Hydrogen and oxygen isotope evidence for fluid–rock interactions in the stages of pre- and post-UHP metamorphism in the Dabie Mountains

Hydrogen and oxygen isotope studies were carried out on high and ultrahigh pressure metamorphic rocks in the eastern Dabie Mountains, China. The δ¹⁸O values of eclogites cover a wide range of −4.2 to +8.8‰, but the δD values of micas from the eclogites fall within a narrow range of −87 to −71‰. Both equilibrium and disequilibrium oxygen isotope fractionations were observed between quartz and the other minerals, with reversed fractionations between omphacite and garnet in some eclogite samples. The δ¹⁸O values of −4 to −1‰ for some of the eclogites represent the oxygen isotope compositions of their protoliths which underwent meteoric water–rock interaction before the high to ultrahigh pressure metamorphism. Heterogeneous δ¹⁸O values for the eclogite protoliths implies not only the varying degrees of the water–rock interaction before the metamorphism at different localities, but also the channelized flow of fluids during progressive metamorphism due to rapid plate subduction. Retrograde metamorphism caused oxygen and hydrogen isotope disequilibria between some of the minerals, but the fluid for retrograde reactions was internally buffered in the stable isotope compositions and could be derived from structural hydroxyls dissolved in nominally anhydrous minerals.     

Experimental synthesis and phase relations of phengitic muscovite from 6.5 to 11 GPa in a calcareous metapelite from the Dabie Mountains, China

The stability and phase relations of phengitic muscovite in a metapelitic bulk composition containing a mixed H₂O+CO₂ fluid were investigated at 6.5–11 GPa, 750–1050°C in synthesis experiments performed in a multianvil apparatus. Starting material consisted of a natural calcareous metapelite from the coesite zone of the Dabie Mountains, China, ultrahigh-pressure metamorphic complex that had experienced peak metamorphic pressures greater than 3 GPa. The sample contains a total of 2.1 wt.% H₂O and 6.3 wt.% CO₂ bound in hydrous and carbonate minerals. No additional fluid was added to the starting material. Phengite is stable in this bulk composition from 6.5 to 9 GPa at 900°C and coexists with an eclogitic phase assemblage consisting of garnet, omphacite, coesite, rutile, and fluid. Phengite dehydrates to produce K-hollandite between 8 and 11 GPa, 750–900°C. Phengite melting/dissolution occurs between 900°C and 975°C at 6.5–8 GPa and is associated with the appearance of kyanite in the phase assemblage. The formation of K-hollandite is accompanied by the appearance of magnesite and topaz-OH in the phase assemblage as well as by significant increases in the grossular content of garnet (average X_grs=0.52, X_py=0.19) and the jadeite content of omphacite (X_jd=0.92). Mass balance indicates that the volatile content of the fluid phase changes markedly at the phengite/K-hollandite phase boundary. At P≤8 GPa, fluid coexisting with phengite appears to be relatively CO₂-rich (XCO₂/XH₂O=2.2), whereas fluid coexisting with K-hollandite and magnesite at 11 GPa is rich in H₂O (XCO₂/XH₂O=0.2). Analysis of quench material and mass balance calculations indicate that fluids at all pressures and temperatures examined contain an abundance of dissolved solutes (approximately 40 mol% at 8 GPa, 60 mol% at 11 GPa) that act to dilute the volatile content of the fluid phase. The average phengite content of muscovite is positively correlated with pressure and ranges from 3.62 Si per formula unit (pfu) at 6.5 GPa to 3.80 Si pfu at 9 GPa. The extent of the phengite substitution in muscovite in this bulk composition appears to be limited to a maximum of 3.80–3.85 Si pfu at P=9 GPa. These experiments show that phengite should be stable in metasediments in mature subduction zones to depths of up to 300 km even under conditions in which aH₂O1. Other high-pressure hydrous phases such as lawsonite, MgMgAl-pumpellyite, and topaz-OH that may form in subducted sediments do not occur within the phengite stability field in this system, and may require more H₂O-rich fluid compositions in order to form. The wide range of conditions under which phengite occurs and its participation in mixed volatile reactions that may buffer the composition of the fluid phase suggest that phengite may significantly influence the nature of metasomatic fluids released from deeply subducted sediments at depths of up to 300 km at convergent plate boundaries.     

大别山双河超高压榴辉岩中的水: 微区红外光谱分析

大陆深俯冲板块到一定深度后(约90~110km), 几乎没有含水矿物存在, 超高压岩石中名义上无水矿物(NAMs) 成为俯冲板块中水的主要载体, 是示踪超高压变质流体的重要途径.对大别山双河地区超高压榴辉岩中的石榴石和绿辉石进行了详细的微区傅立叶变换红外光谱(MicroFTIR) 分析.FTIR结果显示所有石榴石和绿辉石颗粒都含有结构水, 以OH的形式存在, 其含量范围分别为(30~1860)×10-6和(360~620)×10-6.榴辉岩全岩水含量为(300~750)×10-6, 表明即使是在超高压变质作用的温压条件下, 榴辉岩也可以至少携带数百10-6的水进入深部地球.对石榴石颗粒内部的多点观察发现, 结构水含量的分布出现2种情况: (1) 颗粒内部的均一分布; (2) 核部水含量高而边部低.石榴石颗粒边部的低水含量可能是抬升过程中由于压力降低引起的H扩散所致, 扩散出来的H可能构成了早期退变质流体的重要来源.对于同一样品来说, 结构水含量在绿辉石和石榴石之间的比值为0.5~3.5.      

Petrology of ultrahigh-pressure eclogites from the ZK703 drillhole in the Donghai, eastern China

The 558-m-deep ZK703 drillhole located near Donghai in the southern part of the Sulu ultrahigh-pressure metamorphic belt, eastern China, penetrates alternating layers of eclogites, gneisses, jadeite quartzites, garnet peridotites, phengite–quartz schists, and kyanite quartzites. The preservation of ultrahigh-pressure metamorphic minerals and their relics, together with the contact relationship and protolith types of the various rocks indicates that these are metamorphic supracrustal rocks and mafic-ultramafic rock assemblages that have experienced in-situ ultrahigh-pressure metamorphism. The eclogites can be divided into five types based on accessory minerals: rutile eclogite, phengite eclogite, kyanite–phengite eclogite, quartz eclogite, and common eclogite with rare minor minerals. Rutile eclogite forms a thick layer in the drillhole that contains sufficient rutile for potential mining. Two retrograde assemblages are observed in the eclogites: the first stage is characterized by the formation of sodic plagioclase+amphibole symplectite or symplectitic coronas after omphacite and garnet, plagioclase+biotite after garnet or phengite, and plagioclase coronas after kyanite; the second stage involved total replacement of omphacite and garnet by amphibole+albite+epidote+quartz. Peak metamorphic P–T conditions of the eclogites were around 32 to 40 kbar and 720°C to 880°C. The retrograde P–T path of the eclogites is characterized by rapidly decreasing pressure with slightly decreasing temperature. Micro-textures and compositional variations in symplectitic minerals suggest that the decompression breakdown of ultrahigh-pressure minerals is a domainal equilibrium reaction or disequilibrium reaction. The composition of the original minerals and the diffusion rate of elements involved in these reactions controlled the symplectitic mineral compositions.     

Fluid inclusions in granulites, granulitized eclogites and garnet clinopyroxenites from the Dabie–Sulu terranes, eastern China

Minor granulites (believed to be pre-Triassic), surrounded by abundant amphibolite-facies orthogneiss, occur in the same region as the well-documented Triassic high- and ultrahigh-pressure (HP and UHP) eclogites in the Dabie–Sulu terranes, eastern China. Moreover, some eclogites and garnet clinopyroxenites have been metamorphosed at granulite- to amphibolite-facies conditions during exhumation. Granulitized HP eclogites/garnet clinopyroxenites at Huangweihe and Baizhangyan record estimated eclogite-facies metamorphic conditions of 775–805 °C and ≥15 kbar, followed by granulite- to amphibolite-facies overprint of ca. 750–800 °C and 6–11 kbar. The presence of (Na, Ca, Ba, Sr)-feldspars in garnet and omphacite corresponds to amphibolite-facies conditions. Metamorphic mineral assemblages and P–T estimates for felsic granulite at Huangtuling and mafic granulite at Huilanshan indicate peak conditions of 850 °C and 12 kbar for the granulite-facies metamorphism and 700 °C and 6 kbar for amphibolite-facies retrograde metamorphism. Cordierite–orthopyroxene and ferropargasite–plagioclase coronas and symplectites around garnet record a strong, rapid decompression, possibly contemporaneous with the uplift of neighbouring HP/UHP eclogites.

Carbonic fluid (CO₂-rich) inclusions are predominant in both HP granulites and granulitized HP/UHP eclogites/garnet clinopyroxenites. They have low densities, having been reset during decompression. Minor amounts of CH₄ and/or N₂ as well as carbonate are present. In the granulitized HP/UHP eclogites/garnet clinopyroxenites, early fluids are high-salinity brines with minor N₂, whereas low-salinity fluids formed during retrogression. Syn-granulite-facies carbonic fluid inclusions occur either in quartz rods in clinopyroxene (granulitized HP garnet clinopyxeronite) or in quartz blebs in garnet and quartz matrices (UHP eclogite). For HP granulites, a limited number of primary CO₂ and mixed H₂O–CO₂(liquid) inclusions have also been observed in undeformed quartz inclusions within garnet, orthopyroxene, and plagioclase which contain abundant, low-density CO₂±carbonate inclusions. It is suggested that the primary fluid in the HP granulites was high-density CO₂, mixed with a significant quantity of water. The water was consumed by retrograde metamorphic mineral reactions and may also have been responsible for metasomatic reactions (“giant myrmekites”) occurring at quartz–feldspar boundaries. Compared with the UHP eclogites in this region, the granulites were exhumed in the presence of massive, externally derived carbonic fluids and subsequently limited low-salinity aqueous fluids, probably derived from the surrounding gneisses.     

Metamorphic evolution of the Naga Hills eclogite and blueschist, Northeast India: implications for early subduction of the Indian plate under the Burma microplate

Tectonic slices and lenses of eclogite within mafic and ultramafic rocks of the Early Cretaceous–Eocene Naga Hills ophiolite were studied to constrain the physical conditions of eastward subduction of the Indian plate under the Burma microplate and convergence rate prior to the India–Eurasia collision. Some of the lenses are composed of eclogite, garnet-blueschist, glaucophanite and greenschist from core to margin, representing a retrograde hydrothermal alteration sequence. Barroisite, garnet, omphacite and epidote with minor chlorite, phengite, rutile and quartz constitute the peak metamorphic assemblage. In eclogite and garnet-blueschist, garnet shows an increase in Mg and Fe and decrease in Mn from core to rim. In chlorite in eclogite, Mg increases from core to rim. Inclusions of epidote, glaucophane, omphacite and quartz in garnet represent the pre-peak assemblage. Glaucophane also occurs profusely at the rims of barroisite. The matrix glaucophane and epidote represent the post-peak assemblage. The Fe³⁺ content of garnet-hosted omphacite is higher than that of matrix omphacite, and Fe³⁺ increases from core to rim in matrix glaucophane. Albite occurs in late stage veins. P – T pseudosection analysis indicates that the Naga Hills eclogites followed a clockwise P – T path with prograde metamorphism beginning at ∼1.3 GPa/525 °C and peaking at 1.7–2.0 GPa/580–610 °C, and subsequent retrogression to ∼1.1 GPa/540 °C. A comparison of these P – T conditions with numerical thermal models of plate subduction indicates that the Naga Hills eclogites probably formed near the top of the subducting crust with convergence rates of ∼ 55–100 km Myr⁻¹, consistent with high pre-collision convergence rates between India and Eurasia.     

A review and analysis of silicate mineral dissolution experiments in natural silicate melts

We present a database and a graphical analysis of published experimental results for dissolution rates of olivine, quartz plagioclase, clinopyroxene, orthopyroxene, spinel, and garnet in basaltic and andesitic melts covering a range of experimental temperatures (1100–1500°C) and pressures (10⁵ Pa-3.0 GPa). The published datasets of Donaldson (1985, 1990) and Brearly and Scarfe (1986) are the most complete. Experimental dissolution rates from all datasets are recalculated and normalized to a constant oxygen basis to allow for direct comparison of dissolution rates between different minerals. Dissolution rates (ν) range from 5·10⁻¹⁰ oxygen equivalent moles (o.e.m.) cm⁻² s⁻¹ for olivine in a basaltic melt to 1.3·10⁻⁵ o.e.m. cm⁻² s⁻¹ for garnet in a basaltic melt. Values of ln ν are Arthenian for the experiments examined and activation energies range from 118 to 1800 kJ/o.e.m. for quartz and clinopyroxene, respectively.

The relationship between calculated A/RT for the dissolution reactions, where A is the thermodynamic potential affinity, and values of ν is linear for olivine, plagioclase, and quartz. We interpret this as strong evidence in support of using calculated A as a predictor of ν for, at least, superliquidus melt conditions.     

榴辉岩中传统地质温压计新解：来自PT视剖面图的证据

石榴石-单斜辉石(GC)温度计和石榴石-单斜辉石-多硅白云母(GCP)压力计是确定榴辉岩形成温压条件的最常用方法,二者主要依据石榴石、绿辉石和多硅白云母中相组分之间的交换和转换变质反应.依据MORB成分计算的PT视剖面图表明,在不同榴辉岩矿物组合中,控制3个矿物相成分变化的相组分之间的变质反应不同.在低温含绿泥石、滑石和蓝闪石榴辉岩组合中,石榴石和绿辉石的镁含量主要受到含水矿物脱水反应的控制,并都随温度升高而升高,二者之间的铁镁交换反应并不起主要作用.因此,在自然界含有蓝闪石等含水矿物的低温榴辉岩中,由于绿辉石相对富镁而常常导致GC温度计结果偏低.在含有硬柱石的高压-超高压榴辉岩中,石榴石中的钙含量受到硬柱石的控制,随着压力升高或温度降低,硬柱石含量增加,使石榴石中钙降低,此时石榴石-绿辉石-多硅白云母之间的转换反应对石榴石成分的影响会很微弱,由于石榴石相对贫钙而导致GCP压力计结果偏低.在含有蓝晶石的中温高压-超高压榴辉岩中,矿物成分的变化受到石榴石-绿辉石之间的铁镁交换反应和石榴石．绿辉石．多硅白云母-蓝晶石-石英/柯石英之间的一系列转换反应控制,因此,GC和GCP温压计都能给出相对合理的结果.在低压普通角闪石榴辉岩中,石榴石和绿辉石中的镁含量主要反应压力变化,有时并不指示变质作用温度.在含有蓝闪石等含水矿物的低温榴辉岩中,Thermocalc程序中的平均温压(avPT)方法可以给出比较合适的温度,但压力结果与GCP压力计一样也会偏低一些.在蓝闪石和绿帘石等含水矿物消失后的中温蓝晶石榴辉岩中,avPT方法难以给出合理的PT信息.相对来说,视剖面图方法能够给出最多的PT信息,是目前确定变质岩PT条件的最好方法.     

Kyanite eclogite xenolith from the orthogneiss terrane of the Tisza Megaunit, Jánoshalma area, crystalline basement of southern Hungary

New evidence for high-pressure, eclogite facies metamorphism in the crystalline basement of the Tisza Megaunit (southern Hungary) is reported. The retrogressed mafic eclogite forms a small lens in the orthogneiss and it was found in the borehole near Jánoshalma. The carbonated eclogite contains the peak metamorphic assemblage omphacite + garnet + phengite + kyanite + clinozoizite + rutile + K-feldspar + quartz. Omphacite (Xjd_0.40–0.41Xdio_0.52–0.53Xhd_0.05Xaug_1.55–2.85) occurs in the matrix and as inclusions in garnet (Xpy_0.37–0.38Xgrs_0.21–0.22Xalm_0.39–0.40Xsps_0–0.01Xadr_0–0.01) and kyanite. Thermobarometry based on net-transfer reactions between garnet, omphacite, kyanite and phengite yields P–T conditions of 710 ± 10 °C and 2.6 ± 0.75 GPa. Retrogression during decompression is manifested by formation of symplectites; the most typical are diopside + plagioclase after omphacite, corundum + spinel + plagioclase after kyanite and biotite + plagioclase after phengite. Carbonatization along the veins of the retrogressed eclogite was probably coeval with formation of these symplectites. At places where carbonate is absent the rock was completely hydrated and retrogressed down to the greenschist facies with the development of actinolite. Similar eclogites together with abundant orthogneisses occur mainly in the eastern parts of the Tisza Megaunit, suggesting the existence of an ancient (possibly Variscan) subduction/accretionary complex.     

Metamorphic evolution, mineral chemistry and thermobarometry of schists and orthogneisses hosting ultra-high pressure eclogites in the Dabieshan of central China

As is typical of ultra-high pressure (UHP) terrains, the regional extent of the UHP terrain in the Dabieshan of central China is highly speculative, since the volume of eclogites and paragneisses preserving unequivocal evidence of coesite and/or diamond stability is very small. By contrast, the common garnet (X_Mn=0.18–0.45)–phengite (Si=3.2–3.35)–zoned epidote (Ps_38–97)–biotite–titanite–two feldspars–quartz assemblages in the more extensive orthogneisses have been previously thought to have formed under low P–T conditions of ca. 400±50°C at 4 kbar. However, certain orthogneiss samples preserve garnets with X_Ca up to 0.50, rutile inclusions within titanite or epidote and relict phengite inclusions within epidote with Si contents p.f.u. of up to 3.49 — overlapping with the highest values (3.49–3.62) recorded for phengites in samples of undoubted UHP schists. These and other mineral composition features (such as A-site deficiencies in the highest Si phengites, Na in garnets linked to Y+Yb substitution and Al F Ti₋₁ O₋₁ substitution in titanites) are taken to be pointers towards the orthogneisses having experienced a similar metamorphic evolution to the associated UHP schists and eclogites. Re-evaluated garnet–phengite and garnet–biotite Fe/Mg exchange thermometry and calculated 5 rutile+3 grossular+2SiO₂+H₂O=5 titanite+2 zoisite equilibria indicate that the orthogneisses may indeed have followed a common subduction-related clockwise P–T path with the UHP paragneisses and eclogites through conditions of P_max at ca. 690°C–715°C and 36 kbar to T_max at ca. 710°C–755°C and 18 kbar, prior to extensive re-crystallisation and re-equilibration of these ductile orthogneisses at ca. 400°C–450°C and 6 kbar. The consequential conclusion, that it is no longer necessary to resort to models of tectonic juxtapositioning to explain the spatial association of these Dabieshan orthogneisses with undoubted UHP lithologies, has far-reaching implications for the interpretation of controversial gneiss–eclogite relationships in other UHP metamorphic terrains.     

Micro-XANES determination of ferric iron and its application in thermobarometry

Micro-X-ray absorption near-edge structure (XANES) analysis was employed to determine the content of ferric iron in minerals formed in ultrahigh-pressure (UHP) eclogites. It is observed that omphacite and phengite contain significant amounts of Fe³⁺/Fe_tot (0.2–0.6), whereas only very low contents are present in garnet (Fe³⁺/Fe_tot=0.0–0.03), the latter being consistent with results from stoichiometric charge-balance calculations. Furthermore, considerable variations in the Fe³⁺/Fe_tot ratios of omphacite and phengite are observed depending on the textural sites and local bulk chemistry (eclogite and calc-silicate matrix) within one thin section. The oxidation state of isofacial minerals is thus likely to depend on the local fluid composition, which, in the studied case, is controlled by calcareous and meta-basic mineral compositions. These first in-situ measurements of ferric iron in an eclogite sample from the Dabie Shan, E China, are used to recalculate geothermobarometric data. Calculations demonstrate that the temperature during UHP metamorphism was as high as 780 °C, about 80–100 °C higher than previously estimated. Temperatures based on charge balance calculations often give erroneous results. Pressure estimates are in good agreement with former results and confirm metamorphism in the stability field of diamond (43.7 kbar at 750 °C). These P–T data result in a geothermal gradient of ca. 6 °C/km during UHP metamorphism in the Dabie Shan. However, accounting for ferric iron contents in geothermobarometry creates new difficulties inasmuch as calibrations of geothermometers may not be correctable for Fe³⁺ and the actual effect on Mg–Fe²⁺ partitioning is unknown. The present study further shows that micro-XANES is a promising technique for the in situ determination of ferric iron contents without destroying the textural context of the sample: a clear advantage compared to bulk methods.     

A high precision U–Pb age of metamorphic rutile in coesite-bearing eclogite from the Dabie Mountains in central China: a new constraint on the cooling history

This paper first reports a high precision U–Pb age of 218±1.2 Ma for rutile in coesite-bearing eclogite from Jinheqiao in the Dabie Mounteins, east–central China. This work shows that the U–Pb mineral (rutile+omphacite) isochron age of 218±2.5 Ma and conventional rutile U–Pb concordia age of 218±1.2 Ma obtained by common Pb correction based on the Pb isotopic composition of omphacite in the same eclogite sample are consistent, proving that the omphacite with low U/Pb ratio (μ=2.8) can be used for common Pb correction in U–Pb dating of rutile. Oxygen isotope analysis of rutile aliquots gave the consistent δ¹⁸O values of −6.1±0.1%, demonstrating oxygen isotope homogenization in the rutile of different grains as inclusion in garnet and grain in matrix. Oxygen isotope thermometry yields temperatures of 695±35 and 460±15 °C for quartz–garnet and quartz–rutile pairs, respectively. These oxygen isotopic observations suggest that the diffusion of oxygen in rutile as inclusion in garnet is not controlled by garnet. According to field-based thermochronological studies of rutile, an estimate of the T_c of about 460 °C for U–Pb system in rutile under rapid cooling conditions (20 °C/Ma) was advised. Based on this U–Pb age as well as the reported chronological data with their corresponding metamorphic and/or closure temperature, an improved T–t path has been constructed. The T–t path confirms that the UHPM rocks in South Dabie experienced a rapid cooling following the peak metamorphism before 220 Ma and a long isothermal stage from 213 to 180 Ma around 425 °C.     

北秦岭官坡地区高压—超高压榴辉岩岩相学及变质作用研究

北秦岭官坡地区的榴辉岩及含柯石英榴辉岩产在帮岭岩群的北侧，主要由绿辉石和石榴石组成，部分石榴石和绿辉石中含柯石英包体。此外还含有退变质的多硅白云母、角闪石、黝帘石和纳长石等矿物，根据变质矿物之间的替代关系及共生组合规律，榴辉岩退变质作用可划分为四个阶段，各阶段代表性矿物组合依次为：柯石英＋绿辉石＋石榴石；石英＋绿辉石＋石榴石；多硅白云母＋绿辉石＋石榴石＋石英；角闪石＋斜长石＋白云母＋黑云母。这四个     

Antimony in hydrothermal processes: solubility, conditions of transfer, and metal-bearing capacity of solutions

Based on data on the composition of ore-bearing hydrothermal solutions and parameters of ore-forming processes at various antimony and antimony-bearing deposits, which were obtained in studies of fluid inclusions in ore minerals, we investigated the behavior of Sb(III) in the system Sb–Cl–H₂S–H₂O describing the formation of these deposits.

We also performed thermodynamic modeling of native-antimony and stibnite dissolution in sulfide (m_HS⁻ = 0.0001−0.1) and chloride (m_Cl⁻ = 0.1−5) solutions and the joint dissolution of Sb_(s)⁰ and Sb₂S_3(s) in sulfide-chloride solution (m_HS⁻ = 0.01; m_Cl⁻ = 1) depending on Eh, pH, and temperature. All thermodynamic calculations were carried out using the Chiller computer program. Under the above conditions, stibnite precipitates in acid, weakly acid to neutral, and medium redox solutions, whereas native antimony precipitates before stibnite under more reducing conditions in neutral to alkaline solutions.

The metal-bearing capacity of hydrothermal solutions (200–250 °C) of different compositions and origins has been predicted. We have established that the highest capacity is specific for acid (pH = 2–3) high-chloride solutions poor in sulfide sulfur and alkaline (pH = 7–8) low-chloride low-sulfide solutions.     

Origin of retrograde fluid in ultrahigh-pressure metamorphic rocks: Constraints from mineral hydrogen isotope and water content changes in eclogite-gneiss transitions in the Sulu orogen

By taking advantage of having depth profiles between contrasting lithologies from core samples of the Chinese Continental Scientific Drilling (CCSD) project, a combined study was carried out to examine changes in mineral H isotope, total water and hydroxyl contents in garnet and omphacite across the contacts between ultrahigh-pressure (UHP) eclogite and gneiss in the Sulu orogen, east-central China. The samples of interest were from two continuous core segments from the CCSD main hole at depths of 734.21-737.16 and 929.67-932.86 m, respectively. The results show δD values of −116‰ to  − 64‰ for garnet and −104‰ to −82‰ for omphacite, consistent with incorporation of meteoric water into protoliths of UHP metamorphic rocks by high-T alteration. Both equilibrium and disequilibrium H isotope fractionations were observed between garnet and omphacite, suggesting fluid-assisted H isotope exchange at local scales during amphibolite-facies retrogression. While bulk water analysis gave total H₂O concentrations of 522-1584 ppm for garnet and 1170-20745 ppm for omphacite, structural hydroxyl analysis yielded H₂O contents of 80-413 ppm for garnet and 228-412 ppm for omphacite. It appears that significant amounts of molecular H₂O are present in the minerals, pointing to enhanced capacity of water storage in the UHP eclogite minerals. Hydrogen isotope variations in the transition between eclogite and gneiss show correlations with variations in their water contents. Petrographically, the degree of retrograde metamorphism generally increases with decreasing distance from the eclogite-gneiss boundary. Thus, retrograde metamorphism results in mineral reactions and H isotope variation. Because hydroxyl solubility in nominally anhydrous minerals decreases with dropping pressure, significant amounts of water are expected to be released from the minerals during decompression exhumation. Decompression exsolution of structural hydroxyl from 1 m³ volume of eclogite composed of only garnet and omphacite results in release of a quantitative estimate of 3.07-3.44 kg water that can form 140-156 kg amphibole during exhumation. Therefore, it is concluded that fluid for retrogression of the eclogites away from the eclogite-gneiss boundary was derived from the decompression exsolution of structural hydroxyl and molecular H₂O in nominally anhydrous minerals. For the eclogites adjacent to gneiss, in contrast, the retrograde metamorphism was principally caused by aqueous fluid from the gneiss which is relatively rich in water. Consequently, both the origin and availability of metamorphic fluid during exhumation of deeply subducted continental crust are deciphered by this combined study focusing on the transitions and the retrograde processes between the felsic and mafic UHP rocks.     

Paragonite eclogites from Dabie Shan,China: re-equilibration during exhumation?

Abstract Paragonite in textural equilibrium with garnet, omphacite and kyanite is found in two eclogites in the ultrahigh-pressure metamorphic terrane in Dabie Shan, China. Equilibrium reactions between paragonite, omphacite and kyanite indicate a pressure of about 19 kbar at c . 700° C. However, one of the paragonite eclogites also contains clear quartz pseudomorphs after coesite as inclusions in garnet, suggesting minimum pressures of 27 kbar at the same temperature. The disparate pressure estimates from the same rock suggest that the matrix minerals in the ultrahigh-pressure eclogites have recrystallized at lower pressures and do not represent the peak ultrahigh-pressure assemblages. This hypothesis is tested by calibrating a garnet + zoisite/clinozoisite + kyanite + quartz/coesite geobarometer and applying it to the appropriate eclogite facies rocks from ultrahigh- and high-pressure terranes. These four minerals coexist from 10 to 60 kbar and in this wide pressure range the grossular content of garnet reflects the equilibrium pressure on the basis of the reaction zoisite/clinozoisite = grossular + kyanite + quartz/coesite + H₂O. The results of the geobarometer agree well with independent pressure estimates from eclogites from other orogenic belts. For the paragonite eclogites in Dabie Shan the geobarometer indicates pressures in the quartz stability field, confirming that the former coesite-bearing paragonite-eclogite has re-equilibrated at lower pressures. On the other hand, garnets from other coesite-bearing but paragonite-free kyanite-zoisite eclogites show a very wide variation in grossular content, corresponding to a pressure variation from coesite into the quartz field. This wide variation, partly due to a rimward decrease in grossular component in garnet, is caused by partial equilibration of the mineral assemblage during the exhumation.     

Comprehensive chemical analyses of natural cordierites: implications for exchange mechanisms

Cordierite samples from pegmatites and metamorphic rocks have been analysed for major [electron microprobe analysis (EMPA)] and trace elements [inductively coupled plasma mass spectrometry (ICP-MS), secondary ion mass spectrometry analyses (SIMS)] as well as for H₂O and CO₂ (coulometric titration), and the results evaluated in conjunction with published data in order to determine which exchange mechanisms are significant. Apart from the homovalent substitutions FeMg₋₁ and MnMg₋₁ on the octahedral site, some minor KNa₋₁ on the Ch0 channel site, and Fe³⁺Al₋₁ on the T₁1 tetrahedral site, the three most important substitution mechanisms are those for the incorporation of Li on the octahedral sites (NaLi□₋₁Mg₋₁), and of Be and other divalent cations on the tetrahedral T₁1 site (NaBe□₋₁Al₋₁ and Na(Mg,Fe²⁺)□₋₁Al₋₁). The dominant role of the last vector is clearly demonstrated. We propose a new generalized formula for cordierite: ^Ch(Na,K)_0–1 ^VI(Mg,Fe²⁺,Mn,Li)₂ ^IVSi₅ ^IVAl₃ ^IV(Al, Be, Mg, Fe²⁺, Fe³⁺)O₁₈ *x^Ch(H₂O, CO₂…). Our results show that the population of (Mg, Fe²⁺) on the T₁1-site is limited to about 0.08 a.p.f.u. Other exchange mechanisms that were encountered in experiments operate only under P–T conditions or in bulk compositions that are rarely realized in nature. Routine analyses by electron microprobe in which Li and Be are not determined can be plotted as (Mg+Fe+Mn) versus (Si+Al) to assess whether significant amounts of Li and Be could be present. These amounts can be calculated as Li (a.p.f.u.)=Al+Na–4 and Be (a.p.f.u.)=10–2Al–M²⁺–Na.     

Liquid immiscibility and its role at the magmatic–hydrothermal transition: a summary of experimental studies

Several types of fluid immiscibility may affect the evolution of volatile-rich magmatic systems at the magmatic–hydrothermal transition. The topology of silicate–salt–H₂O systems implies that three-fluid immiscibility (silicate melt+hydrosaline melt+vapour) should be stable in a broad range of compositions and P–T conditions. The most important factor controlling the immiscibility appears to be the Coulombic properties (electric charges Z and ionic radii r) of the main network-modifying cations and the capacity for immiscibility appears to decrease in the following sequence: Mg>Ca>Sr>Ba>Li>Na>K. Liquid immiscibility is enhanced in peralkaline compositions and in the presence of nonsilicate anions such as F⁻, Cl⁻, CO₃²⁻ and BO₃³⁻. In volatile-rich magmatic systems, the H₂O is likely to react with the chloride, fluoride, borate and carbonate species and the chemical effects of high-temperature hydrolysis may be greatly enhanced by phase separation in systems with multiple immiscible fluid phases. Natural granitic magmas can thus exsolve a range of chemically and physically diverse hydrosaline liquids and the role of these fluid phases is likely to be especially significant in pegmatites and Li–F rare-metal granites.     

Mineralogical and chemical transformation of Oldoinyo Lengai natrocarbonatites, Tanzania

The minerals of Oldoinyo Lengai natrocarbonatite lavas are unstable under atmospheric conditions. Subsolidus mineral assemblages in natrocarbonatites were studied in 105 samples from contemporary eruptions ranging from present day to about 100 years old. The subsolidus minerals in natrocarbonatites were formed (i) along cracks on the lava surface from hot gases escaping during cooling, (ii) as atmospheric alteration by solution of water-soluble minerals, in particular halides and gregoryite, and by hydration of nyerereite under the influence of meteoric water and (iii) by reaction with fumarole gases. After solidification, the lavas were cut by a network of thin cracks, the edges of which are covered by polymineralic encrustations. Samples collected 2–24 h after eruption contain nahcolite, trona, sylvite, and halite with accessory kalicinite and villiaumite. Atmospheric humidity results immediately (≥ 2 h after eruption) in alteration of black lavas that is marked by the appearance of white powdery thermonatrite with nahcolite on the lava surface. Subsequent reaction (weeks, months, years) of natrocarbonatite with meteoric water and the atmosphere results in the formation of pirssonite, gaylussite, shortite, trona, thermonatrite, nahcolite and calcite. Generally, the first important step is the formation of pirssonite and the end-members are calcite carbonate rocks or loose aggregates. Fumarolic activity is common for the active northern crater of the volcano. Reaction of hot (54–141 °C) fumarolic gases with natrocarbonatite leads to the formation of sulphur, gypsum, calcite, anhydrite, monohydrocalcite, barite and celestine. Changes in mineralogy of the natrocarbonatite lead to substantial chemical transformation. The most obvious chemical changes in this process are the loss of Na, K, Cl and S, combined with an increase in H₂O, Ca, Sr, Ba, F and Mn. The oxygen and carbon isotopic composition of altered natrocarbonatites shows a significant shift from the primary “Lengai Box” to high values of δ¹⁸O and δ¹³C. Calcite exhibits δ¹³C values between − 2‰ and − 4‰ PDB and δ¹⁸O values of + 23‰ to + 26‰ SMOW. The observed assemblages of secondary minerals formed by reaction with atmosphere and meteoric water, the changes in chemical composition of the natrocarbonatite and field observations suggest that alteration of natrocarbonatite is an open-system low-temperature process. It takes place at temperatures between 8 and 43 °C with the addition of H₂O to the system and the removal of Na, K, Cl and S from the carbonatites. Low-temperature thermodynamic models developed for alkali carbonate systems can be used for the interpretation of Oldoinyo Lengai subsolidus mineralization.     

P-T evolution of eclogites from the Agualada Unit (Ordenes Complex, northwest Iberian Massif, Spain): Implications for crustal subduction

Eclogite lenses in the Agualada Unit (western Ordenes Complex, Spain) contain the peak mineral assemblage garnet (prograde rim: Alm = 48 mol%, Prp = 30 mol%), omphacite (Jd max = 36 mol%), quartz, rutile and rare zoisite, which equilibrated at T = 700 °C and P > 12–14 kbar. Garnet shows discontinuous growth zoning, with a pyrope-poor intermediate zone (Alm = 51 mol%, Prp = 10 mol%) between a core zone where pyrope is slightly higher (Alm = 46 mol%, Prp = 16 mol%) and areas just inward from the rims where the maximum pyrope contents (Alm = 48 mol%, Prp = 30 mol%) are recorded. In atoll interiors, garnet contains inclusions of a first generation of omphacite (Jd max = 40 mol%). This omphacite is replaced in the matrix by a second generation (Jd max = 36 mol%) with higher Fe/Fe + Mg ratio. The compositions of garnet and omphacite suggest a complex syneclogitic tectonothermal evolution for the Agualada Unit, characterized by: (1) eclogite-facies metamorphism (T = 585 °C, P > 12–13 kbar), followed by (2) cooling during a slight decompression (T = 500 °C, P > 11–12 kbar), and (3) a final increase in P and T to form the garnet rim-matrix omphacite mineral assemblage. The Agualada Unit is part of a subduction complex which affected the Gondwana margin at the beginning of the Variscan cycle. The P-T evolution of the Agualada eclogites is closely related to the structural evolution of the accretionary complex and the whole orogenic wedge. The cooling event recorded by the Agualada eclogites may have resulted from the accretion of a new colder crustal slice under the unit, whereas the final progradation reflects the emplacement of the Agualada Unit directly under the mantle wedge. This evolution fits well with previously presented the retical models, both for the tectonothermal evolution of accretionary complexes and for the dynamic evolution of orogenic wedges. P-T paths such as the one for the Agualada Unit eclogites, probably reflect a prolonged structural evolution. Although evidently rarely preserved, such paths are probably the rule rather than the exception during plate convergence.