Melting of carbonated pelites at 8–13 GPa: generating K-rich carbonatites for mantle metasomatism

The melting behaviour of three carbonated pelites containing 0–1 wt% water was studied at 8 and 13 GPa, 900–1,850°C to define conditions of melting, melt compositions and melting reactions. At 8 GPa, the fluid-absent and dry carbonated pelite solidi locate at 950 and 1,075°C, respectively; >100°C lower than in carbonated basalts and 150–300°C lower than the mantle adiabat. From 8 to 13 GPa, the fluid-present and dry solidi temperatures then increase to 1,150 and 1,325°C for the 1.1 wt% H₂O and the dry composition, respectively. The melting behaviour in the 1.1 wt% H₂O composition changes from fluid-absent at 8 GPa to fluid-present at 13 GPa with the pressure breakdown of phengite and the absence of other hydrous minerals. Melting reactions are controlled by carbonates, and the potassium and hydrous phases present in the subsolidus. The first melts, which composition has been determined by reverse sandwich experiments, are potassium-rich Ca–Fe–Mg-carbonatites, with extreme K₂O/Na₂O wt ratios of up to 42 at 8 GPa. Na is compatible in clinopyroxene with D_\textNa^{\textcpx/\textcarbonatite} = 10-18 D_{\text{Na}}^{{{\text{cpx}}/{\text{carbonatite}}}} = 10{-}18 at the solidus at 8 GPa. The melt K₂O/Na₂O slightly decreases with increasing temperature and degree of melting but strongly decreases from 8 to 13 GPa when K-hollandite extends its stability field to 200°C above the solidus. The compositional array of the sediment-derived carbonatites is congruent with alkali- and CO₂-rich melt or fluid inclusions found in diamonds. The fluid-absent melting of carbonated pelites at 8 GPa contrasts that at ≤5 GPa where silicate melts form at lower temperatures than carbonatites. Comparison of our melting temperatures with typical subduction and mantle geotherms shows that melting of carbonated pelites to 400-km depth is only feasible for extremely hot subduction. Nevertheless, melting may occur when subduction slows down or stops and thermal relaxation sets in. Our experiments show that CO₂-metasomatism originating from subducted crust is intimately linked with K-metasomatism at depth of >200 km. As long as the mantle remains adiabatic, low-viscosity carbonatites will rise into the mantle and percolate upwards. In cold subcontinental lithospheric mantle keels, the potassic Ca–Fe–Mg-carbonatites may freeze when reacting with the surrounding mantle leading to potassium-, carbonate/diamond- and incompatible element enriched metasomatized zones, which are most likely at the origin of ultrapotassic magmas such as group II kimberlites.     

The influence of water on melting of mantle peridotite

This experimental study examines the effects of variable concentrations of dissolved H₂O on the compositions of silicate melts and their coexisting mineral assemblage of olivine + orthopyroxene ± clinopyroxene ± spinel ± garnet. Experiments were performed at pressures of 1.2 to 2.0 GPa and temperatures of 1100 to 1345 °C, with up to ∼12 wt% H₂O dissolved in the liquid. The effects of increasing the concentration of dissolved H₂O on the major element compositions of melts in equilibrium with a spinel lherzolite mineral assemblage are to decrease the concentrations of SiO₂, FeO, MgO, and CaO. The concentration of Al₂O₃ is unaffected. The lower SiO₂ contents of the hydrous melts result from an increase in the activity coefficient for SiO₂ with increasing dissolved H₂O. The lower concentrations of FeO and MgO result from the lower temperatures at which H₂O-bearing melts coexist with mantle minerals as compared to anhydrous melts. These compositional changes produce an elevated SiO₂/(MgO + FeO) ratio in hydrous peridotite partial melts, making them relatively SiO₂ rich when compared to anhydrous melts on a volatile-free basis. Hydrous peridotite melting reactions are affected primarily by the lowered mantle solidus. Temperature-induced compositional variations in coexisting pyroxenes lower the proportion of clinopyroxene entering the melt relative to orthopyroxene. Isobaric batch melting calculations indicate that fluid-undersaturated peridotite melting is characterized by significantly lower melt productivity than anhydrous peridotite melting, and that the peridotite melting process in subduction zones is strongly influenced by the composition of the H₂O-rich component introduced into the mantle wedge from the subducted slab. Received: 7 April 1997 / Accepted: 9 January 1998     

Melting phase relation of nominally anhydrous,carbonated pelitic-eclogite at 2.5–3.0 GPa and deep cycling of sedimentary carbon

We have experimentally investigated melting phase relation of a nominally anhydrous, carbonated pelitic eclogite (HPLC1) at 2.5 and 3.0 GPa at 900–1,350°C in order to constrain the cycling of sedimentary carbon in subduction zones. The starting composition HPLC1 (with 5 wt% bulk CO₂) is a model composition, on a water-free basis, and is aimed to represent a mixture of 10 wt% pelagic carbonate unit and 90 wt% hemipelagic mud unit that enter the Central American trench. Sub-solidus assemblage comprises clinopyroxene + garnet + K-feldspar + quartz/coesite + rutile + calcio-ankerite/ankerite_ss. Solidus temperature is at 900–950°C at 2.5 GPa and at 900–1,000°C at 3.0 GPa, and the near-solidus melt is K-rich granitic. Crystalline carbonates persist only 50–100°C above the solidus and at temperatures above carbonate breakdown, carbon exists in the form of dissolved CO₂ in silica-rich melts and as a vapor phase. The rhyodacitic to dacitic partial melt evolves from a K-rich composition at near-solidus condition to K-poor, and Na- and Ca-rich composition with increasing temperature. The low breakdown temperatures of crystalline carbonate in our study compared to those of recent studies on carbonated basaltic eclogite and peridotite owes to Fe-enrichment of carbonates in pelitic lithologies. However, the conditions of carbonate release in our study still remain higher than the modern depth-temperature trajectories of slab-mantle interface at sub-arc depths, suggesting that the release of sedimentary carbonates is unlikely in modern subduction zones. One possible scenario of carbonate release in modern subduction zones is the detachment and advection of sedimentary piles to hotter mantle wedge and consequent dissolution of carbonate in rhyodacitic partial melt. In the Paleo-NeoProterozoic Earth, on the other hand, the hotter slab-surface temperatures at subduction zones likely caused efficient liberation of carbon from subducting sedimentary carbonates. Deeply subducted carbonated sediments, similar to HPLC1, upon encountering a hotter mantle geotherm in the oceanic province can release carbon-bearing melts with high K₂O, K₂O/TiO₂, and high silica, and can contribute to EM2-type ocean island basalts. Generation of EM2-type mantle end-member may also occur through metasomatism of mantle wedge by carbonated metapelite plume-derived partial melts.     

Phase relations of phlogopite with magnesite from 4 to 8 GPa

To evaluate the stability of phlogopite in the presence of carbonate in the Earth’s mantle, we conducted a series of experiments in the KMAS–H₂O–CO₂ system. A mixture consisting of synthetic phlogopite (phl) and natural magnesite (mag) was prepared (phl₉₀-mag₁₀; wt%) and run at pressures from 4 to 8 GPa at temperatures ranging from 1,150 to 1,550°C. We bracketed the solidus between 1,200 and 1,250°C at pressures of 4, 5 and 6 GPa and between 1,150 and 1,200°C at a pressure of 7 GPa. Below the solidus, phlogopite coexists with magnesite, pyrope and a fluid. At the solidus, magnesite is the first phase to react out, and enstatite and olivine appear. Phlogopite melts over a temperature range of ~150°C. The amount of garnet increases above solidus from ~10 to ~30 modal% to higher pressures and temperatures. A dramatic change in the composition of quench phlogopite is observed with increasing pressure from similar to primary phlogopite at 4 GPa to hypersilicic at pressures ≥5 GPa. Relative to CO₂-free systems, the solidus is lowered such, that, if carbonation reactions and phlogopite metasomatism take place above a subducting slab in a very hot (Cascadia-type) subduction environment, phlogopite will melt at a pressure of ~7.5 GPa. In a cold (40 mWm⁻²) subcontinental lithospheric mantle, phlogopite is stable to a depth of 200 km in the presence of carbonate and can coexist with a fluid that becomes Si-rich with increasing pressure. Ascending kimberlitic melts that are produced at greater depths could react with peridotite at the base of the subcontinental lithospheric mantle, crystallizing phlogopite and carbonate at a depth of 180–200 km.     

CH4 inclusions in orogenic harzburgite: Evidence for reduced slab fluids and implication for redox melting in mantle wedge

Fluids released from the subducting oceanic lithosphere are generally accepted to cause mantle wedge peridotite melting that produces arc magmas. These fluids have long been considered to be dominated by highly oxidized H₂O and CO₂ as inferred from erupted arc lavas. This inference is also consistent with the geochemistry of peridotite xenoliths in some arc basalts. However, the exact nature of these fluids in the mantle wedge melting region is unknown. Here, we report observations of abundant CH₄ + C + H₂ fluid inclusions in olivine of a fresh orogenic harzburgite in the Early Paleozoic Qilian suture zone in Northwest China. The petrotectonic association suggests that this harzburgite body represents a remnant of a Paleozoic mantle wedge exhumed subsequently in response to the tectonic collision. The mineralogy, mineral compositions and bulk-rock trace element systematics of the harzburgite corroborate further that the harzburgite represents a high-degree melting residue in a mantle wedge environment. Furthermore, existing and new C, He, Ne and Ar isotopes of these fluid inclusions are consistent with their being of shallow (i.e., crustal vs. deep mantle) origin, likely released from serpentinized peridotites and sediments of the subducting oceanic lithosphere. These observations, if common to subduction systems, provide additional perspectives on mantle wedge melting and subduction-zone magmatism. That is, mantle wedge melting may in some cases be triggered by redox reactions; the highly reduced (∼ΔFMQ-5, i.e., 5 log units below the fayalite-magnetite-quartz oxygen fugacity buffer) CH₄-rich fluids released from the subducting slab interact with the relatively oxidized (∼ΔFMQ-1) mantle wedge peridotite, producing H₂O and CO₂ that then lowers the solidus and incites partial melting for arc magmatism. The significance of slab-component contribution to the geochemistry of arc magmatism would depend on elemental selection and solubility in highly reduced fluids, for which experimental data are needed. We do not advocate the above to be the primary mechanism of arc magmatism, but we do suggest that the observed highly reduced fluids are present in mantle wedge peridotites and their potential roles in arc magmatism need attention.     

Fluids in the peridotite–water system up to 6 GPa and 800°C: new experimental constrains on dehydration reactions

The phase assemblages and compositions in a K-free lherzolite + H₂O system were determined between 4 and 6 GPa and 700–800°C, and the dehydration reactions occurring at subarc depth in subduction zones were constrained. Experiments were performed on a rocking multi-anvil apparatus using a diamond-trap setting. The composition of the fluid phase was measured using the recently developed cryogenic LA–ICP–MS technique. Results show that, at 4 GPa, the aqueous fluid coexisting with residual lherzolite (~85 wt% H₂O) doubles its solute load when chlorite transforms to the 10-Å phase between 700 and 750°C. The 10-Å phase breaks down at 4 and 5 GPa between 750 and 800°C and at 6 GPa between 700 and 750°C, leaving a dry lherzolite coexisting with a fluid phase containing 58–67 wt% H₂O, again doubling the total dissolved solute load. The fluid fraction in the system increases from 0.2 when a hydrous mineral is present to 0.4 when coexisting with a dry lherzolite. Our data do not reveal the presence of a hydrous peridotite solidus below 800°C. The directly measured fluid compositions demonstrate a fundamental change in the (MgO + FeO) to SiO₂ mass ratio of fluid solutes occurring at a depth of ca. 120–150 km (in the temperature window of 700–800°C), from (MgO–FeO)-dominated at 4 GPa [with (MgO + FeO)/SiO₂ ratio of 1.41–1.56] to SiO₂-dominated at 5–6 GPa (ratios of 0.61–0.82). The mobility of Al₂O₃ increases by more than one order of magnitude across this P–T interval and demonstrates that Al₂O₃ is compatible in an aqueous fluid coexisting with the anhydrous ol-opx-cpx ± grt assemblage. This shift in the fluid composition correlates with changes in the phase assemblage of the residual silicates. The hitherto unknown fundamental change in (MgO + FeO)/SiO₂ ratio and prominent increase in Al₂O₃ of the aqueous fluid with progressive subduction will likely inspire novel concepts on mantle wedge metasomatism by slab fluids.     

Reply to ‘Comment on “The beginnings of hydrous mantle wedge melting” by Till et al.’ by Green, Rosenthal and Kovacs

The comment of Green et al. debates the interpretation of the temperature of the H₂O-saturated peridotite solidus and presence of silicate melt in the experiments of Till et al. (Contrib Mineral Petrol 163:669–688, 2012) at <1,000?°C. The criticisms presented in their comment do not invalidate any of the most compelling observations of Till et al. (Contrib Mineral Petrol 163:669–688, 2012) as discussed in the following response, including the changing minor element and Mg# composition of the solid phases with increasing temperature in our experiments with 14.5?wt% H₂O at 3.2?GPa, as well as the results of our chlorite peridotite melting experiments with 0.7?wt% H₂O. The point remains that Till et al. (Contrib Mineral Petrol 163:669–688, 2012) present data that call into question the H₂O-saturated peridotite solidus temperature preferred by Green (Tectonophysics 13(1–4):47–71, 1972; Earth Planet Sci Lett 19(1):37–53, 1973; Can Miner 14:255–268, 1976); Millhollen et al. (J Geol 82(5):575–587, 1974); Mengel and Green (Stability of amphibole and phlogopite in metasomatized peridotite under water-saturated and water-undersaturated conditions, Geological Society of Australia Special Publication, Blackwell, pp 571-581, 1989); Wallace and Green (Mineral Petrol 44:1–19, 1991) and Green et al. (Nature 467(7314):448–451, 2010).     

Partitioning of halogens between mantle minerals and aqueous fluids: implications for the fluid flow regime in subduction zones

We have performed phase equilibrium experiments in the system forsterite–enstatite–pyrope-H₂O with MgCl₂ or MgF₂ at 1,100 °C and 2.6 GPa to constrain the solubility of halogens in the peridotite mineral assemblage and the fluid–mineral partition coefficients. The chlorine solubility in forsterite, enstatite and in pyrope is very low, 2.1–3.9 and 4.0–11.4 ppm, respectively, and it is independent of the fluid salinity (0.3–30 wt% Cl), suggesting that some intrinsic saturation limit in the crystal is reached already at very low chlorine concentrations. Chlorine is therefore exceedingly incompatible in upper-mantle minerals. The fluorine solubility is 170–336 ppm in enstatite and 510–1,110 ppm in pyrope, again independent of fluid salinity. Forsterite dissolves 1,750–1,900 ppm up to a fluid salinity of 1.6 wt% F. At higher fluorine contents in the system, forsterite is replaced by the minerals of the humite group. The lower solubility of chlorine by three orders of magnitude when compared to fluorine is consistent with increasing lattice strain. Fluid–mineral partition coefficients are 10⁰–10² for fluorine and 10³–10⁵ for chlorine. Since the latter values are orders of magnitude higher than those for hydroxyl partitioning, fluid flow from the subducting slab through the mantle wedge will lead to an efficient sequestration of H₂O into the nominally anhydrous minerals in the wedge, whereas chlorine becomes enriched in the residual fluid. Simple mass balance calculations reveal that rock–fluid ratios of up to >3,000 are required to produce the elevated Cl/H₂O ratios observed in some primitive arc magmas. Accordingly, fluid flow from the subducted slab into the zone of melting in the mantle wedge does not only occur rapidly in narrow channels, but at least in some subduction zones, fluid pervasively infiltrates the mantle peridotite and interacts with a large volume of the mantle wedge. Together with the Cl/H₂O ratios of primitive arc magmas, our data therefore constrain the fluid flow regime below volcanic arcs.     

Absarokites from the western Mexican Volcanic Belt: constraints on mantle wedge conditions

We have investigated the near liquidus phase relations of a primitive absarokite from the Mascota region in western Mexico. Sample M.102 contains ~11.6 wt% MgO, Mg#=0.73 and the lava contains Fo₉₀ olivine phenocrysts, indicating near equilibrium with the mantle. High-pressure experiments on a synthetic analogue of the absarokite composition containing low and high H₂O abundances of (~2 and ~5 wt%, respectively) were performed in a piston cylinder apparatus over the pressure range of 1.2 to 2.0 GPa. The composition containing ~2 wt% H₂O is multiply saturated with olivine and orthopyroxene at 1.6 GPa and 1,400 °C. At the same pressure, clinopyroxene appears 30 °C below the liquidus. At an H₂O content of ~5 wt% the multiple saturation with olivine and orthopyroxene occurs at 1.7 GPa and 1,300 °C. Assuming a batch-melting process, we suggest that the primitive absarokite was segregated from a depleted lherzolite or harzburgite residue at ~50 km, placing the depth of origin well within the mantle wedge beneath the Jalisco Block. A low degree (<5 %wt%) batch-melt of an original metasomatized depleted lherzolite or harzburgite source would contain the observed trace element abundances found in M.102. The liquidus phase relations are not consistent with the presence of non-peridotitic veins at the depth of last equilibration. Therefore, we propose that the Mascota absarokites segregated at an apparent melt fraction of less than 5% from a depleted peridotitic source. Melting first began at a greater depth as a small degree H₂O- and trace element- rich melt of a metasomatized peridotite that ascended into the overlying wedge and re-equilibrated with shallower, hotter mantle.Editorial responsibility: J. Hoefs     

A revised petrological model for subducted oceanic crust: Insights from phase equilibrium modelling

Many geological and geodynamical studies of metamorphism in subduction zones have relied upon worldwide compilations of modelled slab‐top pressure–temperature (P–T) conditions, although recent evaluation of such data sets suggests that these predictions are ~100–300°C colder at any given pressure than the conditions recorded by exhumed metamorphic rocks. As such, geochemical, petrological and geophysical interpretations formulated using such ‘cold’ assumptions may be subject to error and uncertainty. Here, we apply thermodynamic phase equilibrium calculations to forward‐model how phase assemblages, the P–T conditions of key devolatilization reactions and the effect of densification with depth vary for typical mid‐ocean ridge basalt (MORB) along these newly defined ‘hotter’ subduction zone geotherms for cold, warm and average environments. The depth and extent of devolatilization of MORB is strongly dependent on the geotherm along which the oceanic crust subducts. At the onset of subduction along a warm geotherm, metabasites contain ~3   wt% H₂O and release ~45% of this fluid in a single pulse at ~20 km, correlating with chlorite and epidote breakdown. Below these depths, metamorphosed MORB will dehydrate incrementally due to gradual amphibole breakdown, becoming almost completely dehydrated at ~70 km. Oceanic crust subducting along an average geotherm will contain ~3.5 wt% of H₂O at the onset of subduction and will release ~40% of the bulk‐rock H₂O in two fluid pluses occurring at ~30 and 50 km, correlating with chlorite breakdown. Below these depths, gradual dehydration of ~50% of the bulk‐rock H₂O due to amphibole breakdown leads to near‐complete dehydration at ~80 km. By contrast, in cold subduction zones, metamorphosed MORB will typically be H₂O‐undersaturated and will dehydrate gradually at different depths, transporting ~0.6 wt% H₂O to sub‐arc depths. As the volume of fluid released via these dehydration reactions differs strongly between cold, average and warm scenarios, different degrees of serpentinization of the mantle forearc are expected worldwide and thus, the efficacy of buoyancy‐driven exhumation should vary strongly in space and time. Metabasites subducting along a warm and average geotherm will liberate most of the fluids at shallower depths, suggesting that these lithologies might preferentially exhume, yet MORB subducting along cold geotherms will not dehydrate until greater depths, inhibiting its return to the surface. Critically, while we show that metabasites formed along warmer geotherms are denser than metabasites from colder geotherms at any equivalent depth, buoyancy‐driven exhumation provoked by fluids plays a notably more important role in exhumation potential than the overall bulk‐rock ‘metamorphic’ density. Furthermore, we show that lawsonite does not stabilize in average and warmer subduction zones, which provides a simple but important solution to the mismatch between its predicted abundance in experiments and its rarity in nature and argues against its use as a reliable petrogenetic indicator of subduction throughout deep geological time, as has been suggested by some recent studies.     

A modified iterative sandwich method for determination of near-solidus partial melt compositions. II. Application to determination of near-solidus melt compositions of carbonated peridotite

We performed modified iterative sandwich experiments (MISE) to determine the composition of carbonatitic melt generated near the solidus of natural, fertile peridotite + CO₂ at 1,200–1,245°C and 6.6 GPa. Six iterations were performed with natural peridotite (MixKLB-1: Mg# = 89.7) and ∼10 wt% added carbonate to achieve the equilibrium carbonatite composition. Compositions of melts and coexisting minerals converged to a constant composition after the fourth iteration, with the silicate mineral compositions matching those expected at the solidus of carbonated peridotite at 6.6 GPa and 1,230°C, as determined from a sub-solidus experiment with MixKLB-1 peridotite. Partial melts expected from a carbonated lherzolite at a melt fraction of 0.01–0.05% at 6.6 GPa have the composition of sodic iron-bearing dolomitic carbonatite, with molar Ca/(Ca + Mg) of 0.413 ± 0.001, Ca# [100 × molar Ca/(Ca + Mg + Fe*)] of 37.1 ± 0.1, and Mg# of 83.7 ± 0.6. SiO₂, TiO₂ and Al₂O₃ concentrations are 4.1 ± 0.1, 1.0 ± 0.1, and 0.30 ± 0.02 wt%, whereas the Na₂O concentration is 4.0 ± 0.2 wt%. Comparison of our results with other iterative sandwich experiments at lower pressures indicate that near-solidus carbonatite derived from mantle lherzolite become less calcic with increasing pressure. Thus carbonatitic melt percolating through the deep mantle must dissolve cpx from surrounding peridotite and precipitate opx. Significant FeO* and Na₂O concentrations in near solidus carbonatitic partial melt likely account for the ∼150°C lower solidus temperature of natural carbonated peridotite compared to the solidus of synthetic peridotite in the system CMAS + CO₂. The experiments demonstrate that the MISE method can determine the composition of partial melts at very low melt fraction after a small number of iterations.     

Experimental insights into the formation of high-Mg basaltic andesites in the trans-Mexican volcanic belt

High-Mg basaltic andesites and andesites occur in the central trans-Mexican volcanic belt, and their primitive geochemical characteristics suggest equilibration with mantle peridotite. These lavas may represent slab melts that reequilibrated with overlying peridotite or hydrous partial melts of a peridotite source. Here, we experimentally map the liquidus mineralogy for a high-Mg basaltic andesite (9.6 wt% MgO, 54.4 wt% SiO₂, Mg# = 75.3) as a function of temperature and H₂O content over a range of mantle wedge pressures. Our results permit equilibration of this composition with a harzburgite residue at relatively high water contents (>7 wt%) and low temperatures (1,080–1,150°C) at 11–14 kbar. However, in contrast to the high Ni contents characteristic of olivine phenocrysts in many such samples from central Mexico, those of olivine phenocrysts in our sample are more typical of mantle melts that have fractionated a small amount of olivine. To account for this and the possibility that the refractory mantle source may have had olivine more Fo-rich than Fo₉₀, we numerically evaluated alternative equilibration conditions, using our starting bulk composition adjusted to be in equilibrium with Fo₉₂ olivine. This shifts equilibration conditions to higher temperatures (1,180–1,250°C) at mantle wedge pressures (11–15 kbar) for H₂O contents (>3 wt%) comparable to those analyzed in olivine-hosted melt inclusions from this region. Comparison with geodynamic models shows that final equilibration occurred shallower than the peak temperature of the mantle wedge, suggesting that basaltic melts from the hottest part of the wedge reequilibrated with shallower mantle as they approached the Moho.     

Interaction of model peridotite with H2O-KCl fluid: Experiment at 1.9 GPa and its implications for upper mantle metasomatism

Mineralogical and geochemical data suggest that chloride components play an important role in the transformation and partial melting of upper mantle peridotites. The effect of KCl on the transformation of hydrous peridotite rich in Al₂O₃, CaO, and Na₂O was examined in experiments aimed at studying interaction between model NCMAS peridotite with H₂O-KCl fluid under a pressure of 1.9 GPa, temperatures of 900–1200°C, and various initial H₂O/KCl ratios. The experimental results indicate that KCl depresses the solidus temperature of the hydrous peridotite: this temperature is <900°C at 1.9 GPa, which is more than 100°C lower than the solidus temperature (1000–1025°C) of hydrous peridotite in equilibrium with KCl-free fluid. The reason for the decrease in the melting temperature is that the interaction of KCl with silicates prevails over the effect of chloride on the water activity in the fluid. Experimental data highlight the key role of Al₂O₃ as a component controlling the whole interaction process between peridotite and H₂O-KCl fluid. Garnet, spinel, and pargasite-edenite amphibole in association with aluminous orthopyroxene are unstable in the presence of H₂O-KCl fluid at a chloride concentration in the fluid as low as approximately 2 wt % and are replaced by Cl-bearing phlogopite (0.4–1.1 wt % Cl). Interaction with H₂O-KCl fluid does not, however, affect clinopyroxene and forsterite, which are the Al poorest phases of the system. Chlorine stabilizes phlogopite at relatively high temperatures in equilibrium with melt at temperatures much higher than the solidus (>1200°C). The compositional evolution of melt generated during the melting of model peridotite in the presence of H₂O-KCl fluid is controlled, on the one hand, by the solubility of the H₂O-KCl fluid in the melt and, on the other hand, by phlogopite stability above the solidus. At temperatures below 1050°C, at which phlogopite does not actively participate in melting reactions, fluid dissolution results in SiO₂-undersaturated (35–40 wt %) and MgO-enriched (up to 45 wt %) melts containing up to 4–5 wt % K₂O and 2–3 wt % Cl. At higher temperatures, active phlogopite dissolution and, perhaps, also the separation of immiscible aqueous chloride liquid give rise to melts containing >10 wt % K₂O and 0.3–0.5 wt % Cl. Our experimental results corroborate literature data on the transformation of upper mantle peridotites into phlogopite-bearing associations and the formation of ultrapotassic and highly magnesian melts.     

H<Subscript>2</Subscript>O solubility in basalt at upper mantle conditions

This study presents a new experimental approach for determining H₂O solubility in basaltic melt at upper mantle conditions. Traditional solubility experiments are limited to pressures of ~600 MPa or less because it is difficult to reliably quench silicate melts containing greater than ~10 wt% dissolved H₂O. To overcome this limitation, our approach relies on the use of secondary ion mass spectrometry to measure the concentration of H dissolved in olivine and on using the measured H in olivine as a proxy for the concentration of H₂O in the co-existing basaltic melt. The solubility of H₂O in the melt is determined by performing a series of experiments at a single pressure and temperature with increasing amounts of liquid H₂O added to each charge. The point at which the concentration of H in the olivine first becomes independent of the amount of initial H₂O content of the charge (added + adsorbed H₂O) indicates its solubility in the melt. Experiments were conducted by packing basalt powder into a capsule fabricated from San Carlos olivine, which was then pressure-sealed inside a Ni outer capsule. Our experimental results indicate that at 1000 MPa and 1200 °C, the solubility of H₂O in basaltic melt is 20.6 ± 0.9 wt% (2 × standard deviation). This concentration is considerably higher than predicted by most solubility models but defines a linear relationship between H₂O fugacity and the square of molar H₂O solubility when combined with solubility data from lower pressure experiments. Further, our solubility determination agrees with melting point depression determined experimentally by Grove et al. (2006) for the H₂O-saturated peridotite solidus at 1000 MPa. Melting point depression calculations were used to estimate H₂O solubility in basalt along the experimentally determined H₂O-saturated peridotite solidus. The results suggest that a linear relationship between H₂O fugacity and the square of molar solubility exists up to ~1300 MPa, where there is an inflection point and solubility begins to increase less strongly with increasing H₂O fugacity.     

The importance of talc and chlorite “hybrid” rocks for volatile recycling through subduction zones; evidence from the high-pressure subduction mélange of New Caledonia

The transfer of fluid and trace elements from the slab to the mantle wedge cannot be adequately explained by simple models of slab devolatilization. The eclogite-facies mélange belt of northern New Caledonia represents previously subducted oceanic crust and contains a significant proportion of talc and chlorite schists associated with serpentinite. These rocks host large quantities of H₂O and CO₂ and may transport volatiles to deep levels in subduction zones. The bulk-rock and stable isotope compositions of talc and chlorite schist and serpentinite indicate that the serpentinite was formed by seawater alteration of oceanic lithosphere prior to subduction, whereas the talc and chlorite schists were formed by fluid-induced metasomatism of a mélange of mafic, ultramafic and metasedimentary rocks during subduction. In subduction zones, dehydration of talc and chlorite schists should occur at sub-arc depths and at significantly higher temperatures (∼ 800°C) than other lithologies (400–650°C). Fluids released under these conditions could carry high trace-element contents and may trigger partial melting of adjacent pelitic and mafic rocks, and hence may be vital for transferring volatile and trace elements to the source regions of arc magmas. In contrast, these hybrid rocks are unlikely to undergo significant decarbonation during subduction and so may be important for recycling carbon into the deep mantle. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

H<Subscript>2</Subscript>O storage capacity of olivine and low-Ca pyroxene from 10 to 13 GPa: consequences for dehydration melting above the transition zone

The onset of hydrous partial melting in the mantle above the transition zone is dictated by the H₂O storage capacity of peridotite, which is defined as the maximum concentration that the solid assemblage can store at P and T without stabilizing a hydrous fluid or melt. H₂O storage capacities of minerals in simple systems do not adequately constrain the peridotite water storage capacity because simpler systems do not account for enhanced hydrous melt stability and reduced H₂O activity facilitated by the additional components of multiply saturated peridotite. In this study, we determine peridotite-saturated olivine and pyroxene water storage capacities at 10–13 GPa and 1,350–1,450°C by employing layered experiments, in which the bottom ~2/3 of the capsule consists of hydrated KLB-1 oxide analog peridotite and the top ~1/3 of the capsule is a nearly monomineralic layer of hydrated Mg# 89.6 olivine. This method facilitates the growth of ~200-μm olivine crystals, as well as accessory low-Ca pyroxenes up to ~50 μm in diameter. The presence of small amounts of hydrous melt ensures that crystalline phases have maximal H₂O contents possible, while in equilibrium with the full peridotite assemblage (melt + ol + pyx + gt). At 12 GPa, olivine and pyroxene water storage capacities decrease from ~1,000 to 650 ppm, and ~1,400 to 1,100 ppm, respectively, as temperature increases from 1,350 to 1,450°C. Combining our results with those from a companion study at 5–8 GPa (Ardia et al., in prep.) at 1,450°C, the olivine water storage capacity increases linearly with increasing pressure and is defined by the relation C_{\textH2 \textO}^\textolivine ( \textppm ) = 57.6( ±16 ) ×P( \textGPa ) - 169( ±18 ). C_{{{\text{H}}_{2} {\text{O}}}}^{\text{olivine}} \left( {\text{ppm}} \right) = 57.6\left( { \pm 16} \right) \times P\left( {\text{GPa}} \right) - 169\left( { \pm 18} \right). Adjustment of this trend for small increases in temperature along the mantle geotherm, combined with experimental determinations of D_{\textH2 \textO}^{\textpyx/olivine} D_{{{\text{H}}_{2} {\text{O}}}}^{\text{pyx/olivine}} from this study and estimates of D_{\textH2 \textO}^{\textgt/\textolivine} D_{{{\text{H}}_{2} {\text{O}}}}^{{{\text{gt}}/{\text{olivine}}}} , allows for estimation of peridotite H₂O storage capacity, which is 440 ± 200 ppm at 400 km. This suggests that MORB source upper mantle, which contains 50–200 ppm bulk H₂O, is not wet enough to incite a global melt layer above the 410-km discontinuity. However, OIB source mantle and residues of subducted slabs, which contain 300–1,000 ppm bulk H₂O, can exceed the peridotite H₂O storage capacity and incite localized hydrous partial melting in the deep upper mantle. Experimentally determined values of D_{\textH2 \textO}^{\textpyx/\textolivine} D_{{{\text{H}}_{2} {\text{O}}}}^{{{\text{pyx}}/{\text{olivine}}}} at 10–13 GPa have a narrow range of 1.35 ± 0.13, meaning that olivine is probably the most important host of H₂O in the deep upper mantle. The increase in hydration of olivine with depth in the upper mantle may have significant influence on viscosity and other transport properties.     

High-Mg# andesitic lavas of the Shisheisky Complex,Northern Kamchatka: implications for primitive calc-alkaline magmatism

Primitive arc magmatism and mantle wedge processes are investigated through a petrologic and geochemical study of high-Mg# (Mg/Mg + Fe > 0.65) basalts, basaltic andesites and andesites from the Kurile-Kamchatka subduction system. Primitive andesitic samples are from the Shisheisky Complex, a field of Quaternary-age, monogenetic cones located in the Aleutian–Kamchatka junction, north of Shiveluch Volcano, the northernmost active composite volcano in Kamchatka. The Shisheisky lavas have Mg# of 0.66–0.73 at intermediate SiO₂ (54–58 wt%) with low CaO (<8.8%), CaO/Al₂O₃ (<0.54), and relatively high Na₂O (>3.0 wt%) and K₂O (>1.0 wt%). Olivine phenocryst core compositions of Fo90 appear to be in equilibrium with whole-rock ‘melts’, consistent with the sparsely phyric nature of the lavas. Compared to the Shisheisky andesites, primitive basalts from the region (Kuriles, Tolbachik, Kharchinsky) have higher CaO (>9.9 wt%) and CaO/Al₂O₃ (>0.60), and lower whole-rock Na₂O (<2.7 wt%) and K₂O (<1.1 wt%) at similar Mg# (0.66–0.70). Olivine phenocrysts in basalts have in general, higher CaO and Mn/Fe and lower Ni and Ni/Mg at Fo88 compared to the andesites. The absence of plagioclase phenocrysts from the primitive andesitic lavas contrasts the plagioclase-phyric basalts, indicating relatively high pre-eruptive water contents for the primitive andesitic magmas compared to basalts. Estimated temperature and water contents for primitive basaltic andesites and andesites are 984–1,143°C and 4–7 wt% H₂O. For primitive basalts they are 1,149–1,227°C and 2 wt% H₂O. Petrographic and mineral compositions suggest that the primitive andesitic lavas were liquids in equilibrium with mantle peridotite and were not produced by mixing between basalts and felsic crustal melts, contamination by xenocrystic olivine, or crystal fractionation of basalt. Key geochemical features of the Shisheisky primitive lavas (high Ni/MgO, Na₂O, Ni/Yb and Mg# at intermediate SiO₂) combined with the location of the volcanic field above the edge of the subducting Pacific Plate support a genetic model that involves melting of eclogite or pyroxenite at or near the surface of the subducting plate, followed by interaction of that melt with hotter peridotite in the over-lying mantle wedge. The strongly calc-alkaline igneous series at Shiveluch Volcano is interpreted to result from the emplacement and evolution of primitive andesitic magmas similar to those that are present in nearby monogenetic cones of the Shisheisky Complex.     

Experimental phase and melting relations of metapelite in the upper mantle: implications for the petrogenesis of intraplate magmas

We performed a series of piston-cylinder experiments on a synthetic pelite starting material over a pressure and temperature range of 3.0–5.0 GPa and 1,100–1,600°C, respectively, to examine the melting behaviour and phase relations of sedimentary rocks at upper mantle conditions. The anhydrous pelite solidus is between 1,150 and 1,200°C at 3.0 GPa and close to 1,250°C at 5.0 GPa, whereas the liquidus is likely to be at 1,600°C or higher at all investigated pressures, giving a large melting interval of over 400°C. The subsolidus paragenesis consists of quartz/coesite, feldspar, garnet, kyanite, rutile, ±clinopyroxene ±apatite. Feldspar, rutile and apatite are rapidly melted out above the solidus, whereas garnet and kyanite are stable to high melt fractions (>70%). Clinopyroxene stability increases with increasing pressure, and quartz/coesite is the sole liquidus phase at all pressures. Feldspars are relatively Na-rich [K/(K + Na) = 0.4–0.5] at 3.0 GPa, but are nearly pure K-feldspar at 5.0 GPa. Clinopyroxenes are jadeite and Ca-eskolaite rich, with jadeite contents increasing with pressure. All supersolidus experiments produced alkaline dacitic melts with relatively constant SiO₂ and Al₂O₃ contents. At 3.0 GPa, initial melting is controlled almost exclusively by feldspar and quartz, giving melts with K₂O/Na₂O ~1. At 4.0 and 5.0 GPa, low-fraction melting is controlled by jadeite-rich clinopyroxene and K-rich feldspar, which leads to compatible behaviour of Na and melts with K₂O/Na₂O ≫ 1. Our results indicate that sedimentary protoliths entrained in upwelling heterogeneous mantle domains may undergo melting at greater depths than mafic lithologies to produce ultrapotassic dacitic melts. Such melts are expected to react with and metasomatise the surrounding peridotite, which may subsequently undergo melting at shallower levels to produce compositionally distinct magma types. This scenario may account for many of the distinctive geochemical characteristics of EM-type ocean island magma suites. Moreover, unmelted or partially melted sedimentary rocks in the mantle may contribute to some seismic discontinuities that have been observed beneath intraplate and island-arc volcanic regions.     

Water transportation from the subducting slab into the mantle transition zone

Using a recently developed petrogenetic grid for MORB + H₂O, we propose a new model for the transportation of water from the subducting slab into the mantle transition zone. Depending on the geothermal gradient, two contrasting water-transportation mechanisms operate at depth in a subduction zone. If the geothermal gradient is low, lawsonite carries H₂O into mantle depths of 300 km; with further subduction down to the mantle transition depth (approximately 400 km) lawsonite is no longer stable and thereafter H₂O is once migrated upward to the mantle wedge then again carried down to the transition zone due to the induced convection. At this depth, hydrous β-phase olivine is stable and plays a role as a huge water reservoir. In contrast, if the geothermal gradient is high, the subducted slab may melt at 700–900 °C at depths shallower than 80 km to form felsic melt, into which water is dissolved. In this case, H₂O cannot be transported into the mantle below 80 km. Between these two end-member mechanisms, two intermediate types are present. In the high-pressure intermediate type, the hydrous phase A plays an important role to carry water into the mantle transition zone. Water liberated by the lawsonite-consuming continuous reaction moves upward to form hydrous phase A in the hanging wall, which transports water into deeper mantle. This is due to a unique character of the reaction, because Phase A can become stable through the hydration reaction of olivine. In the case of low-pressure intermediate type, the presence of a dry mantle wedge below 100 km acts as a barrier to prevent H₂O from entering into deeper mantle.     

Distinctive petrological, geochemical, and geodynamic features of subduction-related magmatism

Geological-petrological and geochemical data on subduction-related magmatism (including the volumes and compositions of the corresponding magmatic series) are compared to the results of experiments and numerical simulation. The subduction zone is subdivided into five depth sectors and volcanic zones I, II, and III: 1 is the accretionary wedge that controls the geodynamic stability of subduction; 2 is the sector of dehydration and fluid filtration; 3 is the zone of eclogitization and initial partial melting in the slab above which boninite volcanic zone I is formed during early stages; 4 is the main zone of melting of the sedimentary-basite layer and the development of volcanic zone II with the predominance of andesites; and 5 is the zone of higher degree melting, above which volcanic zone III (basaltic andesite and alkali basalt) is formed. The criterion of volcanism intensity, which was obtained within the scope of the melting model, is proportional to the subduction velocity and the thickness of the melting zone, and the distance between the groups of volcanics along the subduction zone is 75–100 km, at a thickness of the melting zone of 15–20 km. The calculated isotherm of 600°C, which controls the stability of serpentine and chlorite, is not identified at depth above 150 km, and this is confirmed by the composition and P-T conditions of the high-pressure rocks (containing diamond and coesite), which were brought from depths of 150–200 km in subduction zones. Seismic sections constructed with regard for the amplitude characteristics of seismic waves show two melting zones (“wet” melting at a depth of 100–200 km and “dry” melting at a depth of 150–200 km) and a complicated thermal structure of the suprasthenospheric wedge, which can include slant magma conduits. The mineralogical and geochemical features of arc magmatic series are formed at a decisive role of an H₂O-CO₂ fluid and an elevated oxidation potential. The predominant buffer minerals are as follows: garnet in the slab melting zone; magnetite, Ca-pyroxene, and amphibole in intermediate magmatic chambers; and amphibole, protoenstatite-bronzite (in place of olivine), and Cr-spinel (in place of magnetite) for boninite series generated in a “hot” asthenospheric wedge at interaction with fluids or water-rich melts. Actively disputable problems are the interactions scale of melts and fluids generated in a subduction zone with a “hot” mantle wedge, the possibility of transporting water-rich minerals deep into the mantle (to depths greater than 150 km), and the evolution of the scale at which young continental crust is generated by subduction melts.