Craig E. Manning

The solubility of quartz in H2O in the lower crust and upper mantle

The solubility of quartz in H2O has been determined experimentally from 5 to 20 kb and 500 to 900°C. The results double the pressure range over which the molality of aqueous silica (mSiO2(aq)) has been determined and lead to more accurate estimates of quartz solubility in H2O below 5 kb because of the rapid-quench methods employed. At constant temperature, logmSiO2(aq) increases with increasing pressure and (∂logmSiO2(aq)/t6P)T decreases with increasing pressure. Comparison of the new data with previous low-pressure experiments demonstrates that isothermal values of log mSiO2(aq) increase linearly with increasing ρlogmH2O between 200 and 900°C. This observation was used to derive the following expression for the equilibrium constant (K) of the reaction quartz = SiO2(aq)log K = 4.2620 −5764.2T + 1.7513 × 106T2−2.2869 × 108T3 + [2.8454−1006.9T + 3.5689 × 105T2] log ρH2O where logK = logmSiO2(aq). The equation agrees well with previous results, while accurately reproducing measured quartz solubilities over a much wider range in pressure and temperature, from 25°C and 1 bar to the conditions of this study. If the isothermal variation of log mSiO2(aq) with logρH2O is assumed to be linear, the results can be extrapolated to > 20 kb. The equation allows evaluation of aqueous silica transport in Barrovian metamorphic belts, subduction zones, and metasomatized magma source-regions in the mantle.

Geochronologic and thermobarometric constraints on the evolution of the Main Central Thrust, central Nepal Himalaya

The Main Central Thrust (MCT) juxtaposes the high-grade Greater Himalayan Crystallines over the lower-grade Lesser Himalaya Formation; an apparent inverted metamorphic sequence characterizes the shear zone that underlies the thrust. Garnet-bearing assemblages sampled along the Marysandi River and Darondi Khola in the Annapurna region of central Nepal show striking differences in garnet zoning of Mn, Ca, Mg, and Fe above and below the MCT. Thermobarometry of MCT footwall rocks yields apparent inverted temperature and pressure gradients of ∼18°C km−1 and ∼0.06 km MPa−1, respectively. Pressure-temperature (P-T) paths calculated for upper Lesser Himalaya samples that preserve prograde compositions show evidence of decompression during heating, whereas garnets from the structurally lower sequences grew during an increase in both pressure and temperature. In situ (i.e., analyzed in thin section) ion microprobe ages of monazites from rocks immediately beneath the Greater Himalayan Crystallines yield ages from 18 to 22 Ma, whereas late Miocene and Pliocene monazite ages characterize rocks within the apparent inverted metamorphic sequence. A Lesser Himalayan sample collected near the garnet isograd along the Marysandi River transect contains 3.3±0.1 Ma monazite ages (P ≈ 0.72 GPa, T ≈ 535°C). This remarkably young age suggests that this portion of the MCT shear zone accommodated a minimum of ∼30 km of slip over the last 3 Ma (i.e., a slip rate of >10 mm yr−1) and thus could account for nearly half of the convergence across the Himalaya in this period. The distribution of ages and P-T histories reported here are consistent with a thermokinematic model in which the inverted metamorphic sequences underlying the MCT formed by the transposition of right-way-up metamorphic sequences during late Miocene-Pliocene shearing.

Tectonic evolution of the early Mesozoic blueschist‐bearing Qiangtang metamorphic belt, central Tibet

This is the published version. Copyright 2003 American Geophysical Union. All Rights Reserved.

Blueschist-bearing metamorphic core complexes in the Qiangtang block reveal deep crustal structure of northern Tibet

A 500-km-long belt of metamorphic exposures in the Qiangtang block provides an opportunity to study the internal structure of northern Tibetan crust. Metamorphic rocks exposed at two widely separated areas along this belt consist of blueschist-bearing melange and are bounded by Late Triassic–Early Jurassic, domal, low-angle normal faults. We propose that this melange was underplated to the Qiangtang block and was subsequently exhumed by detachment faulting; both the underplating and the exhumation occurred during early Mesozoic southward subduction of oceanic lithosphere along the Jinsha suture. This model predicts that the deeper crust of much of northern Tibet consists of accretionary melange, in contrast to the continental crystalline crust of southern Tibet, and may account for north-south variations of Cenozoic tectonism in Tibet.

Geological implications of a permeability-depth curve for the continental crust

The decrease in permeability ( k ) of the continental crust with depth ( z ), as constrained by geothermal data and calculated fluid flux during metamorphism, is given by log k = −14 − 3.2 log z, where k is in meters squared and z is in kilometers. At moderate to great crustal depths (>∼5 km), this curve is defined mainly by data from prograde metamorphic systems, and is thus applicable to orogenic belts where the crust is being thickened and/or heated; lower permeabilities may occur in stable cratonic regions. This k-z relation implies that typical metamorphic fluid flux values of ∼10−11 m/s are consistent with fluid pressures significantly above hydrostatic values. The k-z curve also predicts that metamorphic CO2 flux from large orogens may be sufficient to cause significant climatic effects, if retrograde carbonation reactions are minimal, and suggests a significant capacity for diffuse degassing of Earth (1015–1016 g/yr) in tectonically active regions.

Quartz solubility in H2O-NaCl and H2O-CO2 solutions at deep crust-upper mantle pressures and temperatures: 2–15 kbar and 500–900°C

Abstract The solubility of quartz in H2O-NaCl solutions was measured at 2, 4.35, 10 and 15 kbar and 500–900°C, and at NaCl concentrations up to halite saturation, usually greater than 75 wt.%. Quartz solubility was also measured in CO2-H2O solutions at 10 kbar and 800°C. Solubilities were determined by weight loss of ground and polished quartz crystal fragments which were equilibrated with solutions in Pt envelopes for one to four days and then rapidly quenched. Experiments at 2 kbar were made with externally heated cold-seal apparatus; higher pressure experiments were done in a 3 4 inch-diameter piston-cylinder apparatus with NaCl pressure medium and graphite heater sleeve. Equilibrium solubility was demonstrated in several ways, and the present results reproduce those of Manning (1994) in pure H2O at selected conditions. At pressures below 4 kbar, NaCl in solution causes an initial “salting-in”, or quartz solubility enhancement, which, at 2 kbar and 700°C, persists to concentrations as great as 70 wt.% NaCl before quartz solubility again becomes as low as in pure H2O. The maximum solubility occurs at X(H2O) ∼ 0.9 and is 50% higher than in pure H2O. At 4.35 kbar and 700°C, however, quartz solubility decreases slightly with initial NaCl concentration, and then begins to drop rapidly with increasing salinity beyond 45 wt.% NaCl. At 10 and 15 kbar there is a steep initial decline in silica molality at all temperatures in the range 500–900°C, leveling off at higher NaCl concentrations. There is thus a pronounced change in solution behavior with pressure, from initial salting-in below 4 kbar to monotonic salting-out above 5 kbar. This pressure-induced change in silica solubility parallels the sharp decrease in H2O activity in NaCl solutions in the same pressure range found by Aranovich and Newton (1996). Therefore, the pressure-induced change in silica solubility is inferred to be a consequence of the dissociation of the neutral NaClo complex to Na+ and Cl− as solution densities increase above about 0.7 gm/cm3. At very high salinities, approaching halite saturation, the isobars of quartz solubility as a function of NaCl mole fraction at 700°C converge, indicating that, for hypersaline fluids having the constitution of molten salts, pressure has only a minor effect on quartz solubility. Quartz solubility at 10 kbar shows exponential decline with increasing salinity at all temperatures in the range 500°C to 900°C. This is the expected behavior of a two-component solvent, in which quartz is sparingly soluble in one component. At 10 kbar, isotherms of log silica molality versus H2O mole fraction are linear between X(H2O) = 1.0 and 0.5, but begin to curve to lower values at 900°C, where high salinities are attained before halite saturation occurs. This behavior implies that the solute silica species is a hydrate that becomes progressively destabilized at low H2O concentrations of the solvent. Plots of log silica molality versus log H2O activity suggest that the solute species is neutral H4SiO4 with no additional solvated H2O molecules, assuming no Na-SiO2 complexing. The solubility of quartz in CO2-H2O fluids at 800°C and 10 kbar is much smaller than in NaCl solutions at the same P,T and H2O activity. Thermodynamic analysis suggests that the solute species in CO2-H2O fluids is H4SiO4 with 1–3 solvated H2O molecules, which is similar to the solute behavior inferred by Walther and Orville (1983) in CO2 and Ar solutions with H2O at lower pressures. The present results show that SiO2 will partition very strongly into a concentrated salt solution in deep crust-upper mantle metamorphic and metasomatic processes, in preference to a coexisting immiscible CO2-rich fluid. The much greater permeability of silicate rocks for salt solutions than for CO2-rich solutions, together with the much higher solubility of silica-rich phases in the former, could be an important factor in geochemical segregation processes involving rising and cooling fluids of magmatic or metamorphic origin.

Structural evolution of the Gurla Mandhata detachment system, southwest Tibet: Implications for the eastward extent of the Karakoram fault system

Field mapping and geochronologic and thermobarometric analyses of the Gurla Mandhata area, in southwest Tibet, reveal major middle to late Miocene, east-west extension along a normal-fault system, termed the Gurla Mandhata detachment system. The maximum fault slip occurs along a pair of low-angle normal faults that have caused significant tectonic denudation of the Tethyan Sedimentary Sequence, resulting in juxtaposition of weakly metamorphosed Paleozoic rocks and Tertiary sedimentary rocks in the hanging wall over amphibolite-facies mylonitic schist, marble, gneisses, and variably deformed leucogranite bodies in the footwall. The footwall of the detachment fault system records a late Miocene intrusive event, in part contemporaneous with top-to-the-west ductile normal shearing. The consistency of the mean shear direction within the mylonitic footwall rocks and its correlation with structurally higher brittle normal faults suggest that they represent an evolving low-angle normal-fault system. 4 0 Ar/ 3 9 Ar data from muscovite and biotite from the footwall rocks indicate that it cooled below 400 °C by ca. 9 Ma. Consideration of the original depth and dip angle of the detachment fault prior to exhumation of the footwall yields total slip estimates between 66 and 35 km across the Gurla Mandhata detachment system. The slip estimates and timing constraints on the Gurla Mandhata detachment system are comparable to those estimated on the right-slip Karakoram fault system, to which it is interpreted to be kinematically linked. Moreover, the mean shear-sense direction on both the Karakoram fault and the Gurla Mandhata detachment system overlap along the intersection line between the mean orientations of the faults, which further supports a kinematic association. If valid, this interpretation extends previous results that the Karakoram fault extends to mid-crustal depths.

Tectonic evolution of the northeastern Pamir: Constraints from the northern portion of the Cenozoic Kongur Shan extensional system, western China

The late Cenozoic Kongur Shan extensional system lies along the northeastern margin of the Pamir at the western end of the Himalayan-Tibetan orogen, accommodating east-west extension in the Pamir. At the northern end of the extensional system, the Kongur Shan normal fault juxtaposes medium- to high-grade metamorphic rocks in both its hanging wall and footwall, which record several Mesozoic to Cenozoic tectonic events. Schists within the hanging wall preserve a Buchan metamorphic sequence, dated as Late Triassic to Early Jurassic (230–200 Ma) from monazite inclusions in garnet. Metamorphic ages overlap with U-Pb zircon ages from local granite bodies and are interpreted to be the result of regional arc magmatism created by subduction of the Paleo-Tethys ocean. The northern portion of the footwall of the extensional system exposes an upper-amphibolite-facies unit (~650 °C, 8 kbar), which structurally overlies a lowgrade metagraywacke unit. The high-grade unit records late Early Cretaceous crustal thickening at ca. 125–110 Ma, followed by emplacement over the low-grade metagraywacke along a north-northeast–directed thrust prior to ca. 100 Ma. Together these results indicate signifi cant middle Cretaceous crustal thickening and shortening in the northern Pamir prior to the Indo-Asian collision. A third Late Miocene (ca. 9 Ma) amphibolite-facies metamorphic event (~650–700 °C, 8 kbar) is recorded in footwall gneisses of the Kongur Shan massif. North of the Kongur Shan massif, rapid cooling in the footwall beginning at 7–8 Ma is interpreted to date the initiation of exhumation along the Kongur Shan normal fault. A minimum of 34 km of east-west extension is inferred along the Kongur Shan massif based on the magnitude of exhumation since the Late Miocene (~29 km) and the present dip of the Kongur Shan normal fault (~40°). Field observations and interpretation of satellite images along the southernmost segment of the Kongur Shan extensional system indicate that the magnitude of late Cenozoic east-west extension decreases signifi cantly toward the south. This observation is inconsistent with models in which east-west extension in the Pamir is driven by northward propagation of the right-slip Karakoram fault, suggesting instead that extension is driven by vertical extrusion due to topographic collapse, radial thrusting along the Main Pamir Thrust, or oroclinal bending of the entire Pamir region.

Low heat flow inferred from >4 Gyr zircons suggests Hadean plate boundary interactions

The first ∼600 million years of Earth history (the ‘Hadean’ eon) remain poorly understood, largely because there is no rock record dating from that era. Detrital Hadean igneous zircons from the Jack Hills, Western Australia, however, can potentially provide insights into the conditions extant on our planet at that time. Results of geochemical investigations using these ancient grains have been interpreted to suggest the presence of a hydrosphere and continental crust before 4 Gyr. An underexploited characteristic of the >4 Gyr zircons is their diverse assemblage of mineral inclusions. Here we present an examination of over 400 Hadean zircons from Jack Hills, which shows that some inclusion assemblages are conducive to thermobarometry. Our thermobarometric analyses of 4.02–4.19-Gyr-old inclusion-bearing zircons constrain their magmatic formation conditions to about 700 °C and 7 kbar. This result implies a near-surface heat flow of ∼75 mW m-2, about three to five times lower than estimates of Hadean global heat flow. As the only site of magmatism on modern Earth that is characterized by heat flow of about one-quarter of the global average is above subduction zones, we suggest that the magmas from which the Jack Hills Hadean zircons crystallized were formed largely in an underthrust environment, perhaps similar to modern convergent margins.

Reevaluating carbon fluxes in subduction zones, what goes down, mostly comes up

Significance This paper reviews carbon fluxes into and out of subduction zones, using compiled data, calculations of carbon solubility in aqueous fluids, and estimates of carbon flux in metasedimentary diapirs. Upper-bound estimates suggest that most subducting carbon is transported into the mantle lithosphere and crust, whereas previous reviews suggested that about half is recycled into the convecting mantle. If upper-bound estimates are correct, and observed output from volcanoes and diffuse outgassing is smaller, then the mantle lithosphere is an important reservoir for carbon. If the subduction carbon cycle remains in balance, then outgassing from ridges and ocean islands is not balanced, so that the carbon content of the lithosphere + ocean + atmosphere has increased over Earth history. Carbon fluxes in subduction zones can be better constrained by including new estimates of carbon concentration in subducting mantle peridotites, consideration of carbonate solubility in aqueous fluid along subduction geotherms, and diapirism of carbon-bearing metasediments. Whereas previous studies concluded that about half the subducting carbon is returned to the convecting mantle, we find that relatively little carbon may be recycled. If so, input from subduction zones into the overlying plate is larger than output from arc volcanoes plus diffuse venting, and substantial quantities of carbon are stored in the mantle lithosphere and crust. Also, if the subduction zone carbon cycle is nearly closed on time scales of 5–10 Ma, then the carbon content of the mantle lithosphere + crust + ocean + atmosphere must be increasing. Such an increase is consistent with inferences from noble gas data. Carbon in diamonds, which may have been recycled into the convecting mantle, is a small fraction of the global carbon inventory.