Effect of grossular on garnet-biotite,Fe–Mg exchange reactions: evidence from garnet with mixed growth and diffusion zoning

Garnets that exhibit mixed growth and diffusion zoning are used to evaluate the effect of grossular content on garnet Fe–Mg exchange reactions. These garnets from the uppermost amphibolite-facies to granulite-facies gneiss of the Wissahickon Group, southeastern Pennsylvania, show variation in grossular content (0.035<X _Ca<0.14) but nearly constant Mg? (X _Mg/(X _Mg+X _Fe) and X _Mn through the interior indicating re-equilibration of garnet and matrix minerals with respect to iron, magnesium, and manganese. Mg? is not correlated with calcium content, evidence that the effect of calcium on garnet Fe–Mg exchange reactions is small or is offset by other interactions in almandine-rich garnets. In either case, the data presented here indicate that correction for calcium content of garnets in the application of garnet-biotite geothermometry to high-grade metapelites is unnecessary and may lead to an overestimate of peak temperature.     

SIMS analyses of oxygen isotopes: Matrix effects in Fe-Mg-Ca garnets

Large instrumental mass fractionation (IMF) may occur during measurements of oxygen isotope ratios by SIMS. Part of this fractionation depends on crystal structure and mineral composition. In order to improve the accuracy of SIMS measurements, we gathered 6 commonly used garnet standards and prepared 6 others to adequately cover the composition range Alm_0-73, Prp_0-99, Grs_0-20. Electron microprobe analyses were performed at UBP-Clermont to check the chemical homogeneity of these standards. Oxygen isotope compositions were determined by laser fluorination and mass spectrometry at UW-Madison. Ten SIMS sessions and 336 δ¹⁸O measurements at CRPG-Nancy, on a Cameca IMS1270 instrument, demonstrate that the standards are homogeneous with external reproducibility of 0.3‰ (1σ). In terms of δ¹⁸O, SIMS measurements indicate that, during a single session, IMF can vary up to 6.3‰ from one garnet standard to another. In most of the sessions, IMF can be correlated with the grossular content. However, for a satisfactory correction scheme, we suggest the combination of the 3 main components (Ca, Fe, Mg). This is done using a simple least square calculation routine. The correction coefficients determined for each session can be used to calculate the IMF and correct the measured isotopic ratio of a garnet of known chemical composition. This way, we were able to reproduce the δ¹⁸O values of most of the Fe-Mg-Ca garnet standards within ± 0.6‰. Interestingly, the use of only 3 end-member standards (AlmCMG, PrpMM, GrsSE) plus a standard of intermediate composition (e.g. UWG-2) is sufficient to reproduce δ¹⁸O within the same precision. Thus, linear interpolation among end-member standards is satisfactory in the case of the garnet solid-solutions. Two studies carried out on zoned garnets from the Alps and the Pyrenees indicate that matrix effects become significant when variations in grossular contents are important (> 10%). In order to obtain reliable isotope ratio measurements on Fe-Mg-Ca garnets using a SIMS, we suggest a correction scheme using at least 3 reliable end-member standards plus a standard of intermediate composition (a garnet standard closest to the average composition of the analysed garnet). This allows cross-checking and incorporates a correction based on the variations in composition of zoned crystals.     

Chemical composition and evolution of the garnets in the Astamal Fe-LREE distal skarn deposit,Qara-Dagh–Sabalan metallogenic belt,Lesser Caucasus,NW Iran

The chemistry of garnet can provide clues to the formation of skarn deposits. The chemical analyses of garnets from the Astamal Fe-LREE distal skarn deposit were completed using an electron probe micro-analyzer. The three types of garnet were identified in the Astamal skarn are: (I) euhedral coarse-grained isotropic garnets (10–30 mm across), which are strongly altered to epidote, calcite and quartz in their rim and core, with intense pervasive retrograde alteration and little variation in the overall composition (Adr_94.3–84.4 Grs_8.5–2.7 Alm_1.9–0.2) (garnet I); (II) anhedral to subhedral brecciated isotropic garnets (5–10 mm across) with minor alteration, a narrow compositional range along the growth lines (Adr_82–65.4 Grs_21.9–11.7 Alm_11.1–2.4) and relatively high Cu (up to 1997 ppm) and Ni (up to 1283 ppm) (garnet II); and (III) subhedral coarser grained garnets (> 30 mm across) with moderate alteration, weak diffusion and irregular zoning of discrete grossular-almandine-rich domains (Adr_84.2–48.8 Grs_32.4–7.6 Alm_19.9–3.5) (garnet III). In the third type, the almandine content increases with increasing grossular/andradite ratio and increasing substitutions of Al for Fe^3 +.Almost all three garnet types have been replaced by fine-grained, dark-brown allanite that is typically disseminated and has the same relief as andradite. The Cu content increases while Ni content decreases slightly towards the rim of garnet II and garnet III. Copper in garnet II is positively correlated with increasing almandine content and decreasing andradite content, indicating that the almandine structure, containing relatively more Fe^2 +, is more suitable than andradite and grossular to host divalent cations such as Cu^2 +. Nickel in garnet II is positively correlated with increasing andradite content, total Fe, and decreasing almandine content. This is because Ni^2 + substitutes for Fe^3 + in the Y (octahedral) position. There are unusual discrete grossular-almandine rich domains within andraditic garnet III, indicating the low diffusivity of Ca compared to Fe at high temperatures.     

Compositional evolution of grossular garnet from leucotonalitic pegmatite at Ruda nad Moravou, Czech Republic; a complex EMPA, LA-ICP-MS, IR and CL study

Five distinct paragenetic, morphological and compositional types of grossular garnet (G1, G2, G3, G4, G5) were distinguished within the individual (sub)units of the zoned leucotonalitic pegmatite cutting serpentinized lherzolite with rodingite dikes at ??ár near Ruda nad Moravou, Staré Město Unit, Northern Moravia. Detailed study using Electron Microprobe Analysis, Laser Ablation Inductively Coupled Plasma Mass Spectrometry, Cathodoluminiscence and Infrared Spectroscopy revealed distinct compositional trends in major, minor and trace elements. The contents of Fe³⁺, Mn, Mg and Ti increase from early garnet (G1) in the outermost grossular subunit through the interstitial garnet (G2) in the leucocratic subunit to graphic intergrowths of quartz+garnet (G3) in the coarse-grained unit. Then these constituents decrease in inclusions of garnet (G4) from the blocky unit and large crystals of garnet (G5) from the quartz core. Some trace elements (V, Ni, Y) exhibit the same trends, only Be evidently increases in garnet from border zone to the centre. Fluorine has negative correlation with Fe³⁺ as well as some trace elements (Ta, Pb). Concentrations of H₂O in garnets, up to 0.22 wt.% H₂O, are comparable with spessartine-almandine garnets from the Rutherford No. 2 pegmatite, Virginia, and grossular garnets from high-temperature calc-silicate rocks (skarns). Water contents correlate positively with Fe³⁺, but inversely with F. The use of water contents in garnet to elucidate the fluctuations of activity of H₂O during the pegmatite formation is only limited; the incorporation of hydrous defects seems to be controlled instead by crystal-structural constraints. However, the sum of all volatile components (H₂O + F) increases about twice from the outermost subunit to the centre of the pegmatite body.     

Metasomatic origin of garnet xenocrysts from the V. Grib kimberlite pipe,Arkhangelsk region,NW Russia

This paper presents new major and trace element data from 150 garnet xenocrysts from the V. Grib kimberlite pipe located in the central part of the Arkhangelsk diamondiferous province (ADP). Based on the concentrations of Cr₂O₃, CaO, TiO₂ and rare earth elements (REE) the garnets were divided into seven groups: (1) lherzolitic “depleted” garnets (“Lz 1”), (2) lherzolitic garnets with normal REE patterns (“Lz 2”), (3) lherzolitic garnets with weakly sinusoidal REE patterns (“Lz 3”), (4) lherzolitic garnets with strongly sinusoidal REE patterns (“Lz 4”), (5) harzburgitic garnets with sinusoidal REE patterns (“Hz”), (6) wehrlitic garnets with weakly sinusoidal REE patterns (“W”), (7) garnets of megacryst paragenesis with normal REE patterns (“Meg”). Detailed mineralogical and geochemical garnet studies and modeling results suggest several stages of mantle metasomatism influenced by carbonatite and silicate melts. Carbonatitic metasomatism at the first stage resulted in refertilization of the lithospheric mantle, which is evidenced by a nearly vertical CaO-Cr₂O₃ trend from harzburgitic (“Hz”) to lherzolitic (“Lz 4”) garnet composition. Harzburgitic garnets (“Hz”) have probably been formed by interactions between carbonatite melts and exsolved garnets in high-degree melt extraction residues. At the second stage of metasomatism, garnets with weakly sinusoidal REE patterns (“Lz 3”, “W”) were affected by a silicate melt possessing a REE composition similar to that of ADP alkaline mica-poor picrites. At the last stage, the garnets interacted with basaltic melts, which resulted in the decrease CaO-Cr₂O₃ trend of “Lz 2” garnet composition. Cr-poor garnets of megacryst paragenesis (“Meg”) could crystallize directly from the silicate melt which has a REE composition close to that of ADP alkaline mica-poor picrites. P-T estimates of the garnet xenocrysts indicate that the interval of ～60–110 km of the lithospheric mantle beneath the V. Grib pipe was predominantly affected by the silicate melts, whereas the lithospheric mantle deeper than 150 km was influenced by the carbonatite melts.     

Single crystal Raman spectrum of uvarovite, Ca3Cr2Si3O12

Single-crystal Raman spectra of synthetic end-member uvarovite (Ca₃Cr₂Si₃O₁₂) and of a binary solution (59% uvarovite, 41% andradite) have been measured using single crystal techniques. For each of these garnets, 22 and 21 of the 25 Raman modes were located, respectively. The spectra for uvarovite garnets closely resemble those of the other calcic garnets, grossular, and andradite. The modes for uvarovites do not fit into the same trends as established by the other five anhydrous end-member garnets: the high energy “internal” Si–O modes do not depend on lattice constant in uvarovite. They exceed frequencies for both andradite and grossular. This is likely due to the large crystal field stabilization energy of trivalent chromium. The low energy and midrange modes are at similar frequencies to the other calcic garnets.     

Garnets in volcanic breccias of the Phlegraean Fields (southern Italy): mineralogical, geochemical and genetic features

Summary ?Post-magmatic garnets occur in volcanic breccias at the base of the Neapolitan Yellow Tuff (NYT) formation in the north-western area of the Phlegraean Fields. We report the results of a comprehensive study of these grandites. Garnet is found on the surfaces of tuffaceous blocks or inside their micropores, and is associated with sodalite, sanidine, marialite and amorphous silica. Garnet samples were examined by scanning electron microscopy (SEM), electron probe microanalysis (EPMA), powder and single-crystal X-ray diffraction (XRD) and infrared spectroscopy (IR). SEM observations on morphology showed typical dodecahedral and icositetrahedral habits. EPM analysis showed that they are close to grossular or andradite end members, with only moderate solid solution between them. X-ray study of single crystals showed cubic cell dimensions a_o of 11.86 ? (grossular) and 12.04 ? (andradite). IR spectroscopy confirmed the presence of hydroxyls in coexisting garnet and sanidine, 0.06 wt% H₂O (garnet) and 0.05–0.07 wt% H₂O (sanidine), respectively. Well-crystallized sanidine of an earlier generation showed significantly higher water contents, in the range 0.13–0.23 wt% H₂O. Type of occurrence and mineralogical features suggest a post-magmatic (pneumatolitic) genesis for these garnets. This is consistent with the physico-chemical processes linked to the eruptive dynamics of the breccias. Experimental studies of garnet synthesis at 550 °C and 2 kbar provide further support for this concept. Received January 16, 2002; accepted March 18, 2002     

The crystal chemistry of birefringent natural uvarovites. Part III. Application of the superposition model of crystal fields with a characterization of synthetic cubic uvarovite

Synthetic, flux-grown uvarovite, Ca₃Cr₂ [SiO₄]₃, was investigated by optical methods, electron microprobe analysis, UV-VIS-IR microspectrometry, and luminescence spectroscopy. The crystal structure was refined using single-crystal X-ray CCD diffraction data. Synthetic uvarovite is optically isotropic and crystallizes in the “usual” cubic garnet space group Ia3¯d [a=11.9973 Å, Z=8; 21524 reflections, R1=2.31% for 454 unique data and 18 variables; Cr–O=1.9942(6), Si–O=1.6447(6), Ca–O_a=2.3504(6), Ca–O_b= 2.4971(6) Å]. The structure of Ca₃Cr₂[SiO₄]₃ complies with crystal-chemical expectations for ugrandite group garnets in general as well as with predictions drawn from “cubically averaged” data of non-cubic uvarovite–grossular solid solutions (Wildner and Andrut 2001). The electronic absorption spectra of Cr³⁺ in trigonally distorted octahedra of synthetic uvarovite were analyzed in terms of the superposition model (SM) of crystal fields. The resulting SM and interelectronic repulsion parameters are =9532 cm^?1, =4650 cm^?1, power law exponent t ₄=6.7, Racah B₃₅=703 cm^?1 at 290 K (reference distance R ₀=1.995 Å; fixed power law exponent t ₂=3 and spin-orbit parameter ζ=135 cm^?1). The interelectronic repulsion parameters Racah B ₅₅=714 cm^?1 and C=3165 cm^?1 were extracted from spin-forbidden transitions. This set of SM parameters was subsequently applied to previously well-characterized natural uvarovite–grossular solid solutions (Andrut and Wildner 2001a; Wildner and Andrut 2001) using their extrapolated Cr–O bond lengths to calculate the energies of the spin-allowed bands. These results are in very good agreement with the experimentally determined band positions and indicate the applicability of the superposition model to natural 3d ^N prevailing systems in geosciences. Single-crystal IR absorption spectra of synthetic uvarovite in the region of the OH-stretching vibration exhibit one isotropic absorption band at 3508 cm^?1 at ambient conditions, which shifts to 3510 cm^?1 at 77 K. This band is caused by structurally incorporated hydroxyl groups via the (O₄H₄)-hydrogarnet substitution. The water content, calculated using an integral extinction coefficient ?=60417 cm^?2 l mol^?1, is c _H2O=33 ppm.     

High-temperature thermal expansion and elasticity of calcium-rich garnets

We present new high temperature elasticity data on two grossular garnet specimens. One specimen is single-crystal, of nearly endmember grossular, the other is polycrystalline with about 22% molar andradite. Our data extend the high temperature regime for which any garnet elasticity data are available from 1000 to 1350 K and the compositional range of temperature data to near endmember grossular. We also present new data on the thermal expansivity of calcium-rich garnet. We find virtually no discernable differences in the temperatureT derivatives at ambient conditions of the isotropic bulkK _S and shearμ moduli when comparing our results between these two specimens. These calcium-rich garnets have the lowest values of ¦(?K _S /?T) _P ¦ = (1.47,1.49) x 10^-2GPa/K, and among the highest values of ¦(?μ/?T) _P ¦ = 1.25 x 10^-2GPa/K, when compared with other garnets. Small, but measurable, nonlinear temperature dependences of most of the elastic moduli are observed. Several dimensionless parameters are computed with the new data and used to illustrate the effects of different assumptions on elastic equations of state extra-polated to high temperatures. We discuss how dimensionless parameters and other systematic considerations can be useful in estimating the temperature dependence of some properties of garnet phases for which temperature data are not yet available. While we believe it is premature to quantitatively predict the temperature variation ofK _S andμ for majorite garnets, our results have bearing on the amount of diopside required to explain the shear velocity gradients in Earth's transition zone.     

REE in skarn systems: A LA-ICP-MS study of garnets from the Crown Jewel gold deposit

Metamorphic and magmatic garnets are known to fractionate REE, with generally HREE-enriched patterns, and high Lu/Hf and Sm/Nd ratios, making them very useful as geochemical tracers and in geochronological studies. However, these garnets are typically Al-rich (pyrope, almandine, spessartine, and grossular) and little is known about garnets with a more andraditic (Fe³⁺) composition, as frequently found in skarn systems. This paper presents LA-ICP-MS data for garnets from the Crown Jewel Au-skarn deposit (USA), discusses the factors controlling incorporation of REE into garnets, and strengthens the potential of garnet REE geochemistry as a tool to help understand the evolution of metasomatic fluids.Garnets from the Crown Jewel deposit range from Adr₃₀Grs₇₀ to almost pure andradite (Adr_>99). Fe-rich garnets (Adr_>90) are isotropic, whereas Al-rich garnets deviate from cubic symmetry and are anisotropic, often showing sectorial dodecahedral twinning. All garnets are extremely LILE-depleted, Ta, Hf, and Th and reveal a positive correlation of ΣREE³⁺ with Al content. The Al-rich garnets are relatively enriched in Y, Zr, and Sc and show “typical” HREE-enriched and LREE-depleted patterns with small Eu anomalies. Fe-rich garnets (Adr_>90) have much lower ΣREE and exhibit LREE-enriched and HREE-depleted patterns, with a strong positive Eu anomaly. Incorporation of REE into garnet is in part controlled by its crystal chemistry, with REE³⁺ following a coupled, YAG-type substitution mechanism , whereas Eu²⁺ substitutes for X²⁺ cations. Thermodynamic data (e.g., H_mixing) in grossular-andradite mixtures suggest preferential incorporation of HREE in grossular and LREE in more andraditic compositions.Variations in textural and optical features and in garnet geochemistry are largely controlled by external factors, such as fluid composition, W/R ratios, mineral growth kinetics, and metasomatism dynamics, suggesting an overall system that shifts dynamically between internally and externally buffered fluid chemistry driven by fracturing. Al-rich garnets formed by diffusive metasomatism, at low W/R ratios, from host-rock buffered metasomatic fluids. Fe-rich garnets grow rapidly by advective metasomatism, at higher W/R ratios, from magmatic-derived fluids, consistent with an increase in porosity by fracturing.     

The thermodynamic properties and phase relations of some minerals in the system CaO-AI2O3-SiO2-H2O

The heat capacities of lawsonite, margante, prehnite and zoisite have been measured from 5 to 350 K with an adiabatic-shield calorimeter and from 320 to 999.9 K with a differential-scanning calorimeter. At 298.15 K, their heat capacities, corrected to end-member compositions, are 66.35, 77.30, 79.13 and 83.84 cal K^?1 mol^?1; their entropies are 54.98, 63.01, 69.97 and 70.71 cal K^?1 mol^?1, respectively. Their high-temperature heat capacities are described by the following equations (in calories, K, mol): Lawsonite (298–600 K): Cp° = 66.28 + 55.95 × 10^?3T ? 15.27 × 10⁵T^?2 Margarite (298–1000 K): Cp° = 101.83 + 24.17 × 10^?3T ? 30.24 × 10⁵T^?2 Prehnite (298–800 K): Cp° = 97.04 + 29.99 × 10^?3T ? 25.02 × 10⁵T^?2 Zoisite (298–730 K): Cp° = 98.92 + 36.36 × 10^?3T ? 24.08 × 10⁵T^?2 Calculated Clapeyron slopes for univariant equilibria in the CaO-Al₂O₃-SiO₂-H₂O system compare well with experimental results in most cases. However, the reaction zoisite + quartz = anorthite + grossular + H₂O and some reactions involving prehnite or margarite show disagreements between the experimentally determined and the calculated slopes which may possibly be due to disorder in experimental run products. A phase diagram, calculated from the measured thermodynamic values in conjunction with selected experimental results places strict limits on the stabilities of prehnite and assemblages such as prehnite + aragonite, grossular + lawsonite, grossular + quartz, zoisite + quartz, and zoisite + kyanite + quartz. The presence of this last assemblage in eclogites indicates that they were formed at moderate to high water pressure.     

On the origin of silicate-bearing diamondites

Garnets and clinopyroxenes, intergrown with diamonds in 37 diamondites (“bort”, “polycrystalline diamond aggregates”, “polycrystalline diamond”, “framesite”), presumably from southern Africa, were analyzed for trace element contents by LA-ICP-MS. The intimate diamond-silicate intergrowths suggest that both precipitated from the same fluids during the same crystallization events. In this study we distinguish 5 chemical garnet groups: “peridotitic” (P), intermediate (I) and 3 “eclogitic” groups (E1, E2 and E3). Chondrite-normalized trace element patterns for the garnet groups roughly correlate with major element abundances. Most of P garnets show complex, mildly sinusoidal REE_N patterns with relatively flat HREE_N-MREE_N, a small hump at Sm-Nd and depleted LREE_N, and have relatively high contents of Nb, Ta, U, and Th. The REE_N abundance patterns of E garnets differ by showing a continuous increase from LREE to HREE and depletion in LREE and highly incompatible elements relative to the P garnets. Of all garnet groups, E3 garnets are the poorest in highly incompatible trace elements and in Mg. Model equilibrium fluids for P garnets suggest crystallization from magnesian carbonate-bearing fluids/melts, which were very rich in incompatible trace elements — similar to kimberlites. Hypothetical equilibrium melts for E1 and E2 garnets are also magnesian and poorer in LREE and highly incompatible elements relative to typical kimberlitic or carbonatitic melts. Fluids that crystallized the P and most of the E garnets have similar mg numbers indicating a peridotitic source for both. The differences in Cr and highly incompatible element contents can be the result of differences in fluid formation and/or evolution rather than different source rock. The positive correlation of Cr₂O₃ and mg with the abundances of highly incompatible elements in garnets indicate fluid-rock fractionation processes rather than igneous fractional crystallization processes being responsible for the evolution of the diamondite-forming fluids.     

Effects of cation substitutions in garnet and pyroxene on equilibrium oxygen isotope fractionations

High-grade metamorphic rocks were used to explore oxygen isotope fractionations between pyroxene and garnet, and to investigate the effects on fractionation factors of the cation substitutions Fe³⁺Al_?1 and Ca(Fe,Mg)_?1. Recrystallized, granulite facies (725 °C) wollastonite ores from the northern Adirondack highlands contain essentially only the minerals clinopyroxene (a Di–Hd solid solution)+garnet (a Grs–Adr solid solution)±wollastonite, and exhibit a systematic dependence of measured fractionations on the Fe³⁺ content of calcic garnet: Δ(Cpx–CaGrt)=(0.14±0.12)+(0.78±0.20)X_Adr and Δ(Wo–CaGrt)=(0.15±0.22)+(0.57±0.33)X_Adr. In eclogites formed at T ≤650 °C, measured compositions of Ca-poor garnet and omphacite combined with experimental data indicate that Ca-poor, Fe-rich garnet is enriched in ¹⁸O compared to both diopside and grossular: extrapolating to 1000 K, Δ(Alm–Di)≈c. 0.2 and Δ(Alm–Grs)≈c. 0.5. Orthopyroxene and clinopyroxene from Gore Mountain, New York, show a constant fractionation that is independent of rock type, as expected if they have the same closure temperature. These data imply Δ(Opx-Cpx)≈c. 0.7 at 1000 K. Measured fractionations among Ca-poor garnet, orthopyroxene, clinopyroxene and hornblende in the Gore Mountain rocks further indicate an ¹⁸O enrichment in Ca-poor garnet over Grs (≈c. 0.5 at 1000 K). The new measurements are indistinguishable from expected equilibrium values based on experiments for the minerals enstatite, diopside, grossular, wollastonite and feldspar, but consistently indicate a significant isotope effect for the simple octahedral cation substitutions Fe³⁺Al_?1 (Grs vs. Adr) and Ca(Fe,Mg)_?1 (Ca-poor garnet vs. Grs; Opx vs. Cpx). Neither cation substitution has been directly investigated for its effect on ¹⁸O/¹⁶O fractionation with experiments in silicates. Chemical characterization of minerals is required prior to petrological interpretation of oxygen isotope trends.     

Local structure of ferric iron-bearing garnets deduced by IR-spectroscopy

Powder IR absorption spectroscopy has been used to characterise cation substitutions in three garnet solid solutions: grossular–andradite, skiagite–andradite and skiagite–almandine. The wavenumber shift of the highest energy mode associated with tetrahedral vibrations depends on the type of cation occupying the adjacent sites in the structure. The wavenumber shifts exhibit positive deviations from linearity that correlate closely with the variations of the Si–O bond distances for all three garnet solid solutions. The autocorrelation function has been used to determine an effective line width (Δcorr) of the absorption bands over a given spectral region. Non-linear behaviour of Δcorr was found for all three solid solutions. An empirical calibration between Δcorr excess and calorimetric enthalpy of mixing data gives an estimate for the symmetric Margules parameters W_spec^H of the three solid solutions. Comparison with the systematics of aluminosilicate garnets in terms of W_spec^H vs. ΔV², where ΔV represents the difference in molar volume between the end members in a binary system, reveals that such a relationship is not generally applicable to garnet solid solutions with an octahedral cation other than Al.     

XAFS characterization of the structural site of Yb in synthetic pyrope and grossular garnets

The incorporation and site preference of minor amounts (about 1 wt%) of Yb³⁺ in synthetic pyrope (Mg₃Al₂Si₃O₁₂) and grossular (Ca₃Al₂Si₃O₁₂) garnet were studied by X-ray Absorption Fine-Structure (XAFS) Spectroscopy. The measurements, performed in the temperature range 77–343 K at both Yb L_I- and L_III-edges, demonstrate that Yb³⁺ enters the garnet structure and is located in the dodecahedral site in both samples. The coordination environment of Yb³⁺ in the two samples was compared to that of the X-site cation in end-member synthetic pyrope and grossular and in Yb₃Al₅O₁₂ as determined by single-crystal X-ray diffraction. The local geometry around Yb³⁺ is different from that of Mg and Ca in the bulk of the garnet, and also from that of Yb³⁺ in Yb₃Al₅O₁₂. Τhe XAFS results indicate that, (1) structural relaxation occurs around Yb³⁺ in the garnet structure; (2) the host garnet matrix exerts a major structural control on the incorporation of Yb³⁺, and (3) minor amounts of Yb³⁺ in garnet are located in structural sites and not in ill-defined defects. Received: 15 January 1998/ Revised, accepted: 21 July 1998     

Hydroxyl defects in garnets from mantle xenoliths in kimberlites of the Siberian platform

A suite of more than 200 garnet single crystals, extracted from 150 xenoliths, covering the whole range of types of garnet parageneses in mantle xenoliths so far known from kimberlites of the Siberian platform and collected from nearly all the kimberlite pipes known in that tectonic unit, as well as some garnets found as inclusions in diamonds and olivine megacrysts from such kimberlites, were studied by means of electron microprobe analysis and single-crystal IR absorption spectroscopy in the v _OH vibrational range in search of the occurrence, energy and intensity of the v _OH bands of hydroxyl defects in such garnets and its potential use in an elucidation of the nature of the fluid phase in the mantle beneath the Siberian platform. The v _OH single-crystal spectra show either one or a combination of two or more of the following major v _OH bands, I 3645–3662 cm⁻¹, II 3561–3583 cm⁻¹, III 3515–3527 cm⁻¹, and minor bands, Ia 3623–3631 cm⁻¹, IIa 3593–3607 cm⁻¹. The type of combination of such bands in the spectrum of a specific garnet depends on the type of the rock series of the host xenolith, Mg, Mg-Ca, Ca, Mg-Fe, or alkremite, on the xenolith type as well as on the chemical composition of the respective garnet. Nearly all garnets contain band systems I and II. Band system III occurs in Ti-rich garnets, with wt% TiO₂ > ca. 0.4, from xenoliths of the Mg-Ca and Mg-Fe series, only. The v _OH spectra do not correspond to those of OH⁻ defects in synthetic pyropes or natural ultra-high pressure garnets from diamondiferous metamorphics. There were no indications of v _OH from inclusions of other minerals within the selected 60 × 60 μm measuring areas in the garnets. The v _OH spectra of pyrope-knorringite- and pyrope-knorringite-uvarovite-rich garnets included in diamonds do not show band systems I to III. Instead, they exhibit one weak, broad band (Δv _OH 200–460 cm⁻¹) near 3570 cm⁻¹, a result that was also obtained on pyrope-knorringite-rich garnets extracted from two olivine megacrysts. The quantitative evaluation, on the basis of relevant existing calibrational data (Bell et al. 1995), of the sum of integral intensities of all v _OH bonds of the garnets studied yielded a wide range of “water” concentrations within the set of the different garnets, between values below the detection limit of our single-crystal IR method, near 2 × 10⁻⁴ wt%, up to 163 × 10⁻⁴ wt%. The “water” contents vary in a complex manner in garnets from different xenolith types, obviously depending on a large number of constraints, inherent in the crystal chemistry as well as the formation conditions of the garnets during the crystallization of their mantle host rocks. Secondary alteration effects during uplift of the kimberlite, play, if any, only a minor role. Despite the very complex pattern of the “water” contents of the garnets, preventing an evaluation of a straightforward correlation between “water” contents of the garnets and the composition of the mantle's fluid phase during garnet formation, at least two general conclusions could be drawn: (1) the wide variation of “water” contents in garnets is not indicative of regional or local differences in the composition of the mantle's fluid phase; (2) garnets formed in the high-pressure/high-temperature diamond-pyrope facies invariably contain significantly lower amounts of “water” than garnets formed under the conditions of the graphite-pyrope facies. This latter result (2) may point to significantly lower f _H2O and f _O2 in the former as compared to the latter facies. Received: 25 November 1997 / Accepted: 9 March 1998     

Partition coefficients for REE between garnets and liquids: implications of non-Henry's Law behaviour for models of basalt origin and evolution

Partition coefficients for the rare earth elements (REE) Ce, Sm and Tm between coexisting garnets and hydrous liquids have been determined at high pressure and temperatures (30 kbar and 1300 and 1500°C). Two synthetic systems were studied, Mg₃Al₂Si₃O₁₂-H₂O and Ca₃Al₂Si₃O₁₂-H₂O, in addition to a natural pyrope-bearing system.Deviations from Henry's Law behaviour occur at geologically relevant REE concentrations. At concentrations < 3 ppm Ce, < 12 ppm Sm, < 80 ppm Tm in pyrope and < 100 ppm Ce, < 250 ppm Sm, < 1000 ppm Tm in grossular (at 30 kbar and 1300°C), D^{garnet liquid}_REE increases as the REE concentration in the garnet decreases. At higher concentrations, D_REE is constant. D^{grossular liquid}_REE also constant when the garnet contains less than about 2 ppm Sm or Tm. The REE concentration at which D_REE becomes constant increases with increasing temperature, decreasing REE ionic radius and increasing Ca content of the garnet.Partitioning behaviour of Ce, Sm and Tm between a natural pyrope-rich garnet and hydrous liquid is analogous to that in the synthetic systems and substantiates the substitution model proposed by Harrison and Wood (1980).Values of D_REE^{garnet/liquid} for which Henry's Law is obeyed are systematically higher for grossular than for pyrope (D^{pyrope/liquid} = 0.067(Ce), 0.108(Sm), 0.155(Tm) and D^{grossular/Liquid} = 0.65(Ce), 0.75(Sm), 4.55(Tm).The implications of non-Henry's Law partitioning of REE for models of basalt petrogenesis involving garnet are far-ranging. Deviations from Henry's Law permit refinements to be made to calculated REE abundances once basic model parameters have been defined.     

Statistical approaches to the discrimination of mantle- and crust-derived low-Cr garnets using major and trace element data

Diamond exploration focuses on geochemical analysis of indicator minerals that are more abundant than diamond itself. Among such indicators, low-Cr (Cr₂O₃ < 1 wt%) garnets from mantle eclogites are problematic since they overlap compositionally with many lower-crust-derived garnets also transported by kimberlite. Misclassification of these garnets may create “false positive” mantle signatures and possible misdirection of exploration efforts. Statistical solutions using major elements in low-Cr garnet (Hardman et al. in J Geochem Explor 186:24–35, 2018) provide improved error rates for the discrimination of low-Cr crustal and mantle garnets recovered from kimberlite. In this study we analysed a large suite of garnets (n = 571) from both crustal and mantle settings, already characterised for major elements, for a wide range of trace elements by laser ablation inductively-coupled plasma mass spectrometry and use these new data along with literature data (n = 169) to evaluate the effectiveness of adding trace elements to garnet-based diamond exploration programs. A new garnet classification scheme, initially using a major-element based filter, uses garnet Sr contents and Eu anomalies to help identify low-Cr garnets that are misclassified using major element methods. Combined with existing methods, our new trace element classifiers offer improvement in classification error rates for low-Cr, crustal and mantle garnets to as low as 4.7% for calibration data.

     

The CaGeO3–Ca3Fe2Ge3O12 garnet join: an experimental study

Germanate garnets are often used as isostructural analogues of silicate garnets to provide insight into the crystal chemistry and symmetry of the less accessible natural garnet solid solutions. We synthesised two series of germanate garnets at 3 GPa along the join^VIIICa₃^VI(CaGe)^IVGe₃O₁₂–^VIIICa₃^VIFe₂^IVGe₃O₁₂ at 900 °C and 1,100 °C. Samples with compositions close to the CaGeO₃ end-member consist of tetragonal garnet with a small amount of triclinic CaGe₂O₅. Samples with nominal compositions between X_Fe=0.4 and 1.0 consist of a mixture of tetragonal and cubic garnets; whereas, single-phase cubic garnets were obtained for compositions with X_Fe>1.2 (X_Fe gives the iron content expressed in atoms per formula unit, and varies between 0 and 2 along the join). Run products which were primarily single-phase garnet were investigated using Mössbauer spectroscopy. Spectra from samples synthesised at 1,100°C consist of one well-resolved doublet that can be assigned to Fe³⁺ in the octahedral site of the garnet structure. A second doublet, present primarily in samples synthesised at 900°C, can be assigned to Fe²⁺ at the octahedral sites of the garnet structure. The relative abundance of Fe²⁺ decreases with increasing iron content. Transmission electron microscopy analyses confirm this tendency and show that the garnets are essentially defect-free. The unit-cell parameters of tetragonal ^VIIICa₃^VI(CaGe)^IVGe₃O₃ garnet decrease with increasing synthesis temperature, and the deviation from cubic symmetry becomes smaller. Cubic garnets show a linear decrease of unit-cell parameter with increasing iron content. The results are discussed in the context of iron incorporation into ^VIIIMg₃^VI(MgSi)^IVSi₃O₃ majorite.