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
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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
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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
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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
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