Abstract Raman spectroscopy is widely used to identify mineral and fluid inclusions in host crystals, as well as to calculate pressure-temperature (P-T) conditions with mineral inclusion elastic thermobarometry, for example quartz-in-garnet barometry (QuiG) and zircon-in-garnet thermometry (ZiG). For thermobarometric applications, P-T precision and accuracy depend crucially on the reproducibility of Raman peak position measurements. In this study, we monitored long-term instrument stability and varied analytical parameters to quantify peak position reproducibility for Raman spectra from quartz and zircon inclusions and reference crystals. Our ultimate goal was to determine the reproducibility of calculated inclusion pressures (“Pinc”) and entrapment pressures (“Ptrap”) or temperatures (“Ttrap”) by quantifying diverse analytical errors, as well as to identify optimal measurement conditions and provide a baseline for interlaboratory comparisons. Most tests emphasized 442 nm (blue) and 532 nm (green) laser sources, although repeated analysis of a quartz inclusion in garnet additionally used a 632.8 nm (red) laser. Power density was varied from <1 to >100 mW and acquisition time from 3 to 270s. A correction is proposed to suppress interference on the ~206 cm–1 peak in quartz spectra by a broad nearby (~220 cm–1) peak in garnet spectra. Rapid peak drift up to 1 cm–1/h occurred after powering the laser source, followed by minimal drift (<0.2 cm–1/h) for several hours thereafter. However, abrupt shifts in peak positions as large as 2–3 cm–1 sometimes occurred within periods of minutes, commonly either positively or negatively correlated to changes in room temperature. An external Hg-emission line (fluorescent light) can be observed in spectra collected with the green laser and shows highly correlated but attenuated directional shifts compared to quartz and zircon peaks. Varying power density and acquisition time did not affect Raman peak positions of either quartz or zircon grains, possibly because power densities at the levels of inclusions were low. However, some zircon inclusions were damaged at higher power levels of the blue laser source, likely because of laser-induced heating. Using a combination of 1, 2, or 3 peak positions for the ~128, ~206, and ~464 cm–1 peaks in quartz to calculate Pinc and Ptrap showed that use of the blue laser source results in the most reproducible Ptrap values for all methods (0.59 to 0.68 GPa at an assumed temperature of 450 °C), with precisions for a single method as small as ±0.03 GPa (2σ). Using the green and red lasers, some methods of calculating Ptrap produce nearly identical estimates as the blue laser with similarly good precision (±0.02 GPa for green laser, ±0.03 GPa for red laser). However, using 1- and 2-peak methods to calculate Ptrap can yield values that range from 0.52 ± 0.06 to 0.93 ± 0.16 GPa for the green laser, and 0.53 ± 0.08 GPa to 1.00 ± 0.45 GPa for the red laser. Semiquantitative calculations for zircon, assuming a typical error of ±0.25 cm–1 in the position of the ~1008 cm–1 peak, imply reproducibility in temperature (at an assumed pressure) of approximately ±65 °C. For optimal applications to elastic thermobarometry, analysts should: (1) delay data collection approximately one hour after laser startup, or leave lasers on; (2) collect a Hg-emission line simultaneously with Raman spectra when using a green laser to correct for externally induced shifts in peak positions; (3) correct for garnet interference on the quartz 206 cm–1 peak; and either (4a) use a short wavelength (blue) laser for quartz and zircon crystals for P-T calculations, but use very low-laser power (<12 mW) to avoid overheating and damage or (4b) use either the intermediate wavelength (green; quartz and zircon) or long wavelength (red; zircon) laser for P-T calculations, but restrict calculations to specific methods. Implementation of our recommendations should optimize reproducibility for elastic geothermobarometry, especially QuiG barometry and ZiG thermometry.more » « less
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Abstract Constraining conditions and mechanisms of the early stages of exhumation from within subduction zones is challenging. Although pressure, temperature, and age can be inferred from the exhumed rock record, it is generally difficult to derive each of these parameters from any single rock, thus demanding assumptions that diverse data from multiple samples can be safely combined into a single pressure‐temperature‐time (
P ‐T ‐t ) path that might then be used to infer tectonic context and mechanisms of exhumation. Here, we present new thermobarometric and geochronologic information preserved in a single sample from Syros, Greece, to deduce the conditions and rates of the earliest phase of exhumation as a part of the well‐preserved high‐pressure metamorphic rocks of the Cycladic Blueschist Unit (CBU). The sample studied here is a garnet‐bearing, quartz‐mica schist that records two distinct metamorphic events. Results from thermodynamic models and quartz‐in‐garnet elastic geobarometry show that metamorphic garnet cores formed asP ‐T conditions evolved from ∼485°C and 2.2 GPa to 530°C and 2.0 GPa, and that garnet rims formed as conditions evolved from ∼560°C and 2.1 GPa to ∼550°C and 1.6 GPa. Sm‐Nd geochronology on garnet cores and rims yields ages of 45.3 ± 1.0 and 40.5 ± 1.9 Ma, respectively, thus indicating a 4.8 ± 2.1 Myr growth span. Given the decompression path calculated based on garnet core and rimP ‐T estimates, we conclude that the distinct phases of garnet growth preserve evidence of the initial exhumation of portions of the CBU. -
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Abstract Eclogite thermobarometry is crucial for constraining the depths and temperatures to which oceanic and continental crust subduct. However, obtaining the pressure and temperature (
P–T ) conditions of eclogites is complex as they commonly display high‐variance mineral assemblages, and the mineral compositions only vary slightly withP–T . In this contribution, we present a comparison between two independent and commonly used thermobarometric approaches for eclogites: conventional thermobarometry and forward phase‐equilibrium modelling. We assess how consistent the thermobarometric calculations are using the garnet–clinopyroxene–phengite barometer and garnet–clinopyroxene thermometer with predictions from forward modelling (i.e. comparing the relative differences between approaches). Our results show that the overall mismatch in methods is typically ±0.2–0.3 GPa and ±29–42°C although differences as large as 80°C and 0.7 GPa are possible for a few narrow ranges ofP–T conditions in the forward models. Such mismatch is interpreted as the relative differences among methods, and not as absolute uncertainties or accuracies for either method. For most of the investigatedP–T conditions, the relatively minor differences between methods means that the choice in thermobarometric method itself is less important for geological interpretation than careful sample characterization and petrographic interpretation for derivingP–T from eclogites. Although thermobarometry is known to be sensitive to the assumedX Fe3+of a rock (or mineral), therelative differences between methods are not particularly sensitive to the choice of bulk‐rockX Fe3+, except at high temperatures (>650°C, amphibole absent) and for very large differences in assumedX Fe3+(0–0.5). We find that the most important difference between approaches is the activity–composition (a–x ) relations, as opposed to the end‐member thermodynamic data or other aspects of experimental calibration. When equivalenta–x relations are used in the conventional barometer,P calculations are nearly identical to phase‐equilibrium models (ΔP < 0.1). To further assess the implications of these results for real rocks, we also evaluate common mathematical optimizations of reaction constants used for obtaining the maximumP–T with conventional thermobarometric approaches (e.g. using the highesta Grs2 ×a Prp in garnet and Si content in phengite, and the lowesta Di in clinopyroxene). These approaches should be used with caution, because they may not represent the compositions of equilibrium mineral assemblages at eclogite facies conditions and therefore systematically biasP–T calculations. Assuming method accuracy, geological meaningfulP maxat a typical eclogite facies temperature of ~660°C will be obtained by using the greatesta Di,a Cel, anda Prp and lowesta Grs anda Ms; garnet and clinopyroxene with the lowest Fe2+/Mg ratios may yield geological meaningfulT maxat a typical eclogite facies pressure of 2.5 GPa.
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.2138/am-2020-7379
