Raman Spectra Of Carbonaceous Material Research Articles

Comparison between Raman spectra of carbonaceous material and carbon isotope thermometries in low-medium grade meta-carbonates: Implications for estimation of metamorphic temperature condition

The changes in the physicochemical conditions of the carbonaceous material during progressive metamorphism in metapelitic rocks is widely used as a geothermometer with the aid of Raman spectroscopy. However, the application of this technique in carbonate rocks has not been established yet. Here, we compare Raman spectroscopy of carbonaceous material thermometry and carbon isotope thermometry in low- to medium-grade metacarbonate rocks from the Archean Chitradurga Schist Belt in the Dharwar Craton, India. The carbonates in the lowermost Bababudan Group have metamorphosed under lower amphibolite facies metamorphic conditions giving consistent estimates for both Raman spectra of carbonaceous material thermometry (460–592 °C) and carbon isotope thermometry (450–560 °C). Contrastingly, in the Vanivilas Formation, the carbonaceous material with very fine flaky morphology in the grain boundary has slightly lower crystallinity, when compared to the coarse-grained ones near the vein boundary. Nevertheless, the carbon isotope thermometry estimated a lower temperature around 400 °C. The inconsistencies between the temperature estimates are ascribed to the pervasive post-metamorphic aqueous hydrothermal fluid infiltration indicated by the presence of numerous criss crossing quartz veins. This is also corroborated by the lowering of the oxygen isotope ratio of the carbonates near the vein boundary by 2.3‰, but without much difference in the carbon isotope ratios. The coarsening of the carbonaceous material near the vein boundary signifies fluid assisted recrystallisation, that enhanced the crystallinity as evidenced in the Raman spectra. Moreover, the negative δ13C shift in the carbonaceous material (c. –8.5 to –13‰) was possibly due to recrystallization following partial CO2 degassing. In the Chitradurga Schist Belt, the Bababudan Group and the Vanivilas Formation have regionally metamorphosed under lower amphibolite facies condition, possibly related to the widespread granitic intrusion at c. 2.61 Ga and later affected by hydrothermal event at c. 2.5 Ga.

An automatic peak deconvolution method for Raman spectra of terrestrial carbonaceous material for application to the geothermometers of Kouketsu et al. (2014)

AbstractCarbonaceous material undergoes changes in its maturity mainly in response to its thermal history. Among the various geothermometers based on Raman spectra of carbonaceous material, those proposed by Kouketsu et al. (2014) have been employed to investigate the temperatures experienced by terrestrial rocks that undergo low‐ to medium‐grade metamorphism. Although their geothermometers use spectral parameters that can be determined only by peak deconvolution, criteria for setting the initial conditions for nonlinear least‐squares fitting have not been specified, which may generate unnecessary errors in the estimated temperatures owing to differences in fitting results among data analysts. To address this issue, we developed a code that automatically calculates the parameters required for the geothermometers of Kouketsu et al. (2014); that is, the widths of the D1‐ and D2‐bands. Our code yields parameter values consistent with those of Kouketsu et al. (2014) for the same Raman data and is applicable to datasets other than those used to develop it. The geothermometers based on the obtained results show a comparable performance to Kouketsu et al. (2014). Errors in the estimated temperatures caused by variation in Raman systems and the subjective selection of the fitting method are smaller than the uncertainties of the geothermometer itself, so long as the temperature is calculated by following the procedures of the present study. Although this study focused only on geothermometers that require peak deconvolution, the development of those based on fitting‐free Raman parameters and on the reaction kinetics of carbonaceous material should be investigated in future studies.

First- and second-order Raman spectra of carbonaceous material through successive contact and regional metamorphic events (Ryoke belt, SW Japan)

The evolution of both the first- and second-order Raman spectra of carbonaceous material (CM) through successive contact and regional metamorphic events is explored in the western part of the Ryoke belt (Iwakuni-Yanai area, SW Japan). Thirty-two metasedimentary rock samples were collected along a N-S gradient locally affected by contact metamorphism before and after the main regional tectono-metamorphic event (DP1). First-order spectra document a decreasing peak area ratio R2 and an increasing temperature TCM towards the south and the surrounding granitoids. Domains with intermediate (535–600 °C) TCM values match the extent of the pre-DP1 contact aureole but also image a so far unclear post-DP1 aureole. The axial part of the belt, likely unaffected by granite intrusions, preserves southward increasing TCM from 425 to 660 °C. Second-order spectra show a single S1 band that splits into two peaks (S1- and S1+) whose frequency difference ΔS1 increases stepwise towards the south. The spatial distribution of ΔS1 follows that of the E–W trending regional metamorphic zones. The splitting of S1 indicates a transition from two-dimensional to three-dimensional CM and occurs at ~500 °C, which seems to be common to all metamorphic belts worldwide. Despite regional metamorphism CM was able to record the post-DP1 contact overprint and there is no clear observation of delayed CM recrystallization, which likely depends on the crystallinity of the CM precursor. A discrepancy between first- and second-order Raman parameters suggests that they partly record the influence of different factors; R2 gives an account of thermal events, particularly those related to localized contact metamorphism, whereas ΔS1 potentially yields information on regional variations in heating duration and pressure. This demonstrates the potential of the full Raman spectrum of CM for deciphering the complex thermal history of orogenic systems.

Deformation fabrics and strain localization mechanisms in graphitic carbon-bearing rocks from the Ailaoshan-Red River strike-slip fault zone

Graphitic carbon-bearing rocks generally occur in low-to high-grade metamorphic units. In many brittle faults, graphitic carbon is often associated with gouge or low-grade metamorphic rocks whereas in ductile faults, graphitic carbon commonly occurs in marble, schist or gneiss. Carbonaceous material gradually transforms from an amorphous into an ordered crystalline structure by increasing thermal metamorphism. The degree of graphitization is believed to be a reliable indicator of peak temperature conditions in the metamorphic rock. In this contribution, based on detailed field observations, the variably deformed and metamorphosed graphitic gneisses to phyllites, located within the footwall and hangingwall unit of the Cenozoic Ailaoshan-Red River strike-slip shear zone are studied. According to lithological features and temperatures determined by Raman spectra of carbonaceous material, these graphitic rocks and deformation fabrics are divided into three types. Type I is represented by medium-grade metamorphism and strongly deformed rocks with an average temperature of 509 °C and a maximum temperature of 604 °C. Type II is affected by low-grade metamorphism and deformed rocks with an average temperature of 420 °C. Type III is affected by lower-grade metamorphism and occurs in weakly deformed/undeformed rocks with an average temperature of 350 °C. Slip-localized micro-shear zones and laterally continuous or discontinuous slip-planes constituted by graphitic carbon aggregates are developed in Types I and II. The electron back-scattered diffraction (EBSD) lattice preferred orientation (LPO) patterns of graphitic carbon grains were firstly observed in comparison with LPO patterns of quartz and switch from basal <a>, rhomb <a> to prism<a> slip systems, which indicate increasing deformation temperatures. Comparison of quartz and graphite LPOs indicates that graphite LPOs show higher temperature conditions. According to the graphitic slip-planes, micro-shear zones with grain-size reduction and mylonitic foliation constituted by graphitic carbon minerals, we also propose that the development of fine-grained amorphous carbon plays an important role in rheological weakening of the whole rock during progressive ductile shearing.

Hydrothermal circulation and oil migration at the root of the heterogeneous micro-structure of carbonaceous material in the 2.0 Ga Zaonega Formation, Onega Basin, Russia

Organic-rich rocks of the 2.0 Ga Zaonega Formation, Karelia, Russia, have been studied extensively to gain understanding of the global carbon cycle and reconstruction of paleo-environments, directly after the Great Oxidation Event (GOE). This formation has a complex history of alteration, involving pervasive hydrothermal circulation, hydrocarbon generation/migration, and mineral authigenesis. Several previous studies have focused on the description of these secondary effects, and the identification of primary geochemical signals in the carbonaceous phases. Migration and infiltration of organic-rich fluids appear to have had only limited effect on the primary carbon isotope record (δ13Corg). However, the structural variability of carbonaceous material (CM) appears to have been strongly affected, with a range of reported structures including carbon onion-shaped nanostructures and mineral-templated graphite films. Here we present a systematic Raman spectroscopy-based study of the structural variability of CM in a drill core representing the middle and upper strata of the Zaonega Formation. The Raman spectra of CM show a systematic difference in structural order between the bulk carbonaceous matrix (Matrix-CM) and the CM occurring near mineral contacts (Contact-CM), indicating that mineral templating was an important process affecting structural order in the formation. The templating effect was observed on the surface of a wide range of minerals. The difference in structural order between Matrix-CM and Contact-CM can be traced throughout the ca. 400 m stratigraphy. The structural order varied with the degree of alteration and hydrothermal circulation, from highly ordered structures directly above a large gabbro intrusion at the bottom of the stratigraphy to less ordered structures higher up in the sequence. This trend directly correlates with the δ18O trend of secondary calcite, and can be attributed to the decreasing influence and temperature regime of hydrothermal circulation upward in the stratigraphy. The results presented here suggest that organic-rich hydrothermal fluids can locally strongly enhance graphitization of carbonaceous materials, and cause sample-scale heterogeneities in the structural order of organic materials. This has implications for the interpretation of carbonaceous materials in other ancient rocks experiencing circulation of organic-rich hydrothermal fluids.

Carbon Sources and the Graphitization of Carbonaceous Matter in Precambrian Rocks of the Keivy Terrane (Kola Peninsula, Russia)

The Precambrian rocks of the Keivy Terrane reveal five types of carbonaceous matter (CM): Fine-grained, flaky, nest, vein, and spherulitic. These types differ in their distribution character, carbon isotope composition, and graphitization temperatures calculated by the Raman spectra of carbonaceous material (RSCM) geothermometry. Supracrustal rocks of the Keivy Terrane contain extremely isotopically light (δ13CPDB = –43 ± 3‰) carbon. Presumably, its source was a methane–aqueous fluid. According to temperature calculations, this carbon matter and the host strata underwent at least two stages of metamorphism in the west of the Keivy Terrane and one stage in the east. The CM isotope signatures of several samples of kyanite schists (δ13CPDB = –33 ± 5‰) are close to those of oils and oil source rocks, and they indicate an additional carbon reservoir. Thus, in the Keivy territory, an oil-and-gas bearing basin has existed. Heavy carbon (δ13CPDB = −8 ± 3‰) precipitated from an aqueous CO2-rich fluid is derived from either the lower crust or the mantle. This fluid probably migrated from the Keivy alkaline granites into the surrounding rocks previously enriched with “methanogenic” carbon.

Slip parameters on major thrusts at a convergent plate boundary: regional heterogeneity of potential slip distance at the shallow portion of the subducting plate

Understanding variations of slip distance along major thrust systems at convergent margins is an important issue for evaluation of near-trench slip and the potential generation of large tsunamis. We derived quantitative estimates of slip along ancient subduction fault systems by using the maturity of carbonaceous material (CM) of discrete slip zones as a proxy for temperature. We first obtained the Raman spectra of CM in ultracataclasite and pseudotachylyte layers in discrete slip zones at depths below the seafloor of 1–4 km and 2.5–5.5 km, respectively. By comparing the area-under-the-peak ratios of graphitic and disordered bands in those Raman spectra with spectra of experimentally heated CM from surrounding rocks, we determined that the ultracataclasite and pseudotachylyte layers had been heated to temperatures of up to 700 and 1300 °C, respectively. Numerical simulation of the thermal history of CM extracted from rocks near the two slip zones, taking into consideration these temperature constraints, indicated that slip distances in the ultracataclasite and pseudotachylyte layers were more than 3 and 7 m, respectively. Thus, potential distance of coseismic slip along the subduction-zone fault system could have regional variations even at shallow depth (≤ 5.5 km). The slip distances we determined probably represent minimum slips for subduction-zone thrusts and thus provide an important contribution to earthquake preparedness plans in coastal areas facing the Nankai and Sagami Troughs.

Detection of increased heating and estimation of coseismic shear stress from Raman spectra of carbonaceous material in pseudotachylytes

AbstractFrictional heat generated during earthquakes provides insight into the coseismic fault strength. To detect increased heating associated with faulting at seismic slip rates, we analyzed the Raman spectra of carbonaceous material in natural and experimental pseudotachylytes derived from argillite. The results indicate that the increased carbonization in pseudotachylytes relative to the host rocks could be detected when the ambient temperature is lower than 280°C. This increased carbonization can occur in ~4–16 s and is preserved even after alteration of pseudotachylytes. The comparison between experiment and Raman data demonstrated that there is a correlation between the average shear stress and the Raman spectra in pseudotachylytes. The average coseismic shear stress estimated from the correlation was 1.8 MPa. The resulting apparent friction coefficient under hydrostatic conditions at depths of 4–6 km was ~0.03–0.05. Raman analysis of carbonaceous material‐bearing pseudotachylytes will be useful for estimation of coseismic fault strength.

The affects of heating time scales and deformation on Raman spectra of carbonaceous material -developments in Raman geothermometry-

The affects of heating time scales and deformation on Raman spectra of carbonaceous material -developments in Raman geothermometry-

Detection of frictional heating on faults using Raman spectra of carbonaceous material

Detection of frictional heating on faults using Raman spectra of carbonaceous material

Detection of frictional heating on faults using Raman spectra of carbonaceous material

Detection of frictional heating on faults using Raman spectra of carbonaceous material

Vitrinite reflectance and Raman spectra of carbonaceous material as indicators of frictional heating on faults: Constraints from friction experiments

Vitrinite reflectance (Ro) and Raman spectra of carbonaceous material (RSCM) are both widely used as indicators of the maximum attained temperatures in sedimentary and metamorphic rocks. However, the potential of these methods to estimate temperature increases associated with fault slip has not been closely studied. To examine this issue, friction experiments were conducted on a mixture of powdered clay-rich fault material and carbonaceous material (CM) at slip rates of 0.15 mm/s and 1.3 m/s in nitrogen (N2) gas with or without distilled water. After the experiments, we measured Ro and RSCM and compared to those in starting material. The results indicate that when fault material suffers rapid heating at >500 °C in ∼9 s at 1.3 m/s, Ro and the intensity ratio of D1 and D2 Raman bands of CM (ID2/ID1) markedly increase. Comminution with very small temperature rise in ∼32 min at 0.15 mm/s is responsible for very limited changes in Ro and ID2/ID1. Our results demonstrate that Ro and RSCM could be useful for the detection of frictional heating on faults when the power density is ≥0.52 MW/m2. However, the conventionally used Ro and RSCM geothermometers are inadequate for the estimation of peak temperature during seismic fault slip. The reaction kinetics incorporating the effects of rapid heating at high slip rates and studies of the original microtexture and composition of CM are required to establish a reliable thermometer for frictional heating on faults.

Change in the Raman spectra of carbonaceous material across the fault: an example from the thrust in the Jurassic Inuyama chert-clastic complex

Change in the Raman spectra of carbonaceous material across the fault: an example from the thrust in the Jurassic Inuyama chert-clastic complex

Thermal structure of low-grade accreted Lower Cretaceous distal turbidites, the Central Pontides, Turkey: insights for tectonic thickening of an accretionary wedge

Abstract: Albian-Turonian subduction-accretionary complexes are exposed widely in the Central Pontides. A major portion of the accretionary complexes is made up of a metaflysch sequence consisting of slate/phyllite and metasandstone intercalation with blocks of marble, Na-amphibole bearing metabasite, and serpentinite. The metaflysch sequence represents distal parts of a large Lower Cretaceous submarine turbidite fan deposited on the Laurasian active continental margin that was subsequently accreted and metamorphosed during the Albian. Raman spectra of carbonaceous material of the metapelitic rocks revealed that the metaflysch consists of metamorphic packets with distinct peak metamorphic temperatures. The majority of the metapelites are low-temperature (ca. 330°C) slates characterized by lack of differentiation of the graphite (G) and D2 defect bands. They possibly represent offscraped distal turbidites along the toe of the Albian accretionary wedge. Other phyllites are characterized by a slightly pronounced G band with a D2 defect band occurring on its shoulder. Peak metamorphic temperatures of these phyllites are constrained to 370-385 °C. The phyllites are associated with a strip of incipient blueschist facies metabasites and are found as a sliver within the offscraped distal turbidites. We interpret the phyllites as underplated continental sediments together with oceanic crustal basalt along the basal dA©collement. Tectonic emplacement of the underplated rocks into the offscraped distal turbidites was possibly achieved by out-of-sequence thrusting causing tectonic thickening and uplift of the wedge.

A new approach to develop the Raman carbonaceous material geothermometer for low‐grade metamorphism using peak width

AbstractThe Raman spectra of carbonaceous material (CM) from 19 metasediment samples collected from six widely separated areas of Southwest Japan and metamorphosed at temperatures from 165 to 655°C show systematic changes with metamorphic temperature that can be classified into four types: low‐grade CM (c. 150–280°C), medium‐grade CM (c. 280–400°C), high‐grade CM (c. 400–650°C), and well‐crystallized graphite (&gt; c. 650°C). The Raman spectra of low‐grade CM exhibit features typical of amorphous carbon, in which several disordered bands (D‐band) appear in the first‐order region. In the Raman spectra of medium‐grade CM, the graphite band (G‐band) can be recognized and several abrupt changes occur in the trends for several band parameters. The observed changes indicate that CM starts to transform from amorphous carbon to crystallized graphite at around 280°C, and this transformation continues until 400°C. The G‐band becomes the most prominent peak at high‐grade CM suggesting that the CM structure is close to that of well‐crystallized graphite. In the highest temperature sample of 655°C, the Raman spectra of CM show a strong G‐band with almost no recognizable D‐band, implying the CM grain is well‐crystallized graphite. In the Raman spectra of low‐ to medium‐grade CM, comparisons of several band parameters with the known metamorphic temperature show inverse correlations between metamorphic temperature and the full width at half maximum (FWHM) of the D1‐ and D2‐bands. These correlations are calibrated as new Raman CM geothermometers, applicable in the range of c. 150–400°C. Details of the methodology for peak decomposition of Raman spectra from the low to medium temperature range are also discussed with the aim of establishing a robust and user‐friendly geothermometer.

Constraints on the geodynamical evolution of Crete: insights from illite crystallinity, Raman spectroscopy and calcite twinning above and below the ‘Cretan detachment’

The Alpine nappes of Crete are commonly subdivided into a Lower and an Upper Nappe pile, both of which are considered to be separated by a low-angle extensional shear zone referred to as ‘Cretan detachment’. The presence of a detachment at the originally suggested position, however, is not supported by our data: (1) Neogene rocks are sandwiched between Tripolitza Unit and the Lower Nappes. (2) Calcite twinning analyses indicate that the major nappes on Crete were largely affected by subhorizontal, layer-parallel shortening rather than subvertical shortening. (3) Metamorphic Tripolitza carbonates resting on top of non-metamorphic Neogene strata on the one hand and illite crystallinity data on the other indicate inverse metamorphism along the ‘Cretan detachment’. (4) Raman spectra of carbonaceous material from rocks below the detachment are locally indicative for very low-grade or an absence of metamorphism within the Lower Nappes, indicating weaknesses of their present tectono-stratigraphical assignment to the Phyllite-Quartzite Unit. (5) Illite crystallinity in the Pindos Unit is substantially lower than in the Tripolitza Unit, although both Units are considered as the Upper Nappes. (6) Oxygene Isotope data indicate precipitation of twinned calcite veins at supercrustal conditions. These findings point to Miocene thrusting at supercrustal conditions, which postdates the exhumation of the Lower Nappes.

Metamorphic evolution of lawsonite eclogites from the southern Motagua fault zone, Guatemala: insights from phase equilibria and Raman spectroscopy

AbstractLawsonite eclogite (metabasalt and metadolerite) and associated metasedimentary rocks in a serpentinite mélange from an area just south of the Motagua fault zone (SMFZ), Guatemala, represent excellent natural records of the forearc slab–mantle interface. Pseudosection modelling of pristine lawsonite eclogite reproduces the observed predominant mineral assemblages, and garnet compositional isopleths intersect within the phase fields, yielding a progradeP–Tpath that evolves from 20 kbar, 470 °C (M1) to 25 kbar, 520 °C (M2). The dominant penetrative foliation within the eclogite blocks is defined by minerals developed during the prograde evolution, and the associated deformation, therefore, took place during subduction. Thermometry using Raman spectra of carbonaceous material in metasedimentary rocks associated with the SMFZ eclogites gives estimates of peak‐Tof ∼520 °C. Barometry using Raman spectroscopy shows unfractured quartz inclusions in garnet rims retain overpressures of up to ∼10 kbar, implying these inclusions were trapped at conditions just below the quartz/coesite transition, in agreement with the results of phase equilibrium analysis. Additional growth of Ca‐rich garnet indicates initial isothermal decompression to 20 kbar (M3) followed by hydration and substantial cooling to the lawsonite–blueschist facies (M4). Further decompression of the hydrated eclogite blocks to the pumpellyite–actinolite facies (3–5 kbar, 230–250 °C) is associated with dehydration and veining (M5). The presence of eclogite as m‐ to 10 m‐sized blocks in a serpentinite matrix, lack of widespread deformation developed during exhumation and derived progradeP–Tpath associated with substantial dehydration of metabasites within the antigorite stability field suggest that the SMFZ eclogites represent the uppermost part of the forearc slab crust sampled by an ascending serpentinite diapir in an active, moderate‐Tsubduction zone.

Extending the applicability of the Raman carbonaceous‐material geothermometer using data from contact metamorphic rocks

AbstractThe degree of graphitization of carbonaceous material (CM) has been widely used as an indicator of metamorphic grade. Previous work has demonstrated that peak metamorphic temperature (T) of regional metamorphic rocks can be estimated by an area ratio (R2) of peaks recognized in Raman spectra of CM. The applicability of this method to low‐pressure (&lt;3 kbar) contact metamorphism was tested using Raman spectroscopic analyses of samples from two contact‐metamorphic aureoles in Japan (Daimonji and Kasuga areas). A suitable measurement procedure allows the dependence of the geothermometer on sample type (thin section, chip) and incident angle of laser beam relative to the c‐axes of CM to be tested. Two important general results are: (i) in addition to standard thin sections, chips are also suitable for spectral analysis; and (ii) the incident angle of the laser beam does not significantly affect the temperature estimation, i.e. spectral measurements for the geothermometer can be carried out irrespective of the crystallographic orientation. A laser wavelength of 532 nm was used in this study compared with 514.5 nm in an independent previous study. A comparison shows that the use of a 532‐nm laser results in a slightly, but systematically larger R2 ratio than that of a 514.5‐nm laser. Taking this effect into account, our results show that there is a slight but distinct difference between the R2–T correlations shown by contact and regional metamorphic rocks: the former are slightly better‐crystallized (have slightly lower R2 values) than the latter at the same temperature. This difference is interpreted as due to the degree of associated deformation. Despite the slight difference, the results of this study coincide within the estimated errors of ±50 °C with those of the previously proposed Raman CM geothermometer, thus demonstrating the applicability of this method to contact metamorphism. To facilitate more precise temperature estimates in regions of contact metamorphism, a new calibration for analyses using a 532‐nm laser is derived. Another important observation is that the R2 ratio of metamorphosed CM in pelitic and psammitic rocks is highly heterogeneous with respect to a single sample. To obtain a reliable temperature estimate, the average R2 value must be determined by using a substantial number of measurements (usually N &gt; 50) that adequately reflects the range of sample heterogeneity. Using this procedure (with 532‐nm laser) and adapting our new calibration, the errors of the Raman CM geothermometer for contact metamorphic rocks decrease to ∼±30 °C.

Estimation of temperature rise in a shallow slip zone of the megasplay fault in the Nankai Trough

A megasplay fault branching from the subduction boundary megathrust in the Nankai Trough is thought to have caused large tsunamis associated with past Tonankai earthquakes. Because the temperature recorded in the fault can constrain parameters of seismic slip, we evaluated several temperature proxies (fluid-mobile trace element concentrations, Sr isotopes, magnetic minerals, inorganic carbon content, and Raman spectra of carbonaceous material) in material from a localized slip zone, sampled at Site C0004 by Integrated Ocean Drilling Program Expedition 316. Our results showed that the shallow part of the megasplay fault has not experienced temperatures above 300 °C. We also found that in addition to shear stress and slip distance, slip rate and porosity are effective parameters for frictional heat, as demonstrated by numerical analysis incorporating thermal diffusion. The slip rate estimated through these proxies may indicate that the fault did not slip with high velocity near the seafloor.

Raman spectroscopic carbonaceous material thermometry of low-grade metamorphic rocks: Calibration and application to tectonic exhumation in Crete, Greece

We present new Raman spectra data of carbonaceous material (CM) to extend the range of the Raman spectra of CM thermometer (RSCM) to temperatures as low as 100 8C. Previous work has demonstrated that Raman spectroscopy is an excellent tool to describe the degree of graphitization of CM, a process that is independent of pressure but strongly dependent on metamorphic temperature. A linear relationship between temperature and the Raman parameter R2 (derived from the area of the defect band relative to the ordered graphite band) forms the basis of a previous thermometer. Because R2 shows little variability in low-temperature samples, 330 8C serves as a lower limit on the existing thermometer. Herein, we present Raman spectra from a suite of low-temperature (100 to 300 8C) samples from the Olympics Mountains and describe other aspects of the Raman spectra of CM that vary over this range. In particular, the Raman parameter R1 (the ratio of heights of the disordered peak to ordered peak) varies regularly between 100 and 350 8C. These data, together with published results from higher-temperature rocks, are used to calibrate a modified RSCM thermometer, applicable from 100 to 700 8C. Application to low-grade metasediments in the Otago region in the South Island of New Zealand gives temperatures consistent with previous estimates, demonstrating the reliability of the modified RSCM thermometer. We apply the modified RSCM thermometer to 53 samples from Crete to evaluate the role of the Cretan detachment fault in exhuming Miocene high pressure/low-temperature metamorphic rocks exposed there. The metamorphic rocks below the detachment (the Plattenkalk and Phyllite–Quartzite units) give metamorphic temperatures that range from 250 to 400 8C, consistent with previous petrologic estimates. We also demonstrate that the Tripolitza unit, which lies directly above the detachment, gives an average metamorphic temperature of about 260 8C. The modest break in metamorphic temperature in central Crete indicates that the Cretan detachment accounts for only 5 to 7 km of exhumation of the underlying HP–LT metamorphic rocks, which were initially accreted at ~35 km. We argue that the bulk of the exhumation (~28 km out of 35 km total) occurred by pervasive brittle stretching and erosion of structural units above the detachment. D 2005 Elsevier B.V. All rights reserved.