Showing papers in "Contributions to Mineralogy and Petrology in 1999"

Petrology and geochemistry of Camiguin Island, southern Philippines: insights to the source of adakites and other lavas in a complex arc setting

Abstract: Camiguin is a small volcanic island located 12 km north of Mindanao Island in southern Philippines. The island consists of four volcanic centers which have erupted basaltic to rhyolitic calcalkaline lavas during the last ∼400 ka. Major element, trace element and Sr, Nd and Pb isotopic data indicate that the volcanic centers have produced a single lava series from a common mantle source. Modeling results indicate that Camiguin lavas were produced by periodic injection of a parental magma into shallow magma chambers allowing assimilation and fractional crystallization (AFC) processes to take place. The chemical and isotopic composition of Camiguin lavas bears strong resemblance to the majority of lavas from the central Mindanao volcanic field confirming that Camiguin is an extension of the tectonically complex Central Mindanao Arc (CMA). The most likely source of Camiguin and most CMA magmas is the mantle wedge metasomatized by fluids dehydrated from a subducted slab. Some Camiguin high-silica lavas are similar to high-silica lavas from Mindanao, which have been identified as “adakites” derived from direct melting of a subducted basaltic crust. More detailed comparison of Camiguin and Mindanao adakites with silicic slab-derived melts and magnesian andesites from the western Aleutians, southernmost Chile and Batan Island in northern Philippines indicates that the Mindanao adakites are not pure slab melts. Rather, the CMA adakites are similar to Camiguin high-silica lavas which are products of an AFC process and have negligible connection to melting of subducted basaltic crust.

Internal morphology, habit and U-Th-Pb microanalysis of amphibolite-to-granulite facies zircons: geochronology of the Ivrea Zone (Southern Alps)

Abstract: Several types of growth morphologies and alteration mechanisms of zircon crystals in the high-grade metamorphic Ivrea Zone (IZ) are distinguished and attributed to magmatic, metamorphic and fluid-related events. Anatexis of pelitic metasediments in the IZ produced prograde zircon overgrowths on detrital cores in the restites and new crystallization of magmatic zircons in the associated leucosomes. The primary morphology and Th-U chemistry of the zircon overgrowth in the restites show a systematic variation apparently corresponding to the metamorphic grade: prismatic (prism-blocked) low-Th/U types in the upper amphibolite facies, stubby (fir-tree zoned) medium-Th/U types in the transitional facies and isometric (roundly zoned) high-Th/U types in the granulite facies. The primary crystallization ages of prograde zircons in the restites and magmatic zircons in the leucosomes cannot be resolved from each other, indicating that anatexis in large parts of the IZ was a single and short lived event at 299 ± 5 Ma (95% c. l.). Identical U/Pb ages of magmatic zircons from a metagabbro (293 ± 6 Ma) and a metaperidotite (300 ± 6 Ma) from the Mafic Formation confirm the genetic context of magmatic underplating and granulite facies anatexis in the IZ. The U-Pb age of 299 ± 5 Ma from prograde zircon overgrowths in the metasediments also shows that high-grade metamorphic (anatectic) conditions in the IZ did not start earlier than 20 Ma after the Variscan amphibolite facies metamorphism in the adjacent Strona–Ceneri Zone (SCZ). This makes it clear that the SCZ cannot represent the middle to upper crustal continuation of the IZ. Most parts of zircon crystals that have grown during the granulite facies metamorphism became affected by alteration and Pb-loss. Two types of alteration and Pb-loss mechanisms can be distinguished by cathodoluminescence imaging: zoning-controlled alteration (ZCA) and surface-controlled alteration (SCA). The ZCA is attributed to thermal and/or decompression pulses during extensional unroofing in the Permian, at or earlier than 249 ± 7 Ma. The SCA is attributed to the ingression of fluids at 210 ± 12 Ma, related to hydrothermal activity during the breakup of the Pangaea supercontinent in the Upper Triassic/Lower Jurassic.

Growth, annealing and recrystallization of zircon and preservation of monazite in high-grade metamorphism: conventional and in-situ U-Pb isotope, cathodoluminescence and microchemical evidence

Abstract: Zircon and monazite from granulite- to amphibolite-facies rocks of the Vosges mountains (central Variscan Belt, eastern France) were dated by ion-microprobe and conventional U-Pb techniques. Different granulites of igneous (so-called leptynites) and sedimentary origin (kinzigites) and their leucosomes were dated at 334.9 ± 3.6, 335.4 ± 3.6 and 336.7 ± 3.5 Ma (conventional age 335.4 ± 0.6 Ma). Subsequent growth stages of zircon were distinguished by secondary electron (SEM) and cathodoluminescence (CL) imaging: (1) subsolidus growth producing round anhedral morphologies and sector zoning; (2) appearance of an intergranular fluid or melt phase at incipient dehydration melting that first resulted in resorption of pre-existing zircons, followed by growth of acicular zircons or overgrowths on round zircons consisting of planar growth zoning; (3) advanced melting producing euhedral prismatic zircons with oscillatory zoning overgrowing the sector zones. Two further lithologies, the Kaysersberg granite and the Trois-Epis units, were both formerly considered as migmatites. The intrusion of the Kaysersberg granite was dated at 325.8 ± 4.8 Ma. The Trois-Epis unit was found to be the product of volume recrystallization of a former granulite, which occurred under amphibolite-facies conditions 327.9 ± 4.4 Ma ago. The amphibolite-facies overprint of the Trois-Epis zircons led to the complete rejuvenation of most of the zircon domains by annealing and replacement/recrystallization processes. Annealing is assumed to occur in strained lattice domains, which are possibly disturbed by high trace element contents and/or large differences in decay damage between adjacent growth zones. Investigation of cathodoluminescence structures reveals that the replacement occurs along curved chemical reaction fronts that proceed from the surface towards the interior of the zircon. The monazite U-Pb system still records the age of high-grade metamorphism at around 335 Ma. The chemical reagent responsible for the rejuvenation of zircon obviously left the monazite unaffected.

P -T paths from anatectic pelites

Abstract: A relatively simple petrogenetic grid for partial melting of pelitic rocks in the NCKFMASH system is presented based on the assumption that the only H2O available for melting is through dehydration reactions. The grid includes both discontinuous and continuous Fe-Mg reactions; contours of Fe/(Fe+Mg) for continuous reactions define P-T vectors along which continuous melting will occur. For biotite-bearing assemblages (garnet+biotite + sillimanite + K-feldspar + liquid and garnet + biotite + cordierite + K-feldspar + liquid), Fe/(Fe+Mg) contours have negative slopes and melting will occur with increasing temperature or pressure. For biotite-absent assemblages (garnet + cordierite + sillimanite + K-feldspar + liquid or garnet + cordierite + orthopyroxene + K-feldspar + liquid) Fe/(Fe + Mg) contours have flat slopes and melting will occur only with increasing pressure. The grid predicts that abundant matrix K-feldspar should only be observed if rocks are heated at P 3.8 kbar, and that generation of late biotite + sillimanite replacing garnet, cordierite, or as selvages around leu- cosomes should be common in rocks in which melt is not removed. There is also a predicted field for dehydration melting of staurolite between 5 and 12 kbar. Textures in migmatites from New Hampshire, USA, suggest that prograde dehydration melting reactions are very nearly completely reversible during cooling and crystallization in rocks in which melt is not removed. Therefore, many reaction textures in “low grade” migmatites may represent retrograde rather than prograde reactions.

Priscoan (4.00–4.03 Ga) orthogneisses from northwestern Canada

Abstract: Ancient crustal rocks provide the only direct evidence for the processes and products of early Earth differentiation. SHRIMP zircon U-Th-Pb dating has identified, amongst the Acasta gneisses of the western Slave Province, Canada, two metatonalites and a metagranodiorite that have igneous ages of 4002 ± 4, 4012 ± 6 and 4031 ± 3 Ga respectively. These are the first identified Priscoan terrestrial rocks. A record of metamorphic events at ∼3.75, ∼3.6 and ∼1.7 Ga also is preserved. These discoveries approximately double, to ∼40 km2, the area over which ∼4.0 Ga gneisses are known to occur. A single older zircon core in one sample suggests that rocks as old as 4.06 Ga might yet be found in the region. As early as 4.03 Ga, terrestrial differentiation was already producing tonalitic magmas, probably by partial melting of pre-existing, less differentiated crust.

Stability and chemical composition of pargasitic amphibole in MORB pyrolite under upper mantle conditions

Abstract: The stability field of pargasitic amphibole in a model mantle composition (MORB pyrolite) has been experimentally determined for a fixed water content. A solidus for a pargasite-bearing lherzolite has been defined at pressures below the limit of amphibole stability of 30 kbar at T = 925 °C. The maximum temperature for pargasitic amphibole in MORB pyrolite occurs at 1075 °C between P = 18 and 25 kbar. This maximum lies between that determined for a fertile peridotite composition (Hawaiian pyrolite) and a depleted peridotite composition (Tinaquillo lherzolite). A comparison of the new results with those from earlier studies suggests that the stability for a particular bulk H2O content is mostly controlled by alkali content of the lherzolite composition. The systematic compositional variation of pargasitic amphibole as a function of pressure and temperature can be represented as an increase of the richterite component with increase in both pressure and temperature. For a given pressure the tschermakite component increases with increasing temperature. The compositions of coexisting clinopyroxenes also show a systematic variation with pressure and temperature. The phase relationships in MORB pyrolite combined with the modal abundance of coexisting phases show that the breakdown reactions of pargasitic amphibole occur continuously throughout the subsolidus region studied. The temperature stability limit of pargasitic amphibole coincides with the water-undersaturated solidus (amphibole-dehydration solidus) at pressures below 30 kbar. The experimental results are applicable to pargasitic amphibole-bearing natural peridotites. Cooling and decompression paths and heating events observed in natural peridotites can be interpreted from changes in the composition of pargasitic amphibole. The data are also applicable to a model for peridotite melting and hydration process in the subduction environment.

The Finero phlogopite-peridotite massif: an example of subduction-related metasomatism

Abstract: The Finero peridotite massif is a harzburgite that suffered a dramatic metasomatic enrichment resulting in the pervasive presence of amphibole and phlogopite and in the sporadic occurrence of apatite and carbonate (dolomite)-bearing domains. Pyroxenite (websterite) dykes also contain phlogopite and amphibole, but are rare. Peridotite bulk-rock composition retained highly depleted major element characteristics, but was enriched in K, Rb, Ba, Sr, LREE (light rare earth elements) (LaN/YbN = 8–17) and depleted in Nb. It has high radiogenic Sr (87Sr/86Sr(270) = 0.7055–0.7093), low radiogenic Nd (ɛNd(270) = −1 to −3) and EMII-like Pb isotopes. Two pyroxenite – peridotite sections examined in detail show the virtual absence of major and trace element gradients in the mineral phases. In both rock types, pyroxenes and olivines have the most unfertile major element composition observed in Ivrea peridotites, spinels are the richest in Cr, and amphibole is pargasite. Clinopyroxenes exhibit LREE-enriched patterns (LaN/YbN ∼16), negative Ti and Zr and generally positive Sr anomaly. Amphibole has similar characteristics, except a weak negative Sr anomaly, but incompatible element concentration ∼1.9 (Sr) to ∼7.9 (Ti) times higher than that of coexisting clinopyroxene. Marked geochemical gradients occur toward apatite and carbonate-bearing domains which are randomly distributed in both the sections examined. In these regions, pyroxenes and amphibole (edenite) are lower in mg## and higher in Na2O, and spinels and phlogopite are richer in Cr2O3. Both the mineral assemblage and the incompatible trace element characteristics of the mineral phases recall the typical signatures of “carbonatite” metasomatism (HFSE depletion, Sr, LILE and LREE enrichment). Clinopyroxene has higher REE and Sr concentrations than amphibole (amph/cpxDREE,Sr = 0.7–0.9) and lower Ti and Zr concentrations. It is proposed that the petrographic and geochemical features observed at Finero are consistent with a subduction environment. The lack of chemical gradients between pyroxenite and peridotite is explained by a model where melts derived from an eclogite-facies slab infiltrate the overhanging harzburgitic mantle wedge and, because of the special thermal structure of subduction zones, become heated to the temperature of the peridotite. If the resulting temperature is above that of the incipient melting of the hydrous peridotite system, the slab-derived melt equilibrates with the harzburgite and a crystal mush consisting of harzburgite and a silica saturated, hydrous melt is formed. During cooling, the crystal mush crystallizes producing the observed sequence of mineral phases and their observed chemical characteristics. In this context pyroxenites are regions of higher concentration of the melt in equilibrium with the harzburgite and not passage-ways through which exotic melts percolated. Only negligible chemical gradients can appear as an effect of the crystallization process, which also accounts for the high amphibole/clinopyroxene incompatible trace element ratios. The major element refractory composition is explained by an initially high peridotite/melt ratio. The apatite, carbonate-bearing domains are the result of the presence of some CO2 in the slab-derived melt. The CO2/H2O ratio in the peridotite mush increased by crystallization of hydrous phases (amphibole and phlogopite) locally resulting in the unmixing of a late carbonate fluid. The proposed scenario is consistent with subduction of probably Variscan age and with the occurrence of modal metasomatism before peridotite incorporation in the crust.

Harzburgite to lherzolite and back again: metasomatic processes in ultramafic xenoliths from the Wesselton kimberlite, Kimberley, South Africa

Abstract: Garnets from phlogopite harzburgite xenoliths from the Wesselton kimberlite show zoning from low-Ca harzburgitic cores to rims with lherzolitic Ca-Cr relations. Garnet cores are depleted in Y and HREE, but have sinuous REE patterns enriched in the MREE. Rimwards increase in Ca and decrease in Cr and Mg is accompanied by increases in Zr, Y, Ti and HREE. Secondary replacement rims on some garnets consist of garnet with low Ca and Cr, but high Mg, Ti and HREE. The zoning, and the secondary replacement rims, are attributed to different stages of a metasomatic process that has converted harzburgite to lherzolite, at temperatures near 1000 °C. Modelling of zoning profiles suggests that the process can be divided into three parts: (a) Inwards diffusion of Ca, Zr and Y over periods of 10,000–30,000 years, from a fluid depleted in Ti, Ga and Y; (b) formation of overgrowths high in Ca, Zr, Y and Ti, followed by annealing over periods of several thousand years; (c) formation of secondary reaction rims of low-Ca garnet, on very short timescales prior to eruption. The sinuous REE patterns of the garnet cores are regarded as “primary” features reflecting an ancient metasomatic event superimposed on a depleted protolith. The high Zr/Y, Zr/Ti and Zr/Ca of the fluids corresponding to stage (a) are ascribed to the presence of phlogopite and garnet in the matrix near the fluid source (presumed to be a melt, possibly a kimberlite precursor), leading to the development of concentration fronts in the percolating fluid. The overgrowths of stage (b) appear to coincide with the precipitation of phlogopite in the rock. The low Ca of the fluid responsible for the secondary replacement rims of stage (c) may reflect the late precipitation of clinopyroxene or Ca-carbonate as part of the metasomatic assemblage. These processes have significantly modified the modal, major- and trace-element composition of the mantle volume sampled by the Wesselton kimberlite, within <1 Ma of eruption. Recognition of such effects and their distribution in time and space is essential to understanding of the evolution of the subcontinental lithospheric mantle.

40Ar-39Ar and Rb-Sr geochronology of high-pressure metamorphism and exhumation history of the Tavsanli Zone, NW Turkey

Abstract: Geochronological investigations in high- and ultra-high-pressure metamorphic rocks are problematic since firstly the low temperatures lead to fine grain size and disequilibrium assemblages, and secondly the problem of “excess argon” affects 40Ar-39Ar systematics, the most commonly used isotopic system. The Tavsanli Zone is a belt of high-pressure low-temperature (HP-LT) rocks spanning NW Turkey and is one such region where previous geochronological studies have produced a range of estimates for the age of HP-LT metamorphism, raising the question of whether they are geologically significant. This study presents new data from the Tavsanli Zone; 40Ar-39Ar ages are in the range 60 Ma to 175 Ma, whilst Rb-Sr ages are restricted to 79.7 Ma to 82.8 Ma, confirming the presence of excess argon. Detailed ultra-violet laser ablation microprobe (UVLAMP) studies have revealed younger 40Ar-39Ar ages in the cores of coarser white micas, which in conjunction with 40Ar-39Ar ages from the finest grained lithologies and the Rb-Sr white mica crystallisation ages, constrain the post-HP-LT metamorphism exhumation rates of these rocks. Petrological and regional constraints suggest that syn-subduction exhumation and cooling took place initially by synchronous subduction and exhumation by underplating. This is followed by a phase of syn-continent-continent collision at a rate of approximately 1.5 mma−1 and exhumation to the surface via thrusting. The 40Ar-39Ar hornblende data from a granodiorite intruding the HP-LT rocks constrain the later parts of exhumation path. This study highlights the importance of a multi-system geochronological approach when attempting to determine the history of HP-LT rocks.

Age and origin of magmatism along the Cenozoic Red River shear belt, China

Abstract: To decipher the geodynamic significance of Cenozoic magmatism along the Red River shear belt, geochemical analyses, U-Pb and Rb-Sr dating, and Pb-Sr-Nd isotope tracing were undertaken. Zircon, monazite, titanite, and a Ti-U-oxide from foliated granitoid intrusions in the shear belt gneisses yield U-Pb emplacement ages of 33.1 ± 0.2 (2σ), 31.9 ± 0.3, 25.8 ± 0.2 and 24.7 ± 0.2 Ma, and an age of 35.0 ± 0.3 Ma was obtained for the roughly 100 km long, adjacent Jinping (Phan Si Pang) alkali granite. Together with our previous data the new ages suggest that magmatism and left-lateral strike-slip movements occurred coevally during latest Eocene–Oligocene times from 33 to 22 Ma. The Rb-Sr dating of muscovite and biotite from the northernmost gneisses indicates that cooling to 500 °C occurred at 52.6 ± 1.1 Ma, pre-dating the onset of magmatism, whereas further cooling to 300 °C took place at 28.9 ± 0.6. This shows that unroofing in the north took place almost 9 million years earlier than in the central gneiss segments of the shear zone. Geochemical data substantiate two types of magmas: (1) amphibole-bearing intrusions of alkaline trend which are derived from sources with Isr: 0.7065–0.7089 and i Nd: −3.7 to −6.6; (2) leucogranitic layers and bodies having Isr: 0.7084–0.7354 and i Nd: −3.3 to −13.4. The former type of intrusion is found in both the gneisses and the adjacent unmetamorphosed cover rocks, whereas leucogranites are restricted to the shear belt gneisses. Source signatures of the alkaline intrusions lie adjacent to the those of OIB, plotting at the lower end of the Mantle Array. Contamination of these melts by continental material seems to be very limited. On the other hand, the leucogranitic layers are essentially crustal derived but none of the them has country rock isotope signatures, requiring melting of crust different from the actually exposed gneisses. Magma sources similar to those of ocean island basalt indicate magmatism to involve melting of light rare earth element and large ion lithophile element enriched mantle domains, most likely present in the lithosphere underneath the region. Since lithospheric thickening or subduction can be ruled out to produce both types of magmas, the presence of an important thermal anomaly is required, which is coevally active with left-lateral strike-slip shear. Adiabatic decompression and melting within the rising anomaly is the most plausible mechanism to produce the mantle magmas, which successively migrate through the crust to induce anatectic melting at 20–15 km crustal depth. Alkaline magmas largely dominate the volume of magmatism along the belt, being continuously present in the shear zone for millions of years. Such lubrication potentially explains how very large amounts of displacement can be absorbed in surprisingly narrow shear zones such as the Red River belt, possibly also playing a role for where and when zones of plate-scale lateral extrusion develop.

Constraining the prograde and retrograde P-T-t path of Eocene HP rocks by SHRIMP dating of different zircon domains: inferred rates of heating, burial, cooling and exhumation for central Rhodope, northern Greece

Abstract: Ion microprobe (SHRIMP) dating was carried out on different zircon domains from metamorphic rocks of the HP-HT terrane of central Rhodope, northern Greece, to constrain the timing of prograde and retrograde stages within a single tectono-metamorphic cycle. A well determined P-T-t(relative) path for the metamorphic rocks of this terrane was used as a petrological basis for the geochronological investigations. Ion microprobe work was assisted by cathodoluminescence (CL) images of the zircon crystals. The geochronological results revealed that Hercynian continental crust was subducted during the Eocene. Several stages of the Eocene tectono-metamorphic cycle – including both the prograde and retrograde parts of the P-T path above ca 300 °C, 0.3 GPa – were dated using zircons from the following rock types: (1) A deformed quartz vein probably formed at ca 300 °C, 0.3 GPa. Zircons in this vein precipitated from a hydrothermal fluid; they yielded an age of 45.3 ± 0.9 Ma which corresponds to the time of a low-T prograde stage of metamorphism. (2) In kyanite eclogites, zircons were entirely reset during eclogite-facies metamorphism. Resetting was very probably enhanced by the presence of fluids derived by H2O liberating reactions close to the P-peak. They yielded an age of 42.2 ± 0.9 Ma. (3) Orthogneisses surrounding the kyanite eclogites contained zircons with magmatic oscillatory zoned cores, which yielded Hercynian ages of 294 ± 8 Ma (age of granitic protolith formation), whereas CL-bright, metamorphic rims yielded, like the eclogite zircons, ages of 42.0 ± 1.1 Ma. Therefore, both the eclogites and orthogneisses are interpreted to have approached maximum depth at around 42 Ma. (4) In a leucosome of a migmatized orthogneiss, oscillatory zoned zircons yielded an age of 40.0 ± 1.0 Ma. At this time the rocks reached maximum temperatures during early decompression. (5) A late pegmatite crosscutting the schistosity of amphibolites contained oscillatory zoned zircons that yielded a crystallization age of 36.1 ± 1.2 Ma. Thus, the whole tectono-metamorphic cycle above ca 300 °C, 0.3 GPa lasted from 45.3 ± 0.9 Ma to 36.1 ± 1.2 Ma, that is 9.2 Ma with an extreme error value of 2.1 Ma. Based on combined SHRIMP and petrological data, the average rates of heating and burial during subduction (above ca 300 °C, 0.3 GPa) are >94 °C/Ma and >15 mm/a, respectively. Rates of cooling and exhumation (also above 300 °C, 0.3 GPa) are calculated to be >128° C/Ma and >7.7 mm/a. The Eocene age of metamorphism in central Rhodope implies that the terrane of, at least, central Rhodope and the Cyclades very probably was part of the same continental crust.

Origin of peraluminous granites and granodiorites, Iberian massif, Spain: an experimental test of granite petrogenesis

Abstract: The discrimination between potential source materials involved in the genesis of Iberian granites and granodiorites, as well as the role of mantle-crust inter- actions, are examined using constraints imposed by melting experiments, melting-assimilation experiments and Sr-Nd isotope systematics. The Sr-Nd isotope re- lationships indicate the existence of diAerent genetic trends in which juvenile mantle materials are involved by diAerent mechanisms: (1) a source trend, traced by a particular evolution of the pre-Hercynian basement and indicating mantle participation at the time of sedimen- tation; (2) a set of magmatic trends traced by gabbro- tonalite-enclave-granodiorite associations, implying the incorporation of new mantle material at the time of granite generation. These relationships strongly support a pure crustal origin for the peraluminous leucogranites, derived from partial melting of crustal protoliths, and a hybrid origin for the peraluminous granodiorites. These granodiorites are the most abundant granitic rocks of the Central Iberian zone (CIZ) of the Iberian massif, implying that processes of hybridisation by assimilation and/or magma mixing played an important role in granitoid production during the Hercynian orogeny. These hypotheses have been tested by means of melting and assimilation experiments. Melting experiments in the range 800-900 ∞C and at pressures of 3, 6, 10 and 15 kbar indicate that: (1) several potential source materials such as Bt-Ms gneisses and metagreywackes are suitable for the production of peraluminous leucogranite melts; (2) the melt compositions are always leucogranitic, re- gardless of pressure; (3) pressure exerts a strong influ- ence on the fertility of the source: experiments at 3 kbar produce more than 20 vol% of melt, compared with less than 5 vol% of melt produced at 10 and 15 kbar and at the same temperature. The melting-assimilation experi- ments carried out at 1000 ∞C and 4, 7 and 10 kbar and using a proportion of 50% gabbro and 50% gneiss give high melt proportions (more than 50 vol.%) and noritic residues. These melts have the composition of le- ucogranodiorites, and overlap with part of the compo- sitional range of peraluminous granodiorites of the Iberian massif. The generation of more mafic granodiorites may be explained by the incorporation of some residual orthopyroxene to the granodiorite mag- mas. The low solubility of Fe + Mg prevents the gen- eration of granodiorite melts with more than 3 wt% of MgO + FeO at all crustal pressures. The large volumes of peraluminous, hybrid granodiorites, produced by assimilation of crustal rocks by mantle magmas, imply that an important episode of crustal growth took place during the Late-Palaeozoic Hercynian orogeny in the Iberian massif.

Clinopyroxene + liquid equilibria to 100 kbar and 2450 K

Abstract: One of the most active issues in igneous petrology is the investigation of mantle melting, and subsequent differentiation To evaluate alternative hypotheses for melting and differentiation it is essential to accurately predict clinopyroxene compositions in natural systems Expressions have thus been derived that describe clinopyroxene-melt equilibria, and allow equilibrium clinopyroxene compositions to be calculated These equations were constructed from least-squares regression analysis of experimental clinopyroxene-liquid pairs The calibration database included clinopyroxenes synthesized from both natural and synthetic basalt compositions; experimental conditions ranged from 0 to 100 kbar and 1350 to 2450 K Regression equations were based on thermodynamic functions Empirical expressions were also derived, since such models yield more precise estimates of clinopyroxene compositions, and may be easily incorporated into existing liquid line-of-descent models Such equations may be useful for calculation of high pressure liquid fractionation, or for constraining P-T conditions for basalts produced by partial melting of a pyroxene-bearing source Models of mantle melting often rely on expressions involving simple element ratios Partition coefficients (K d cpx/liq ) for the minor elements, Na and Ti, were thus also calibrated as a function of P, T and composition K Ti cpx/liq , while sensitive to composition was relatively insensitive to P and T In contrast, K Na cpx/liq increases substantially with increasing P, and exceeded 1 in some experiments Since oceanic basalts show variations in Na/Ti ratios, the potential exists for partial melting depths to be inferred from K Na cpx/liq

Clinopyroxene geobarometry of magmatic rocks. Part 2. Structural geobarometers for basic to acid, tholeiitic and mildly alkaline magmatic systems

Abstract: The crystal structures of 212 experimentally synthesized, igneous clinopyroxenes were modeled from electronprobe chemical data The coexisting melts span a wide range of petrologically relevant, dry and hydrous compositions, characterized by variable enrichment in silica and alkalis Experimental conditions pertain to Earth's crust and uppermost mantle (P = 0–24 kbar; garnet absent) and a variety of f O2 values (from CCO-buffered to air-buffered) and mineral assemblages (Cpx ± Opx ± Pig ± Ol ± Plag ± Spl ± Mt ± Amp ± Ilm) Unit-cell volume (Vcell) versus M1-polyhedron volume (VM1) relations were investigated over a range of pressures and temperatures using data derived from structure modeling and corrected for thermal expansivity and compressibility The relationships between pressure and clinopyroxene structural parameters were found to be dependent on the nature of the coexisting melt To reduce compositional effects, only clinopyroxenes belonging to mildly alkaline (MA) and tholeiitic (TH) series were considered Pressure was modeled as a linear function of Vcell, VM1, and Mg/(Mg + Fe2+)Cpx ratio A calibration based on the whole data set (MA+ TH) reproduced the experimental pressures within 14 kbar at the 1-σ level The maximum residuals were 35 kbar and 39 kbar for MA- and TH-clinopyroxenes, respectively Better statistics were obtained by considering MA- and TH-clinopyroxenes separately A calibration based on the 69 MA-clinopyroxenes reproduced the experimental pressures within 11 kbar (1σ) and with a maximum residual of 27 kbar A calibration based on the 143 TH-clinopyroxenes reproduced the experimental pressures within 10 kbar (1σ) and with a maximum residual of 34 kbar When these geobarometers are applied to natural samples for which P is unknown, the correction for compressibility is necessarily made through a trial-and-error procedure This expedient propagates an additional error that increases the above uncertainties and residuals by a factor of about 2 Applications to natural, igneous rocks for which the pressures of crystallization could be constrained based on experimental, petrological or geological evidence yielded pressure estimates that reproduced the expected values to within ca 2 kbar Compared to the MA-formulation, the TH-formulation appears to be less robust to variations in magma composition When applied to high-pressure (>10 kbar) clinopyroxenes synthesized from very low Na (Na2O < 15%) melts, the latter geobarometer can underestimate P by as much as 6 kbar Calculation of P through the present geobarometers requires clinopyroxene major-element composition and an independent, accurate estimate of crystallization T Underestimating T by 20 °C propagates into a 1-kbar increase in calculated P The proposed geobarometers are incorporated in the CpxBar software program, which is designed to retrieve the pressure of crystallization from a clinopyroxene chemical analysis

Systematics of calcium partitioning between olivine and silicate melt: implications for melt structure and calcium content of magmatic olivines

Abstract: A systematic characterization of the chemical factors that control calcium partitioning between olivine and melt in a magmatic environment was undertaken using experiments performed on compositionally simple systems (CaO-MgO-SiO2, CaO-MgO-Al2O3-SiO2, CaO-MgO-Al2O3-SiO2-Cr2O3, CaO-MgO-Al2O3-SiO2-TiO2, CaO-MgO-Al2O3-SiO2-Na2O, CaO-MgO-Al2O3-SiO2-FeO, CaO-MgO-Al2O3-SiO2-FeO-Na2O) over a wide range of temperature (1050–1530 °C) at one bar pressure. The calcium concentration of olivines is shown to be dependent not only on the forsterite content of the olivine but to a large extent on melt composition. For a fixed CaO content of the melt, these results show that the CaO concentration of olivine is strongly sensitive to the amount of alumina, alkali and ferrous iron present in the coexisting melt. Oxygen fugacity and temperature are not found directly to affect Ca partitioning. It is thus proposed that the systematic variations of the calcium content of olivine may be used as an “in-situ chemical potentiometer” of the lime activity of the melt. Based upon these data in synthetic systems, an empirical model describing Ca partitioning between olivine and melt is developed. When applied to natural olivines this model reproduces their Ca content, where melt composition is known, to within ±10% relative. The model may therefore be used to predict changes in melt composition during olivine crystallization and/or to assess whether an olivine is in equilibrium with its host magma. Finally, the wide range of Ca partitioning observed at fixed crystal composition confirms that minor element partitioning between crystal and melt cannot be predicted from the physical characteristics of the crystal alone, and that the non-ideality of the melt has to be taken into account.

Meta-igneous (non-gneissic) tonalites and quartz-diorites from an extensive ca. 3800 Ma terrain south of the Isua supracrustal belt, southern West Greenland: constraints on early crust formation

Abstract: In the Itsaq Gneiss Complex south of the Isua supracrustal belt (West Greenland) some areas of early Archaean tonalite and quartz-diorite are non-gneissic, free of pegmatite veins, and in rarer cases are undeformed with relict igneous textures and hence were little modified by heterogeneous ductile deformation under amphibolite facies conditions in several Archaean events. Such well-preserved early Archaean rocks are extremely rare. Tonalites are high Al, and have bulk compositions close to experimental liquids. Trace element abundances and modelling suggest that they probably originated as melts derived from basaltic compositions at sufficiently high pressures to require residual garnet + amphibolites ± clinopyroxene in the source. The major element characteristics of the quartz-diorites suggest these were derived from more mafic magmas than the tonalites, and underwent either igneous differentiation or mixing with crustal material. As in modern arc magmas, high relative abundances of Sr, Ba, Pb, and alkali elements cannot be generated simply from a basaltic source formed by large degrees of melting of a depleted mantle. This may indicate an important role for fluids interacting with mafic rocks in generating the earliest preserved continental crust. The high Ba/Th, Ba/Nb, La/Nb and low Nb/Th, Ce/Pb, and Rb/Cs ratios of these tonalites are also observed in modern arc magmas. SHRIMP U-Pb zircon geochronology was undertaken on seven tonalites, one quartz-diorite, a thin pegmatitic vein and a thin diorite dyke. Cathodoluminescence images show the zircon populations of the quartz-diorite and tonalites are dominated by single-component oscillatory-zoned prismatic grains, which gave ages of 3806 ± 5 to 3818 ± 8 Ma (2σ) (quartz-diorite and 5 tonalites) and 3795 ± 3 Ma (1 tonalite). Dating of recrystallised domains cutting oscillatory-zoned zircon indicates disturbance as early as 3800–3780 Ma. There are rare ca. 3600 Ma and 3800–3780 Ma (very high U and low Th/U) ≤ 20 μm wide partial overgrowths on the prismatic grains. Given likely Zr-undersaturation of precursor melts and evidence of zircon recrystallisation and metamorphic regrowth as early as 3800–3780 Ma, the age determinations on the prismatic oscillatory-zoned zircon populations give the igneous crystallisation age of the tonalite and quartz-diorite protoliths. When the coherency of the geochemistry is considered, these samples represent the best preserved suites of ca. 3800 Ma felsic igneous rocks yet documented.

Quaternary volcanism near the Valley of Mexico: implications for subduction zone magmatism and the effects of crustal thickness variations on primitive magma compositions

Abstract: The Valley of Mexico and surrounding regions of Mexico and Morelos states in central Mexico contain more than 250 Quaternary eruptive vents in addition to the large, composite volcanoes of Popocatepetl, Iztaccihuatl, and Nevado de Toluca. The eruptive vents include cinder and lava cones, shield volcanoes, and isolated andesitic and dacitic lava flows, and are most numerous in the Sierra Chichinautzin that forms the southern terminus of the Valley of Mexico. The Chichinautzin volcanic field (CVF) is part of the E-W-trending Mexican Volcanic Belt (MVB), a subduction-related volcanic arc that extends across Mexico. The crustal thickness beneath the CVF (∼50 km) is the greatest of any region in the MVB and one of the greatest found in any arc worldwide. Lavas and scoriae erupted from vents in the CVF include alkaline basalts and calc-alkaline basaltic andesites, andesites, and dacites. Both alkaline and calc-alkaline groups contain primitive varieties that have whole rock Mg#, MgO, and Ni contents, and liquidus olivine compositions (≤Fo90) that are close to those expected of partial melts from mantle peridotite. Primitive varieties also show a wide range of incompatible trace element abundances (e.g. Ba 210–1080 ppm; Ce 25–100 ppm; Zr 130–280 ppm). Data for primitive calc-alkaline rocks from both the CVF and other regions of the MVB to the west are consistent with magma generation in an underlying mantle wedge that is depleted in Ti, Zr, and Nb and enriched in large ion lithophile (K, Ba, Rb) and light rare earth (La, Ce) elements. Extents of partial melting estimated from Ti and Zr data are lower for primitive calc-alkaline magmas in the CVF than for those from the regions of the MVB to the west where the crust is thinner. The distinctive major element compositions (low CaO and Al2O3, high SiO2) of the primitive calc-alkaline magmas in the CVF indicate a more refractory mantle source beneath this region of thick crust. In contrast, primitive alkaline magmas from the CVF and other regions of the MVB show compositional similarities to intraplate-type alkali basalts erupted behind the arc in the Mexican Basin and Range province. These similarities are consistent with the hypothesis that slab-induced convection in the mantle wedge beneath the MVB causes advection of asthenospheric mantle from behind the arc to the region of magma generation. Trace element systematics of primitive magmas in the MVB reveal substantial variability in both the extent of mantle wedge enrichment by subduction processes and in the composition of mantle heterogeneities that are related to previous extraction of alkaline to sub-alkaline basaltic melts.

Plagioclase residence times at two island arc volcanoes (Kameni islands, Santorini, and Soufriere, St. Vincent) determined by Sr diffusion systematics

Abstract: The diffusive relaxation of trace element profiles in plagioclase phenocrysts may provide important constraints on magma residence times in crustal magma chambers. Initial trace element profiles in plagioclase phenocrysts are governed by variations in the concentration of a trace element in the melt and by the plagioclase-melt partition coefficient. Trace element diffusion will subsequently act to modify this initial profile and – given enough time – produce a profile that is in equilibrium with the anorthite variations within the crystal. We argue that the trace element partition coefficient Da/b between two parts a and b of a plagioclase crystal of variable anorthite content is equal to the ratio of their crystal-liquid partition coefficients, and that the equilibrium profile of the crystal can be calculated. The time required to establish diffusive equilibrium is dependent on the wavelength and amplitude of the initial trace element concentration range and on the diffusivity of the trace element in plagioclase. Strontium plagioclase-melt partition coefficients and diffusivities are calculated for a range of magmatic temperatures and plagioclase compositions. A one-dimensional diffusion model is developed that describes the diffusive destruction of oscillatory trace element zoning with time and allows the calculation of upper limits for plagioclase crystal residence times in a magma reservoir. The model is tested using major and trace element concentrations measured along crystal traverses of plagioclase phenocrysts from the Kameni Island dacites, Santorini, and from the 1979 Soufriere andesite, St. Vincent. Three out of eight plagioclase phenocrysts have Sr concentration profiles that are not in diffusive equilibrium. For these, the diffusion model is employed to calculate maximum crystal residence times from incomplete diffusive equilibration of trace element zoning in plagioclase. Maximum crystal residence times range from 100 to 450 years. This is in good agreement with estimates from crystal size distribution and from Ra-Th disequilibrium studies for the Kameni Islands. For Soufriere, however, such short residence times are incompatible with U-Th mineral errorchron data that suggest residence times of >40 ka in a thermally buffered magma reservoir. To reconcile these apparently different ages, we invoke a more complicated magmatic history for Soufriere where an initially buffered magma reservoir is disturbed by magma mixing and suffers limited additional crystal fractionation prior to eruption.

Monazite chemical composition: some implications for monazite geochronology

Abstract: An investigation of the chemical composition of monazite from a number of localities has been carried out. Samples used include monazites from metamorphic rocks, granitic rocks and a hydrothermal ore deposit. The REE distribution pattern of monazite varies greatly in accordance with its geological environment. A remarkable feature of the monazites studied is that their chondrite-normalised REE distribution patterns are mostly uniform between grains within the same sample, but differ significantly from sample to sample. This characteristic apparently indicates that there is an important effect on the REE distribution of monazite exerted by the host rock or source material from which monazite crystallised. Another important feature shown by the monazites studied is that monazites in rocks containing garnet as a major mineral show extreme depletion of HREE, whereas monazites in rocks without garnet or monazite that formed after the garnet breakdown contain significantly higher amounts of Y and HREE. This suggests that the phase assemblage, especially garnet, plays an important role in the REE distribution of monazites in these rocks. The value of REE distribution in monazite is exemplified with regard to the origin of monazite in the Lewisian metamorphic rocks, which is a fundamental issue in monazite geochronology.

Distinct site preferences for heavy and light REE in amphibole and the prediction of (Amph/L)D(REE)

Abstract: New experimental amphibole/melt partition coefficients from a variety of geologically relevant amphibole (pargasite, kaersutite, and K-richterite) and melt compositions obtained under conditions of interest to upper-mantle studies are combined with the results of X-ray single-crystal structure refinement. The ideal cation radii (r0), calculated using the lattice-site elastic-strain model of Blundy and Wood (1994) under the hypothesis of complete REE (rare earth elements) ordering at [8]M4, mostly differ significantly from those obtained from both the structure refinement and the ionic radius of [8]Ca2+. Heavier REE may also strongly deviate from the parabolic trends defined by the other REE. On the basis of the crystal-chemical knowledge of major-element site-preference in amphibole and the occurrence of two sites with different co-ordination within the M4 cavity (M4 for Ca and Na, M4′ for Fe2+ and Mg), we propose a new model for REE incorporation. LREE order at the [8]M4 site, whereas HREE prefer the M4′ site with lower co-ordination in amphiboles with a significant cummingtonite component, and may also enter the M2 octahedron, at least in richterite. This more complex model is consistent with the observed Amph/LD, and drops the usual assumption that REE behave as a homogeneous group and order at the M4 site. The availability of multiple crystal-chemical mechanisms for REE3+ incorporation explains why measured and estimated Amph/LDHREE may differ by up to one order of magnitude. When REE enter two different sites within the same cavity, a fit performed on the basis of a single curve may appear correct, but the values obtained for r0 are biased towards those of the dominant site, and the Young's modulus is underestimated. When REE are incorporated in multiple sites in different cavities, the observed pattern cannot be reduced to a single curve, and the partition coefficients of heavy REE would be strongly underestimated by a single-site fit. The simplistic assumption that REE occupy a single site within the amphibole structure can thus substantially bias predictive models based on the elastic-strain theory. Our combined approach allows linkage between fine-scale site preference and the macroscopic properties of minerals and provides more reliable predictive models for mineral/melt partitioning. After the possible site-assignments have been identified, the shape of the Onuma curves constructed from accurately determined Amph/LDREE now allows the active mechanisms for REE incorporation in amphiboles to be recognised even where site populations are not available. The REE preference for polyhedra with smaller size and lower co-ordination than those occupied by Ca invalidates the general idea that Ca acts as a “carrier” for REE.

Hercynian, Pan-African, Proterozoic and Archean ion-microprobe zircon ages for a Betic-Rif core complex, Alpine belt, W Mediterranean - consequences for its P-T-t path

Abstract: Ion-microprobe analysis of zircons from an andalusite-bearing orthogneiss within the major Alpujarride nappe complex in the central part of the Betic Cordilleras has yielded a Hercynian age of 285 ± 5 (2σ) Ma for euhedral rims, interpreted as the magmatic age of the andalusite-bearing biotite granite parent rock for the gneisses. Zircon age zoning systematics suggest a Paleozoic sedimentation age for the parent material for the anatectic source rock. Zircon cores represent several groups of ages: (1) Archean, c. 2.7 Ga; (2) Early Proterozoic, 2.2–2.0 Ga; (3) Middle Proterozoic, 1.1–0.9 Ga; (4) Pan-African, 0.8–0.5 Ga; including a well-defined event at 612 ± 13 (2σ) Ma. Paragenetic and textural relations indicate that gneissification took place during a high-P (12–13 kbar) low-T (450–500 °C) collisional event during which the primary Alpine nappe pile was produced. The second and final Alpine tectono-metamorphic event led to reorganization of the primary nappe pile by extensional tetonics with coeval very fast rock uplift and cooling (from c. 8? to c. 1 kbar and c. 600 to 100 °C within the period 19.5–18.5 Ma). The fast uplift/cooling stage was triggered by slab break-off which is thought to have induced diapiric underplating by high-T asthenospheric material. This may have heated the collisional wedge, causing thermal weakening which might have advanced the late stage fast uplift/cooling. The Alpine events did not leave a zircon crystallization record. The inherited, Archean–Pan-African zircon age pattern corresponds to that established for the Hercynian basement in central and southern Europe which is considered as reworked Gondwana crust. Deeper levels of core complexes within the Betic-Rif belt thus belong to the pre-Triassic basement of the Tethyan realm (Betic-Ligurian lithosphere) and represent reworked material ultimately derived from Archean and Proterozoic rock complexes from the Gondwana crustal domain. This study implies that thermobarometry of rock complexes which went through several phases of tectono-metamorphic reworking may render ambiguous results if based upon field observations and petrography alone. Zircon ion-microprobe dating may provide additional constraints required to arrive at a feasible tectono-metamorphic history, that is P-T-t trajectory, for such rock complexes.

Mobility and H2O loss from fluid inclusions in natural quartz crystals

Abstract: Petrographic observations on quartz crystals from the Mole Granite (Australia) and other localities shed new light on the mechanisms of post-entrapment modification of fluid inclusions. These modifications include migration away from pseudosecondary trails, changes in fluid salinity and density, shape distortion and the formation of “sweat-haloes” around strongly deformed inclusions. Increases in fluid salinity, which usually are associated with inclusion migration, indicate water-losses of up to 50%. However, LA-ICP-MS-analysis of unmobilized and mobilized inclusions of the same trail reveals basically unchanged ratios of major – and trace element cations, with the exception of Li, which seems to be incorporated into the crystal lattice during migration. Despite the fact that all these modifications are closely related to deformation processes, they occur not only in mechanically deformed quartz, but also in free-standing crystals. In the latter samples, stress has been generated internally as a result of brazil-twinned growth and compositional zonation. These observations and their interpretation leads to a list of practical criteria that should help in differentiating between reliable and suspect fluid inclusions in other samples.

Geochemistry and age of ultrahigh pressure metamorphic rocks from the Kokchetav massif (Northern Kazakhstan)

Abstract: Isotopic and geochemical data of the Zerenda series metamorphic rocks from the Kokchetav massif are reported. Some of these rocks contain microdiamond inclusions in garnets and other indicators of ultrahigh pressure metamorphism (P > 40 kbar, T = 900–1000 °C). The diamond-bearing rocks exhibit distinctive geochemical characteristics compared to typical crustal rocks. The REE patterns range from LREE depleted to slightly LREE enriched [chondrite normalized (La/Yb)N– 0.1–5.4] with a negative Eu anomaly. They are depleted in incompatible elements (e.g. Sr, Ba, U, Th) with respect to the upper crust. In contrast non-diamondiferous rocks of the Zerenda series exhibit normal crustal geochemistry. All rocks of the Zerenda series have very radiogenic lead isotopes. The measured μ values (238U/204Pb) compared with those calculated for the interval between crust formation and ultrahigh pressure (UHP) metamorphism suggest a decrease by factors of up to 200 during the UHP metamorphism. The Sm-Nd mineral isochrons from the diamond-bearing rocks and other rock types of the Zerenda series give a Middle Cambrian (524–535 Ma) age of metamorphism. The Nd model ages show that crust formation occurred about 2.3 Ga ago. Significant fractionation of Sm and Nd and loss of incompatible elements may be due to partial melting of the protoliths. The Ar-Ar age determinations of secondary biotite and muscovite from the diamond-bearing rocks yield an age of 517 ± 5 Ma. This cooling age requires a short time interval between UHP metamorphism and uplift to a crustal level. Ultrahigh pressure metamorphism might be a significant source of Pb for the mantle. We propose that the radiogenic Pb of the oceanic array is the contamination traces of numerous UHP events. Beside the geological aspect we demonstrate a method of dating a high grade metamorphic terrain using Nd isotopes. We compare whole rock isochrons and mineral isochrons and in this way get some insight into the behaviour of the Sm-Nd system during very high grade metamorphic events.

The dependence of the partitioning of iron and europium between plagioclase and hydrous tonalitic melt on oxygen fugacity

Abstract: The dependence of iron and europium partitioning between plagioclase and melt on oxygen fugacity was studied in the system SiO2(Qz)—NaAlSi3O8(Ab)—CaAl2Si2O8(An)—H2O. Experiments were performed at 500 MPa and 850 °C/750 °C under water saturated conditions. The oxygen fugacity was varied in the log f O2-range from −7.27 to −15.78. To work at the most reducing conditions the classical double-capsule technique was modified. The sample and a C—O—H bearing sensor capsule were placed next to each other within a BN jacket to minimise loss of hydrogen to the vessel atmosphere. By this setup redox conditions slightly more reducing than the FeO—Fe3O4 buffer could be maintained even in 96 h runs. Raman spectra showed that the BN was modified by reaction with hydrogen resulting in a low hydrogen permeability. The partition coefficients determined for Eu at 850 °C and 500 MPa vary from 0.095 at conditions of the Cu—Cu2O buffer to 1.81 at the most reducing conditions (C—O—H sensor). In the same f O2 interval the partition coefficient for Fe varies from 0.55 at oxidising conditions to 0.08 at the most reducing conditions. The partitioning of Sm, which was added as a reference for a trivalent REE, does not vary with the oxygen fugacity, yielding an average value for D = 0.07. Lowering the temperature to 750 °C for a given f O2 decreases the partition coefficient of Eu and increases that of Fe. Comparison with published data at 1 atm and at higher temperatures shows that both temperature and composition of the melt have strong effects on the partitioning behaviour. As the change of the partition coefficients in the geologically relevant f O2 range is quite strong, element partitioning of Eu and Fe might be used to estimate redox conditions for the genesis of igneous rocks. Furthermore, by modelling the partitioning data it is possible to extract information about the redox state of the melt. Resulting ferric-ferrous ratios show significant differences from those predicted by empirical models.

Silicic magmas from the continental Cameroon Volcanic Line (Oku, Bambouto and Ngaoundere): 40 Ar- 39 Ar dates, petrology, Sr-Nd-O isotopes and their petrogenetic significance

Abstract: The intraplate Cameroon Volcanic Line (CVL) straddles the African-South Atlantic continent-ocean boundary and is composed mainly of alkaline basic volcanic rocks. Voluminous silicic volcanics characterize the continental sector of the CVL. We present here new geochemical, isotopic (Sr-Nd-O) and 40Ar/39Ar geochronological data on the main silicic volcanic centres of the Western (Mt. Oku, Sabga and Mt. Bambouto) and Eastern (Ngaoundere plateau) Cameroon Highlands. The silicic volcanism of Mt. Oku, Sabga and Mt. Bambouto occurred between 25 and 15 Ma and is represented by voluminous quartz-normative trachytes and minor rhyolitic ignimbrites. At Mt. Bambouto central volcano about 700 m of silicic volcanics erupted in less than 2.7 million years. These silicic volcanics are associated with slightly to moderately alkaline basalts and minor basanites. In general, onset of the silicic volcanism migrated from NE (Oku: 25 Ma) to SW (Sabga: 23 Ma; Bambouto: 18 Ma; and Mt. Manengouba: 12 Ma). The silicic volcanism of the Ngaoundere plateau (eastern branch of the CVL) is instead dominated by nepheline-normative trachytes which are associated with strongly alkaline basalts and basanitic rocks. These Ne-trachytes are younger (11-9 Ma) than the Q-trachytes of the Western Highlands. The least differentiated silicic volcanics are isotopically similar (87Sr/86Sr 0.51278) to the associated alkaline basalts suggesting differentiation processes without appreciable interaction with crustal materials. Such interactions may, however, have played some role in the genesis of the most evolved silicic volcanics which have 87Sr/86Sr as high as 0.705–0.714. Fractional crystallization is the preferred mechanism for genesis of the silicic melts of both Western and Eastern Highlands, as shown by modeling major and trace element variations. The genesis of the least evolved Q-trachytes from the Western Highlands, starting from slightly to moderately alkaline basalts, is compatible with fractionation of dominantly plagioclase, clinopyroxene and magnetite. Crystal fractionation may have occurred at low pressure and at QFM buffer f O2conditions. Parental magmas of the Ngaoundere Ne-trachytes are likely instead to have been strongly alkaline basalts which evolved through crystal fractionation at higher P (6-2 kbar) and f O2 (QFM + 2). The migration (25 to 12 Ma) of the silicic volcanism from NE to SW in the continental sector of the CVL is reminiscent of that (31-5 Ma) of the onset of the basic volcanism in the oceanic sector (Principe to Pagalu islands) of the CVL. These ages, and that (11-9 Ma) of the silicic volcanism of the Ngaoundere plateau, indicate that the Cameroon Volcanic Line as a whole may not be easily interpreted as the surface expression of hot-spot magmatism.

Chromatographic separation of the platinum-group elements, gold, base metals and sulfur during degassing of a compacting and solidifying igneous crystal pile

Abstract: The major platinum-group elements (PGE) concentrations in layered intrusions are typically associated with zones in which the sulfide abundance begins to increase. In a number of layered intrusions, there is also a distinct stratigraphic separation in the peak concentrations of the PGE from those of the base metals, gold and sulfur through these zones. These stratigraphic “offsets” are characterized by a lower, typically S-poor, Pt- and Pd-enriched zone overlain by a zone enriched in the base metals, S and Au. The separations amount to a few decimeters to several tens of meters. In some instances, the high Pt and Pd concentrations are associated with trivial amounts of sulfide. Theoretical considerations suggest that these offsets can be modeled as chromatographic peaks that develop during an infiltration/reaction process. Using Pd as a typical PGE and Cu as a typical base metal, a numeric model is developed that illustrates how metal separations can develop in a vapor-refining zone as fluid evolved during solidification of a cumulus pile leaches sulfide and redeposits it higher in the crystal pile. The solidification/degassing ore-element transport is coupled with a compaction model for the crystal pile. Solidification resulting from conductive cooling through the base of the compacting column leads to an increasing volatile concentration in the intercumulus liquid until it reaches fluid saturation. Separation and upward migration of this fluid lead to an upward-migrating zone of increasingly higher bulk water contents as water degassed from underlying cumulates enriches overlying, fluid-undersaturated interstitial liquids. Sulfide is resorbed from the degassing regions and is reprecipitated in these vapor-undersaturated interstitial liquids, producing a zone of relatively high modal sulfide that also migrates upward with time. Owing to its strong preference for sulfide, Pd is not significantly mobile until all sulfide is resorbed. The result is a zone of increasing PGE enrichment that follows the sulfide resorption front as solidification/degassing continues. In detail, the highest Pd concentrations occur stratigraphically below the peak in S and base metals. The high Pd/S ratio mimics values conventionally interpreted as the result of high (silicate liquid)/(sulfide liquid) mass ratios (“R” values). However, in this case, the high Pd/S ratio is the result of a chromatographic/reaction front enrichment and not a magmatic sulfide-saturation event.

The causes and petrological significance of cathodoluminescence emissions from alkali feldspars

Abstract: The cathodoluminescence (CL) of a variety of alkali feldspars from South Greenland has been examined in an attempt to understand the causes of the CL and its petrological significance. Analytical methods have included CL spectroscopy, secondary ion mass spectrometry (SIMS) and electron paramagnetic resonance (EPR) to correlate the presence of certain CL emissions to the presence of certain trace element and point defects. Where possible, blue and red luminescent fractions of the same rock samples have been separated and analysed separately. Blue CL appears to relate to the presence of electron holes on bridging oxygens, particularly on the Al-O-Al bridge, as determined from EPR studies. No correlation with other proposed activators for blue CL such as Eu2+, Ga3+ or Ti4+ was observed. Some blue luminescent feldspars also have an emission in the infra-red (IR), invisible during normal visible CL petrography. The red and IR CL emissions correspond to features in EPR spectra attributed to Fe3+ and support previous suggestions that Fe3+ is related to this emission. However, our studies indicate that the visible red CL relates specifically to Fe3+ on the T1 site, whereas the equivalent CL from disordered feldspars lies in the IR. The difference between red and IR CL emissions therefore relates to the state of Fe3+ order across the tetrahedral sites. These data allow more meaningful interpretations of CL as a petrographic tool in alkali feldspar-bearing rocks.

Petrologic and experimental evidence for the movement and heating of the pre-eruptive Minoan rhyodacite (Santorini, Greece)

Abstract: Hydrothermal experiments combined with petrologic observations form the basis for a new two-stage model for the evolution of the pre-eruption Minoan magma chamber at Santorini, Greece. Ninety-nine percent of the erupted volume is two-pyroxene, rhyodacitic magma that had been stored at a temperature of ∼885 °C, based on magnetite-ilmenite and QUILF geothermometry. The rest of the volume is basaltic to andesitic magma, which occurs as 200 MPa. In addition, the composition of the plagioclase hosts (An56 ± 6) of the inclusions require temperatures of 825 ± 25 °C at pressures >200 MPa. This demonstrates that the Minoan rhyodacitic magma underwent a two-stage evolution, first crystallizing at ∼825∘C and >200 MPa, and then rinsing to a shallow ∼50 MPa storage region with a concomitant rise in temperature to ∼885 °C. We suggest that the episodic intrusion of mafic magmas provided the necessary heat and perhaps contributed to the ascent of the magma to shallow crustal depths where it reequilibrated before the cataclysmic eruption. Phase equilibria suggest that much of the heating of the rhyodacite occurred in the shallow storage region. Thermal budget calculations suggest that the rhyodacite magma could have been heated by intrusions of basalt rising at reasonable upwelling rates and injected into the storage zone over several hundred years. Preservation of amphibole in the mafic scoria indicate that injection of mafic magma continued up until days before the cataclysmic eruption, perhaps triggering the event.

Crystallization of the Little Three layered pegmatite-aplite dike, Ramona District, California

Abstract: Subhorizontally layered pegmatite-aplite bodies are characterized by fine-grained, sodic to granitic aplite that is usually juxtaposed abruptly above by much coarser-grained, commonly graphic potassic pegmatite. Although well studied, there currently is little concensus as to how such dikes form. The Little Three dike near Ramona, California, is representative of such zoned bodies in this and other regions, and contains discontinuous miarolitic pockets near the base of the graphic pegmatite zone. Tourmaline, garnet, biotite, and muscovite show no changes in major- or minor-element compositions indicative of progressive magmatic fractionation until the immediate vicinity of the main miarolitic zone, where they record abrupt and extreme enrichments in Li, F, and Mn. There is no correlation of chemical changes in the dike with the appearance of small miarolitic vugs well below the main miarolitic zone, nor is there any indication that the aplite, graphic pegmatite, or miarolitic pockets represent separate magma injections. The chemistries of tourmaline, garnet, and micas, however, preclude conventional models of Rayleigh fractionation or traditional zone refining. Textural features and modeled cooling histories indicate that the dike cooled quickly and might have solidified partially or totally to glass before crystallization commenced. Geothermometry based on the compositions of coexisting plagioclase and homogeneous, nonperthitic K-feldspar indicates inward crystallization of the dike, from ∼400–435 °C at the margins to ∼350–390 °C within 20–30 cm of the pocket horizon, then a sharp decrease to 240–275 °C in the pockets where K-feldspar is perthitic. We interpret the feldspar geothermometry (except perhaps in the miarolitic cavities) to reflect the temperatures at crystallization fronts that advanced into the pegmatite, first from the foot wall and eventually joined by a similar front downward from the hanging wall. Crystallization down from the hanging wall may have commenced after ∼70–80% of the foot wall aplite had crystallized. The very abrupt increases of Li, Mn, and F in tourmaline and garnet near the miarolitic zone appear to be explained best by the process of constitutional zone refining, in which a fluxed crystallization front sweeps an incompatible element-enriched boundary layer through a solid or semi-solid. After these two highly fluxed boundary layers merged near the main miarolitic zone, compositional evolution could have proceeded by crystal-melt fractionation.

Dissolution of orthopyroxene in basanitic magma between 0.4 and 2 GPa: further implications for the origin of Si-rich alkaline glass inclusions in mantle xenoliths

Abstract: A large body of recent work has linked the origin of Si-Al-rich alkaline glass inclusions to metasomatic processes in the upper mantle. This study examines one possible origin for these glass inclusions, i.e., the dissolution of orthopyroxene in Si-poor alkaline (basanitic) melt. Equilibrium dissolution experiments between 0.4 and 2 GPa show that secondary glass compositions are only slightly Si enriched and are alkali poor relative to natural glass inclusions. However, disequilibrium experiments designed to examine dissolution of orthopyroxene by a basanitic melt under anhydrous, hydrous and CO2-bearing conditions show complex reaction zones consisting of olivine, ± clinopyroxene and Si-rich alkaline glass similar in composition to that seen in mantle xenoliths. Dissolution rates are rapid and dependent on volatile content. Experiments using an anhydrous solvent show time dependent dissolution rates that are related to variable diffusion rates caused by the saturation of clinopyroxene in experiments longer than 10 minutes. The reaction zone glass shows a close compositional correspondence with natural Si-rich alkaline glass in mantle-derived xenoliths. The most Si-and alkali-rich melts are restricted to pressures of 1 GPa and below under anhydrous and CO2-bearing conditions. At 2 GPa glass in hydrous experiments is still Si-␣and alkali-rich whereas glass in the anhydrous and CO2-bearing experiments is only slightly enriched in SiO2 and alkalis compared with the original solvent. In the low pressure region, anhydrous and hydrous solvent melts yield glass of similar composition whereas the glass from CO2-bearing experiments is less SiO2 rich. The mechanism of dissolution of orthopyroxene is complex involving rapid incongruent breakdown of the orthopyroxene, combined with olivine saturation in the reaction zone forming up to 60% olivine. Inward diffusion of CaO causes clinopyroxene saturation and uphill diffusion of Na and K give the glasses their strongly alkaline characteristics. Addition of Na and K also causes minor SiO2 enrichment of the reaction glass by increasing the phase volume of olivine. Olivine and clinopyroxene are transiently stable phases within the reaction zone. Clinopyroxene is precipitated from the reaction zone melt near the orthopyroxene crystal and redissolved in the outer part of the reaction zone. Olivine defines the thickness of the reaction zone and is progressively dissolved in the solvent as the orthopyroxene continues to dissolve. Although there are compelling reasons for supporting the hypothesis that Si-rich alkaline melts are produced in the mantle by orthopyroxene – melt reaction in the mantle, there are several complications particularly regarding quenching in of disequilibrium reaction zone compositions and the mobility of highly polymerized melts in the upper mantle. It is considered likely that formation of veins and pools of Si-rich alkaline glass by orthopyroxene – melt reaction is a common process during the ascent of xenoliths. However, reaction in situ within the mantle will lead to equilibration and therefore secondary melts will be only moderately siliceous and alkali poor.