the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Hydroxyl in eclogitic garnet, orthopyroxene and oriented inclusion-bearing clinopyroxene, W Norway
Abstract. Ten West Norwegian eclogites, whose mineral chemistry records metamorphism of up to 850 °C and 5.5 GPa, were investigated for structural hydroxyl content in nominally anhydrous minerals. Garnet shows pronounced absorption in the wavenumber ranges of 3596–3633 cm−1, 3651–3694 cm−1 and 3698–3735 cm−1, and minor absorption centred at about 3560 cm−1. Clinopyroxene with aligned inclusions of either quartz, albite or quartz + pargasite has major absorption at 3450–3471 cm−1 and 3521–3538 cm−1 and minor absorption centred at 3350 cm−1 and approximately 3625 cm−1. The latter band is strongest in a sample with minute lamellar inclusions rich in Al, Fe and Na and was excluded from hydroxyl quantification. Orthopyroxene has large, narrow absorption peaks centred at 3415 cm−1 and 3515 cm−1 and smaller peaks at 3555 cm−1, 3595 cm−1 and 3625 cm−1. Five orthopyroxene-bearing eclogites exhibit relatively homogeneous amounts of structural hydroxyl in garnet (13–32 μg g−1), clinopyroxene (119–174 μg g−1) and orthopyroxene (4–17 μg g−1). The outer 200 μm wide rims of the orthopyroxene grains illustrate a late hydroxyl loss compared to core values of about 30 %, which is not evident in garnet and clinopyroxene. In contrast, the other five orthopyroxene-free eclogites exhibit variable amounts of hydroxyl in garnet (8–306 μg g−1 ) and clinopyroxene (58–711 μg g−1). Apart from extreme values, the structural hydroxyl content of clinopyroxene in the eclogites studied is lower than in comparable ultra-high pressure metamorphic samples, e.g. pristine (non-metasomatised) eclogite xenoliths from the lithospheric mantle underneath the Siberian and Slave cratons (by about 200 μg g−1) and coesite- and quartz-eclogites from the Erzgebirge and the Kokchetav massifs (by several hundred μg g−1). The low structural hydroxyl contents, the deficiency of molecular water and the preservation of diffusion-sensitive evidence from the mineral chemistry for metamorphism well beyond the stability field of amphibole suggest that oriented inclusions of quartz + pargasite were formed isochemically during decompression. In addition, structural hydroxyl content in clinopyroxene is inversely correlated with metamorphic pressure estimates obtained from orthopyroxene of the same samples. Therefore, structural hydroxyl in nominally anhydrous eclogite minerals can serve as an indicator of the effectiveness of retrogression.
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RC1: 'Comment on egusphere-2024-2734', Anonymous Referee #1, 12 Nov 2024
General Comments
The manuscript presents extensive FTIR data on well-characterized samples of UHP and HP eclogites from the Western Gneiss Region in Norway, previously detailed in Spengler et al. (2023, https://doi.org/10.5194/ejm-35-1125-2023). The sampling spans a substantial portion of this complex, making it significant and representative of large-scale processes. The unpolarized FTIR spectra are of high quality, providing an intriguing dataset for clinopyroxene, orthopyroxene, and garnet. The manuscript is well-written, clear, and effectively illustrated. In particular, several observations are noteworthy: (1) The sample containing hydrous phases at peak conditions exhibits two orders of magnitude more hydrogen in garnet than other samples, while clinopyroxene does not follow this trend. This discrepancy causes the partition D_Cpx/Grt to approach 1, contrasting significantly with other samples where values are around 40; (2) There is an observed anticorrelation between hydrogen content and pressure for clinopyroxene, interpreted as reflecting retrogression conditions (during exhumation?).
The first conclusion is compelling, suggesting local preservation of high hydrogen in samples that likely achieved the highest (H2O) activity. This sample (DS1438) lacks Opx, so only temperature is constrained (Spengler et al., 2023). It would be insightful to compare the measured hydrogen content in this sample to experimental data at saturation for the given temperature and varying pressure. An agreement under UHP conditions might then suggest local H2O saturation, at least for this sample.
The second conclusion is also valuable, as one might expect samples close to saturation to decrease their hydrogen content (since at H2O saturation, hydrogen content correlates positively with pressure. Samples far from saturation values (as argued here for the WGR) might, conversely, maintain constant hydrogen content or increase it if water activity rises during retrogression.
Specific Comments
The manuscript places considerable emphasis on the presence or absence of orthopyroxene in the eclogites. However, the influence of bulk chemistry on hydrogen distribution at peak conditions receives limited exploration in the discussion. Could the chemical composition of pyroxene in differing bulk compositions partially govern hydrogen distribution?
As the authors likely recognise, measuring absorbance in anisotropic minerals like pyroxenes is challenging, typically limiting measurements to 4-6 grains with ideally random orientations. Please consider addressing the potential impact of anisotropy on the observed hydrogen content across samples with varying numbers of measured grains. For the same reason, core/rim measurements may be compromised if performed on differently oriented grains. I am confident the increase in clinopyroxene hydrogen content during exhumation is valid; however, including some discussion on potential errors due to anisotropy would strengthen this argument (i.e., that the increase in hydrogen content surpasses possible orientation effects).
Please consider adding a table (e.g., Table 1) detailing geothermobarometric constraints (presumably from Spengler et al., 2023) for samples with FTIR data, to facilitate the interpretation of Figure 9.
Technical Corrections
- Figures 6 and 7: Presumably, "lg" denotes "log." The minor ticks on the vertical axis are missing in Figure 8.
- Line 89: "clinopyroxenen" should be corrected.
- Line 95: Add a parenthesis after "Liu and Massonne, 2022)."
- Line 176: "Chapter" should be replaced with "Section."Citation: https://doi.org/10.5194/egusphere-2024-2734-RC1 -
AC1: 'Reply on RC1', Dirk Spengler, 13 Nov 2024
Thank you for your comments on our manuscript, we really appreciate them.
The sample with the highest hydroxyl content in garnet (DS1438) comes from an outcrop previously studied by Terry et al. (2000; 10.2138/am-2000-11-1207), which provides metamorphic estimates of 34-39 kbar and 820 °C (sample 1066b). These estimates are based on the garnet-clinopyroxene thermometer of Krogh Ravna (2000; 10.1046/j.1525-1314.2000.00247.x) in combination with multi-equilibrium thermobarometry using the TWQ program version 2.02 of Berman (1991; Can. Min. 29:833). Both samples contain polycrystalline inclusions in clinopyroxene of quartz, which are interpreted to be after coesite and thus can be considered as independent evidence of earlier UHP metamorphism. The enstatite-in-clinopyroxene thermometer of Nimis and Taylor (2000; 10.1007/s004100000156) applied to sample DS1438 suggests 788+/-30 °C (for a choosen pressure of 40 kbar, Spengler et al., 2023), which overlaps in error with the temperature derived from sample 1066b. Therefore, the metamorphic temperatures and (minimum) pressures applicable to sample DS1438 are fairly well constrained. However, a low H2O activity of 0.00036 is included in the estimates of Terry et al. (2000), who argue that "This low activity of H2O may be consistent with the proposed very low or proposed absence of H2O content in fluid inclusions in garnet in the [nearby] microdiamond-bearing kyanite gneiss." This may suggest that the reason for the high hydroxyl content in the garnet of sample DS1438 is less an indication of the availability of external fluids during UHP metamorphism than of (the presence or type of nominally hydrous minerals in) the prograde mineral composition (whole rock chemistry), which differs markedly between the eclogite samples studied and the nearby microdiamond-bearing kyanite gneiss. Since sample DS1438 is the only one in the set of 10 eclogite samples that contains a nominally hydrous mineral during UHP metamorphism, we consider this sample less suitable to compare with systematics in the other samples. Unfortunately, we are not aware of any experimental study on the influence of water saturation on the hydroxyl content of nominally anhydrous minerals during UHP metamorphim.
All clinopyroxene grains analysed contain oriented inclusions of quartz (some together with pargasite), which may indicate a Ca-Eskola component in the precursor clinopyroxene, which in turn, as experimentally determined, dramatically increases the incorporation (saturation level) of hydroxyl in clinopyroxene (Bromiley and Keppler, 2004; 10.1007/s00410-003-0551-1). If one considers the reverse process, i.e. the reduction of the Ca-Eskola component by exsolution of quartz during early decompression, the hydroxyl content can be above the HP saturation level, so that a nominally hydrous phase is formed at the same time. Such pargasite (in close association with quartz) was found, with the exception of sample DS1438, only in clinopyroxene of Opx-bearing eclogite. This is consistent with the view that the hydroxyl in clinopyroxene of DS1438 was close to saturation (or at least comparably high) during UHP conditions, as in all Opx-bearing eclogites, but different from the remaining Opx-free eclogites (which have oriented quartz but no pargasite in clinopyroxene). Once pargasite has formed by exsolution in clinopyroxene, the hydroxyl content in the clinopyroxene host grain is expected to have decreased. However, further decompression allows for an increase in the hydroxyl content in clinopyroxene, as the (new) saturation level (of Ca-Eskola-free clinopyroxene) increases with decreasing pressure (Bromiley and Keppler, 2004). In a natural environment, such an increase may require the availability of water, which we believe may be related to the degree of retrogression in the samples (our Fig. 9). For clarity, it is perhaps better to note that the hydroxyl content in clinopyroxene measured and shown in Fig. 9 is not the hydroxyl content that was present at UHP conditions (because at UHP, the oriented inclusions of quartz + pargasite were still dissolved and therefore the OH content in clinopyroxene was higher). All OH amounts refer to post-exsolution. Plotting theses against pressure estimates of orthopyroxene (which is very sensitive to retrogression) illustrate how these OH contents vary with the accumulated retrogression in individual samples (i.e. the progression of Al diffusion in orthopyroxene).
Since the hydroxyl content in orthopyroxene is lower than that in garnet and clinopyroxene, the presence or absence of orthopyroxene in the peak metamorphic mineral assemblage is expected to have little affect on the hydroxyl distribution. However, an in-situ origin of pargasite in clinopyroxene in a chemically closed system implies that the Opx-bearing eclogite samples (all af which contain such pargasite) and most Opx-free eclogites (which do not contain such pargasite) had different hydrogen contents in the bulk rock during UHP metamorphism. The reason for this difference is unkown, but is probably related to the origin of the two groups of eclogite. The Opx-free eclogites were considered to be part of the Baltica crust, while the Opx-bearing eclogites show a garnet Ca-Cr-systematics known for mantle rocks (Spengler et al., 2023).
We agree that a small number of anisotropic grains with different orientations analysed using unpolarised light has a significant impact on the uncertainty of the hydroxyl content determined for each sample. The recent study by Qiu et al. (2018; 10.2138/am-2018-6620) suggests that the uncertainty of the hydroxyl content is +/-25% in most cases when averaging 2 grains. Since we used averages of 3-6 grains of clinopyroxene for the Opx-bearing eclogites shown in Fig. 9, the uncertainty per sample is expected to be less than 25%. The average clinopyroxene hydroxyl content in the samples with the highest metamorphic estimates (4.7-5.2 GPa) shown in Fig. 9 is 132 µg/g, while that with the lowest metamorphic estimate (2.2 GPa) is 174 µg/g, about 30% higher. Therefore, the inferred increase in structural hydroxyl content with decreasing metamorphic pressure may outweigh possible orientation effects.
We will be pleased to add information on the determination of metamorphic pressures to facilitate the interpretation of Fig. 9.
Citation: https://doi.org/10.5194/egusphere-2024-2734-AC1
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AC1: 'Reply on RC1', Dirk Spengler, 13 Nov 2024
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RC2: 'Comment on egusphere-2024-2734', Anonymous Referee #2, 14 Nov 2024
Review of manuscript 'Hydroxyl in eclogitic garnet, orthopyroxene...' by Spengler et al. egusphere-2024-2734
This ms. provides new data on H2O in coexisting garnet, clinopyroxene, and orthopyroxene in ten samples of eclogite from Western Norway. The data are used to identify the source of H2O that enabled the formation of hydrous minerals during retrogression. In particular, the major aim is to explain the formation of calcic amphibole (+quartz) lamellae observed in eclogitic clinopyroxene. The formation of such lamellae is a matter of debate, concerning both the underlying PT trend (decompression of cooling) and the source of H2O (internal or external). Thus, this timely and a welcome contribution to better understand metamorphic processes in subduction zones.
Concerning the formation of amphibole lamellae in clinopyroxene, the authors conclude that the process was driven by decompression and the consumption of internal H2O. By contrast, Konzett et al. (2008) came to the opposite conclusion, based on the H2O and trace element contents (Li, K) in eclogitic cpx from the Eastern Alps. Unfortunately, no data on mineral composition are given in the present contribution. If trace element data are available it is recommended to include such elements, especially those being indicative of fluid transfer.
Furthermore, the authors report that H2O in cpx is inversely correlated with pressure which they attribute to H2O incorporation during decompression. While this may be the case, there is a problem that needs to be considered. True, the experimental study by Bromiliy & Keppler (2004; cited by the authors) has shown that H2O in jadeite decreases with pressure (from 2 to 10 GPa) so that the mineral should be able to take up more H2O during decompression (compared to its content at Pmax). However, experiments with jd-di (± Ca-Eskola) solid solutions, which incorporate more H2O than pure jadeite, clearly demonstrated that clinopyroxene composition has a much greater effect on H2O content compared to P and T (Bromiley & Keppler, 2004). This is highlighted by the contrasting findings from natural cpx: H2O decrease with P (Koch-Müller et al. 2004), H2O increase (Katayama & Nakashima, 2003)), no depenence at all (Gose & Schmädicke, 2021).
Thus, at least the major element composition has to be included in order to justity the conclusions. This also applies to garnet. The authors report exceptionally high H2O of some 300 ppm in one sample (compared to <27 ppm in all other samples). This could simply be due to more Ca in the exceptional sample, as Ca has long been known to strongly enhance H2O (see papers by Rossman).
To sum up, the subject is cleary interesting and the manuscript well written (including good figures), but without incorporating major (and minor) element composition, it is problematic to draw far-reaching conclusions concerning the metamorphic evolution (including H2O).
Specific comments:
lines 10-14: The authors state that the structural hydroxyl content of clinopyroxene (some 60-700 ppm) is lower compared the literature reports for 'pristine eclogite xenoliths'. However, there are a number of such pristine samples with equally low contents (e.g., Bizimis & Peslier, 2015: 260-576 ppm; Huang et al. 2014: most samples have well below 1000 ppm).line 18-20: The authors state: 'structural hydroxyl content in clinopyroxene is inversely correlated with metamorphic pressure estimates obtained from orthopyroxene of the same samples. Therefore, structural hydroxyl ... can serve as an indicator ... of retrogression.' Clinopyroxene composition needs to be considered (see above).
line 29: Decomposition of jadeite cannot result in symplectite - it just produces albite.
line 95-96: 'Since the outcrop size is only 5 × 8 m2, we assume that sample DS1438 was in equilibrium with hydrous minerals during peak metamorphism.' What has the outcrop size to do with the assemblage? This statement requires explanation.line 100: Here, the authos list the secondary minerals (bio, amph, plag). If plag is present in decompressed eclogite, it should coexist with Na-poor cpx, unless it is heavily retrogressed in the amphibolite facies in which case all cpx (primary and secondary) is replaced by amph. However, this cannot be the case, as the authors report hydroxyl from cpx.
pages 6-7: It is important to give the number of grains from which IR spectra were collected to determine the H2O content for each mineral in a sample. What is the uncertainty of H2O contents in anisotropic minerals and garnet?
In case that H2O is obtained from anisotropic minerals by unpolarised radiation, at least ten grains with different orientations should be analysed. Are the pyroxenes randomly oriented? If not, the approach gives unreliable data. This information has to be added.
line 168: The authors mention element concentration variations in cpx in relation to albite lamellae. While there is little doubt that albite formed by precipitation from the host cpx, it would be much more interesting to provide such data for cpx with amp lamellae. After all, the formation of amp lamellae is one of the issues in the contribution.lines 183-190: Here, the authors evaluate the significance of the ambiguous band at 3618-3633 cm-1 in cpx, which they ascribe to inclusions of sheet silicates (similar as in a paper by Koch-Müller et al. 2004). It would be interesting to know, which mineral in particular could be responsible. It was shown that phengite could be behind such absorption bands. Is there any phengite in the samples?
line 209: The concentrations of rim and core (4–15 µgg−1 and 5– 18 µgg−1) are identical within the limits of uncertainty.
lines 212-213: Are all seven bands present in all samples? From Fig. 3, this does not seem to be the case. If not, is there a correlation with mineral composition or the paragenesis?
lines 251-254: The authors state that orthopyroxene rims show lower H2O contents than cores and thus experienced late hydrogen loss.However, this is not quite supported by the results in Table 1. The differences are not significant because they do not exceed the limits of uncertainty (at least 20 %). For cpx, there is a significant difference between cor and rim composition in 5 samples. In two samples, rim and core compositions are identical. But this is not discussed.
lines 273-274: The term 'inherited' is misleading. Are contents related to peak metamorphism or inherited from a prograde stage? Clarify.
lines 275-278: What caused the exceptionally high H2O in garnet of sample 1438?
The interpretation given (more hydrous conditions for the whole-rock during peak metamorphism) is not convincing unless other factors are evaluated. What about garnet compostion?
Fig. 8: Informative plot. Misprint in caption (exlogite).
line 282: Simply say what you mean by 'independent mineral-chemical evidence for equilibration at UHP metamorphic conditions'. Opx-barometry, coesite?
lines 283-284: What are the properties of 'All other samples'. Are they non-UHP, or indication of non-equilibrium?
lines 284-285: Here you conclude that hydroxyl was modified by the post-peak metamorphic evolution. The evidence for this - cpx in the zo-eclogite has not the highest H2O content (in contrast to garnet) - is not convincing. This may be the case, but without giving the mineral composition this is not justified. The high H2O content in garnet could just be due to high Ca.line 288: ... opx, which shares a mineral paragenesis with garnet. What do you mean? Rephrase.
lines 302-308'However, the samples with the highest hydroxyl content in clinopyroxene of orthopyroxene-free eclogite (DS2217) and orthopyroxene-bearing eclogite (DS2216) are exposed only a few hundred metres apart (Figure 1). This suggests that the structural hydroxyl variation in orthopyroxene-free eclogite is in part also related to different degrees of retrogression. It follows from the spatial proximity of chemically different samples with highest structural hydroxyl content in clinopyroxene, their lowest metamorphic pressure estimates (Figure 9) and independent textural and mineralogical evidence for strong retrogression of these samples (Spengler et al., 2023)' etcRephrase.line 316: What is precursor cpx? You mean the host cpx that previously contained more H2O?
lines 317-319: This reference to opx in order to exclude an external fluid rather farfetched. It is much more logical that fluid from an external source, first of all, reacts with the rim of cpx to form matrix pargasite by consumption of cpx rims. Such pargasite contains inclusions of vermicular quartz as seen in numerous examples of UHP eclogite. If such features are not observed, an external fluid is highly unlikely.
lines 322-323: This argument is good.
line 333: The volume of such lamellae is often overestimated. One per cent presumably is an upper limit. A rough estimation is easily done in BSE images.
line 342: '...samples thought to have formed by metasomatism...' Which samples? Reference?
lines 353-355: 'The source of the hydrous fluid is... likely related to partial melting of eclogite...' Unlikely. Partial melting draws all the fluid out of the rock because H2O strongly partitions into the melt. As a result, H2O will be depleted in the solid restite and not enriched.Citation: https://doi.org/10.5194/egusphere-2024-2734-RC2 -
AC2: 'Reply on RC2', Dirk Spengler, 18 Nov 2024
We would like to thank reviewer 2 for the detailed comments on our manuscript. The critical view constructively scrutinises the argumentation presented and leads to further improvements. We would like to respond to all comments below.
The mineral trace elements were not analysed in the samples examined and are not available. However, the previous study Spengler et al. (2023; 10.5194/ejm-35-1125-2023) includes EMPA data, which show that the K2O content of Cpx does not exceed 0.02 wt% (analysed in spot mode, Table 4) and that of re-integrated Cpx containing Qz+Amp inclusions has a range of 0.01-0.03 wt% (analysed with a widened beam, Table 5). In addition, we had also analysed in sample DS1438, but not reported, the composition of two types of Amp that occur as inclusions in Cpx together with Qz and as a retrograde phase between Cpx and Grt. The former Amp type contains 0.01-0.03 wt% K2O and the latter 0.07-0.17 wt%. These data suggest that the oriented inclusion-bearing Cpx, the Amp inclusions and the re-integrated Cpx all contain K as a trace element component with quantities lower than those reported form the Alpine samples CM31/03 and SKP31 (Konzett et al., 2008; 10.1016/j.lithos.2008.09.002).
The cited study of Bromiley & Keppler (2004; 10.1007/s00410-003-0551-1) makes two major conclusions, i.e. the H2O storage capacity in Jd increases with decreasing P and a Ca-Eskola bearing Jd-Di solid solution dramatically increases the H2O storage capacity in Cpx. We refer to both in our reply to RC1. In short, the initial decompression of WGR eclogite (from the stability fields of Coe and Ca-Eskola to that of Qz) is expected to decrease the storage capacity for H2O in Cpx, from which follows that the release of Qz may be associated with that of H2O. This is consistent with the joint exsolution of Qz+Amp in WGR Cpx, before further decompression caused an increase in the now Ca-Eskola-free Cpx (as shown in Figure 9). The finding from Bromiley & Keppler (2004) is consistent with the other study of Katayama & Nakashima (2003; 10.2138/am-2003-0126) showing that the hydroxyl absorbance in Cpx correlates positively (clearly increases) with the Ca-Eskola component. Conversely, this means that the decomposition of Ca-Eskola (by decompression) is accompanied by a release of H2O (provided there was enough H2O stored in Cpx prior to decompression). The study of Koch-Müller et al. (2004; 10.2138/am-2004-0701) shows that eclogite xenoliths from different depth levels of the Siberian lithospheric mantle differ in H2O content. Samples from the deepest levels contain less H2O in Cpx than those from shallower levels. However, these measurements illustrate a systematic of the regional SCLM, which does not necessarily reflect a systematic for the H2O storage capacity in Cpx, because the samples studied do neither share their evolution nor environment (the deep and shallow SCLM levels may chemically differ). Nevertheless, high H2O contents in Cpx from the shallow Siberian SCLM are consistent with our finding that H2O increases in WGR Cpx during decompression. The study of Gose & Schmädicke (2022; 10.1111/jmg.12642) on eclogite from the Erzgebirge shows indeed no major difference in H2O content between HP and UHP samples, but the difference in P of their samples account also only to about 10 kbar and clusters at the Qz/Coe phase transition. This is very different from the WGR samples that document >30 kbar decompression, from the stability field of diamond to that of Qz. This difference in P seems to be large enough to show (i) the release of H2O (by formation of oriented Qz+Amp during Ca-Eskola breakdown) and (ii) the subsequent uptake of H2O (as structural hydroxyl) in Cpx during further retrogression along the exhumation path. In summary, we cannot recognise the criticism raised by the reviewer when looking at the details of the studies mentioned.
The major element mineral chemistry of the samples studied is described in the previous study by Spengler et al. (2023). In fact, sample DS1438 has Grt with the highest CaO content in the sample set, 12.5 wt.%. The remaining Opx-free eclogites contain Grt, whose CaO content ranges between 7.8 and 10.9 wt%. Since the difference in H2O content between the former and the latter Grt is about an order of magnitude, the rather small difference in CaO content is probably not the cause of the difference in H2O content. For reasons of clarity for the reader, we are happy to add a corresponding note in the revised version of the manuscript.
To the specific comments:
lines 10-14: Correctly we said "Apart from extreme values ...". Figure 8 shows that, apart from three samples (Zo-bearing, retrogressed), the H2O content in WGR eclogitic Cpx is <200 ppm, while that of pristine eclogite xenoliths is dominantly above, consistent with the studies mentioned by the reviewer: Bizimis & Peslier (2015; 10.1016/j.chemgeo.2015.01.008) 260-576 ppm in Cpx of Hawaiian garnet-pyroxenite, Huang et al. (2014; 10.1007/s00410-014-1092-5) 211-1496 ppm in Cpx of Roberts Victor eclogite (the range covers Type I = metasomatised and Type II = non-metasomatised). To make this point even clearer to the reader, we would also like to include the data from these other references.
line 18-20: We will add some explanatory sentences to the revised version regarding the Cpx mineral chemistry described above.
line 29: The reviewer rightly stresses that the decomposition of (pure) Jd cannot lead to the formation of symplectite. However, what we meant, and what should be made clearer in the revised version, is that in practice the isochemical decomposition of the Jd component in Omp (which changes the composition of the Cpx from omphacitic to diopsidic) often occurs in the form of symplectites consisting of diopsidic Cpx and Pl (Anderson & Moecher, 2007; 10.1007/s00410-007-0192-x). This is a fairly typical mineral texture for eclogite, which, unlike a kimberlite eruption, was exhumed by a tectonic process.
line 95-96: The sentence preceding the quotation refers to "... hydrous minerals as part of the peak UHP metamorphic mineral assemblage ... could not be identified in the thin sections prepared." Therefore, we assume that the attentive reader understands without further words that due to the small outcrop size, chemical equilibration of the sample studied (DS1438) with hydrous peak metamorphic minerals can reasonably be assumed.
line 100: The reviewer is correct in the conclusion that Cpx in sample DS2217 should be Na-poor. Table 4 of Spengler et al. (2023) shows that this Cpx contains only 6-7 mol% Na-pyroxene.
pages 6-7: The reviewer raises an important point. The number of grains from which IR spectra were collected is given for each sample, mineral phase and grain domain in Table 1. The 1 sigma uncertainties of the quantified hydroxyl contents shown in Figure 8 were obtained from the calibration of Bell et al. (1995; 10.2138/am-1995-5-608), who reported uncertainties for the integral molar absorption coefficients of 10% for Grt, 4.4% for Cpx and 4.0% for Opx. However, these may be too low to be applied to our analytical results. The uncertainty in determining the thickness of the relatively thick grains (rock slabs) is estimated to be 1% or less. Major sources of error are the baseline correction of the spectra and the absorption variations resulting from the limited number of different orientations of anisotropic grains in unpolarised light (see also AC1 to RC1). Both uncertainties are reflected in the variation of the sample-specific hydroxyl contents determined per mineral domain, which are shown in Figure 6 and estimated to be 10% (1 sigma). The uncertainty in the accuracy of the values due to the calibration of the absorption coefficients is 10% or less (Bell et al., 1995; Libowitzky & Rossman, 1997; 10.2138/am-1997-11-1208). This gives a total uncertainty of 20%. Therefore, the error bars in Figure 9 should be updated.
line 168: The reason for including the mineral chemical variation in Cpx of sample DS2217 as Figure 5 was to highlight presumably hydrous phases of sub-micron width occurring in peripheral grain domains. These phases appear to be responsible for the absorption around 3622 1/cm, which is absent in most spectra of the other samples (Figure 3a). However, we can comply with the reviewer's request and include an example of an elemental distribution map of Cpx with Qz+Amp inclusions as Supplementary Information, as the information content is more likely to serve healthy curiosity than the subject of the manuscript.
lines 183-190: Sample 1066b from Fjørtoftvika, reported by Terry et al. (2000; 10.2138/am-2000-11-1207), contains phengite and comes from the same outcrop as sample DS1438. However, we could not detect phengite in any of our samples, but secondary biotite (in the matrix).
line 209: The reviewer is correct: looking at the entire data set, the ranges of the measured hydroxyl contents in the grain cores and grain rims are similar (as described in this sentence) and overlap in error. Looking at individual samples, the ranges between the two differ outside the error (as shown in Figure 6b and noted in the following sentence).
lines 212-213: As the reviewer correctly recognised, the number of bands in each sample is not always 7, as can also be seen in Figure 4, and varies between 4 and 7 depending on the sample and analysed grain domain (area), as shown in Table 1. As also shown in Table 1, the presence of specific bands in Grt does not depend on the presence of Opx in the mineral assemblage, which subdivides the dataset and reflects two distinct mineral chemistry trends of Grt (Figure 6a,b in Spengler et al., 2023). Therefore, we see no evidence of a clear correlation between bands and mineral assemblage or Grt chemistry. However, looking at the total number of absent bands in the entire dataset, the Opx-bearing eclogite has fewer than the Opx-free eclogite. Whether this is random or significant is beyond the scope of the study.
lines 251-254: We appreciate the reviewer's critical view and would like to note that even if the uncertainty of the individual measurement of hydroxyl is 20%, the Opx rims always show the lowest individual hydroxyl content and the Opx cores always the highest, with the exception of the strongly retrogressed sample DS2216 (Figure 6b, for a photo of Opx from this sample see Figure 8c in Spengler et al., 2023). This difference leads to different average values in Opx rims and cores per sample (Table 1), whose ratio OH_rim/OH_core is less than 1 (Figure 7). The two average values per sample do indeed have a large overlap in terms of uncertainty (although the uncertainty of the average values is slightly lower than that of the individual measurements). However, this overlap does not call into question the systematic nature of (i) the lower average values of the rims compared to the cores and (ii) the lower individual minimum and maximum values in the rims compared to the cores. Both indicate that the Opx rims have suffered a loss of hydroxyl - within the limits of analytical uncertainty, unless the obverved systematic would be by chance.
We would like to thank the reviewer for the other point raised, which relates to the different hydroxyl contents in rims and cores of Cpx. Actually, we refer in lines 254-255 to: "Ratios for clinopyroxene cluster from unity upwards, are consistent with uptake of hydroxyl at grain rims in some samples." Opx-bearing eclogite has Cpx with the highest difference in hydroxyl content between rim and core precisely in those two samples that have the lowest pressure estimates, DS0326 and DS2216. This ratio between rim and core can thus be considered an independent argument for hydroxyl uptake in Cpx during decompression-assisted retrogression, a relationship that we overlooked when analysing the data.
lines 273-274: Obviously, the use of the term "inherited" leads to confusion with a presumed prograde history (for which we actually provide no evidence at all). To increase clarity, we would like to replace the title of the subsection with "Differences in hydroxyl content during peak metamorphism" and reword this subsection slightly.
lines 275-278: Our answer is given in the same lines: "... the high structural hydroxyl content in its garnet is most likely related to the more hydrous conditions for the whole-rock during peak metamorphism." In principle, two possibilities are conceivable: Either the composition of the whole-rock (outcrop) of sample DS1438 differs in that it was inherently more hydroxyl-rich during UHP metamorphism, or the whole-rock was exposed to local fluids during UHP metamorphism, unlike the other samples. However, the subject of this study is not the cause of the exceptionally high hydroxyl content in the Grt of sample DS1438. More important, this sample shares oriented mineral inclusions in Cpx with the other samples, suggesting that the observed mineral microstructure appears to be independent of differences in hydrous conditions (either "inherited" from whole-rock chemistry during crystallisation at the peak of metamorphism or caused by local fluids during crystallisation at the peak of metamorphism). The main conclusions are drawn from the other samples. The data does not seem to be able to provide a deeper answer, although it would be interesting to explore this, we fully agree. A few additional explanatory sentences should make this clearer.
Fig. 8: As mentioned in our answer above (lines 10-14), the information on the xenolith data can be expanded.
line 282: We will use the term "Opx-barometry" in a rephrased sentence for clarity.
lines 283-284: The reviewer draws our attention to a point, which is described in our AC1 and which should be explained in more detail (in this and the next subsections). Following the logic, "All other samples" contain either retrogressed Opx (i.e. there is evidence of regression) or no Opx (they differ in overall rock chemistry from the Opx-bearing eclogites). The point is that, prior to exsolution of Qz, Opx-bearing eclogite appears to have been more "wet" compared to Opx-free eclogite (with the exception of DS1438). Thus, the former could, during initial decompression from the stability field of Ca-Eskola & Coe to that of Qz, exsolve Amp (together with Qz) while the latter did not (Qz only). Subsequent decompression increased the hydroxyl content of Cpx in those samples that accumulated retrogression. We will reword this part of the manuscript in the revised version to increase clarity.
lines 284-285: A reference to the previous study by Spengler et al. (2023) will allow the reader to obtain details of the desired mineral chemistry.
lines 302-308: The quoted sentence is indeed long. It will be reworded in the revised version.
line 316: Yes. The Cpx that now hosts the oriented Amp inclusions used to be without them, as Amp is not stable under UHP conditions. The same logic applies to the orientated Qz inclusions, as Qz is also not stable at UHP and the Opx-bearing eclogites do not contain grains of free silica (i.e. SiO2 was not part of the metamorphic mineral assemblage, making "overgrowth" of SiO2 during Cpx growth unlikely). Thus, Qz+Amp in Cpx are of secondary origin, for which two main scenarios can be considered: either the source of the chemical components that formed the orientated inclusions is external or internal. In the latter case, the (solid solution) precursor Cpx is expected to be more hydrous than the current (exsolved) host Cpx.
lines 317-319: The reviewer puts forward an interesting alternative hypothesis, which is challenged by the following remarks, which in turn could be added to the revised version:
- Amp, which occurs as lamellae together with Qz in Cpx grain cores, has a lower K content than Amp grains in the matrix (see first comment in this reply).
- Oriented inclusions of Qt+Amp in Cpx were never observed exclusively at the rims of the Cpx grains, as would be expected if they originated from an external fluid source. Instead, they occur either homogeneously in whole Cpx crystals (e.g. sample DS1438 in Figure 4c in Spengler et al., 2023) or with variable density in the grain cores, while they disappear towards the grain rims (e.g. sample M65 in Figure 2c,e in Spengler et al., 2023).
- All oriented Qz inclusions in Cpx that occur together with Amp have a crystallographic orientation relationship with the Cpx host (recognisable by a common angle of extinction under crossed-polarised light).
- The hydroxyl loss in Opx rims (Figure 7) seems to be inconsistent with an infiltration by an external fluid.
- It is highly unlikely that a penetrating fluid that partially alters the core of a Cpx crystal would leave the core of a neighbouring Opx crystal untouched, so that the latter retains a very low alumina content, indicating metamorphic conditions in the stability field of diamond, i.e. where Amp is not stable.line 333: The requested chemically integrated analyses of the microstructure were presented in the previous study (Spengler et al., 2023).
line 342: The reviewer's question can be answered by repeating the reference from line 337.
lines 353-355: The reviewer is correct, and we fully agree, that partial melting is likely to result in partitioning of H2O into the melt. In response, we replace the passage on melting with a sentence suggesting that the infiltration of fluids can explain the crystallisation of hydrous phases such as the matrix biotite, which is a source of rheological weakening and thus strain partitioning.
Citation: https://doi.org/10.5194/egusphere-2024-2734-AC2
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AC2: 'Reply on RC2', Dirk Spengler, 18 Nov 2024
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RC3: 'Comment on egusphere-2024-2734', Anonymous Referee #2, 04 Dec 2024
Thank you for this thoughtful response. I am confident that the manuscript will benefit from the envisaged changes and amendments. However, I strongly recommend adding compositional data and including them in the discussion (even though they were previously published). Only few people will bother to look this up elsewhere. No need to add comprehensive tables. Just giving XMg for all minerals, jd for cpx and grs for garnet in the same table with the H2O data is perfect. This makes the contribution more convenient for the reader and also gives it more impact (and possibly more insight concerning the relation between H2O and mineral composition).
Comment: K content in Cpx is usually too low to get reliable results from microprobe analysis.
Citation: https://doi.org/10.5194/egusphere-2024-2734-RC3 -
AC3: 'Reply on RC3', Dirk Spengler, 08 Dec 2024
The compositional data of the three minerals can easily be inserted into the manuscript and briefly included in the discussion, but require 5 additional columns to be presented. Since Table 1 is already page-filling, a new table for the compositional data is probably advisable.
We fully agree that the K content in Cpx is generally too low to be reliably analysed with EPMA. To clarify for the less informed reader, we can note that quantified values close to the detection limit are rather indicative.
Citation: https://doi.org/10.5194/egusphere-2024-2734-AC3
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AC3: 'Reply on RC3', Dirk Spengler, 08 Dec 2024
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