Enrichment In Incompatible Elements Research Articles

The influence of melt infiltration on the Li and Mg isotopic composition of the Horoman Peridotite Massif

We have analysed the Li and Mg isotope ratios of a suite of samples from the Horoman Peridotite Massif. Our results show that most Li and all Mg isotopic compositions of the Horoman peridotites are constant over 100metres of continuous outcrop, yielding values for pristine mantle of δ7Li=3.8±1.4‰ (2SD, n=9), δ25Mg=−0.12±0.02‰ and δ26Mg=−0.23±0.04‰ (2SD, n=17), in keeping with values for undisturbed mantle xenoliths. However, there are also some anomalously low δ7Li values (−0.2‰ to 1.6‰), which coincide with locations that show enrichment of incompatible elements, indicative of the prior passage of small degree melts. We suggest Li diffused from infiltrating melts with high [Li] into the low [Li] minerals and kinetically fractionated 7Li/6Li as a result. Continued diffusion after the melt flow had ceased would have resulted in the disappearance of this isotopically light signature in less than 15Ma. In order to preserve this feature, the melt infiltration must have been a late stage event and the massif must have subsequently cooled over a maximum of ∼0.3Ma from peak temperature (950°C, assuming the melts were hydrous) to Li closure temperature (700°C), likely during emplacement. The constant δ26Mg values of Horoman peridotites suggest that chemical potential gradients caused by melt infiltration were insufficient to drive associated δ26Mg fractionation greater than our external precision of 0.03‰.

The global chemical systematics of arc front stratovolcanoes: Evaluating the role of crustal processes

Petrogenetic models for convergent margins should be consistent with the global systematics of convergent margin volcanic compositions. A newly developed tool for compiling and screening data from the GEOROC database was used to generate a global dataset of whole rock chemical analyses from arc front stratovolcano samples. Data from 227 volcanoes within 31 volcanic arc segments were first averaged by volcano and then by arc to explore global systematics. Three different methods of data normalization produce consistent results that persist across a wide range of Mg# [Mg#=Mg/(Mg+Fe)]. Remarkably coherent systematics are present among major and trace element concentrations and ratios, with the exception of three arcs influenced by mantle plumes and Peru/N. Chile, which is built on exceptionally thick crust. Chemical parameters also correlate with the thickness of the overlying arc crust. In addition to previously established correlations of Na6.0 with Ca6.0 and crustal thickness, correlations are observed among major elements, trace elements, and trace element ratios (e.g. La/Yb, Dy/Yb, Zr/Sm, Zr/Ti). Positive correlations include “fluid mobile,” “high field strength,” and “large ion lithophile” element groups, with concentrations that vary by a factor of five in all groups. Incompatible element enrichments also correlate well with crustal thickness, with the greatest enrichment found at arcs with the thickest crust. Intra-crustal processes, however, do not reproduce the global variations. High pressure fractionation produces intermediate magmas enriched in aluminum, but such magmas are rare. Furthermore, differences among magma compositions at various volcanic arcs persist from primitive to evolved compositions, which is inconsistent with the possibility that global variations are produced by crystal fractionation at any pressure. Linear relationships among elements appear to be consistent with mixing between depleted primary magma and an enriched contaminant, but the required composition of the theoretical enriched end-member is not similar to compositions expected in the deep crust or to any known rock composition. The large-scale chemical variations among volcanic arcs are therefore likely to be generated by processes in the subducting slab or mantle wedge, rather than the crust. While crustal processes are important in the differentiation of convergent margin magmas, they do not account for the systematics presented here. Models that attribute the chemical variability of arc magmas to slab or wedge processes are also constrained to be consistent with the global chemical systematics, and are discussed in Turner and Langmuir (2015).

Petrogenesis of the Ultrapotassic Fanshan Intrusion in the North China Craton: Implications for Lithospheric Mantle Metasomatism and the Origin of Apatite Ores

The Fanshan intrusion in the North China Craton (NCC) is concentrically zoned with syenite in the core (Unit 1), surrounded by ultramafic rocks (clinopyroxenite and biotite clinopyroxenite; Unit 2), and an outer rim of garnet-rich clinopyroxenite and orthoclase clinopyroxenite and syenite (Unit 3). The intrusive rocks are composed of variable amounts of Ca-rich augite, biotite, orthoclase, melanite, garnet, magnetite and apatite, with minor primary calcite. Monomineralic apatite rocks, nelsonite and glimmerite exclusively occur in Unit 2. Geochemically, the Fanshan rocks are highly enriched in light rare earth elements (LREE) and large ion lithophile elements (LILE), moderately depleted in high field strength elements (HFSE), and have a limited range of Sr‐Nd‐O isotopic compositions. The similar mineralogy, mineral compositions, and trace element characteristics of the three units suggest that all the rocks are co-magmatic. The parental magma is ultrapotassic and is akin to kamafugite. Very low-degree partial melting of metasomatized lithospheric mantle best explains the geochemistry and petrogenesis of the parental magmas of the Fanshan intrusion. We propose that the mantle source may have been metasomatized by a hydrous carbonate-bearing melt, which has imprinted the enriched Sr‐Nd isotopic signature and incompatible element enrichment with conspicuous negative Nb‐Ta‐Zr‐Hf‐Ti anomalies and LREE enrichments. The mantle source enrichment may be correlated with oceanic sediment recycling during southward subduction of the Paleo-Asian oceanic plate during the Carboniferous and Permian. We propose that crystal settling and mechanical sorting combined with repeated primitive magma replenishment and mixing with previously fractionated magma is the predominant process responsible for the formation of the apatite ores.

Carbonate-silicate composition of diamond-forming media of fibrous diamonds from the Snap Lake area (Canada)

This study presents new data on the compositions of microinclusions in fibrous diamonds from the Snap Lake area in the eastern part of the Slave Craton (Canada). The compositional trends of diamond microinclusions are consistent with those of diamond-forming media ranging continuously between a highly carbonatitic endmember and a highly silicic endmember. The microinclusions exhibit general enrichment of most incompatible elements, which is probably indicative of their crystallization during partial melting of mantle peridotites and eclogites. Our results also suggest that the diamond analyzed in this study may have formed as a result of interaction between carbonate-silicate melts and peridotitic wall-rocks at the base of a thick lithospheric mantle at depths below 300 km. The trace element distributions in the studied diamond microinclusions show a general similarity to those previously found in the parental kimberlites and carbonatites. These data suggest that diamonds may have crystallized either directly from a kimberlitic/carbonatitic melt or from a proto-kimberlitic fluid/melt, which was derived from a source also common to kimberlites. This is supported by differences in the major element compositions of diamond-forming fluids/melts and kimberlites.

The Yanaurcu volcano (Western Cordillera, Ecuador): A field, petrographic, geochemical, isotopic and geochronological study

The Yanaurcu volcanic center in the Ecuadorian frontal arc is characterized by several epochs of activity from the Early Pliocene to approx. 61ka, with important changes in geochemistry and isotope ratio values throughout its history. Most of its units have high Sr/Y and La/Yb signatures. We present a comprehensive study of this volcano involving morphological and stratigraphical observations, sampling, petrography, whole rock and in situ geochemistry, whole rock radiogenic isotope analysis and 40Ar/39Ar geochronology. We identify three magmatic series: (1) Early Pliocene andesitic and dacitic volcanics, (2) Pliocene andesitic flows (~3.6Ma), and (3) two Pleistocene andesitic domes (~172ka and ~61ka). Radiogenic isotope data suggest an increasing amount of basement assimilation through the evolution of Yanaurcu, as well as lower rates of ascent and increasing recharge at upper crustal levels, with the Pleistocene domes representing a thermally more mature state of the crust (deep and mid-crust becoming warmer with time when fluxed by a continuous magmatic supply).We also investigate the deep and mid-crustal magma evolution of Yanaurcu by modeling REE+Sr+Y with the Monte Carlo approach in order to get constraints on the fractionating assemblage. We highlight the importance of fractionating garnet in the development of high Sr/Y and La/Yb signatures, and propose a changing regional stress to modify the depth of magma evolution, and therefore the stability of garnet in the fractionating assemblage. Switches from transtensional to compressional regimes in Ecuador have been highlighted by various studies based on tectonic and thermochronological evidences.We conclude that (1) Yanaurcu high Sr/Y and La/Yb ratios can be fully explained by crustal processes and do not need an enriched mantle source nor slab melting, and (2) local thermal maturation of the crust is responsible for an enrichment of incompatible elements through time via recharge processes, whereas heavy rare earth element (HREE) depletion is controlled by regional tectonics.

Lithospheric mantle evolution in the Afro-Arabian domain: Insights from Bir Ali mantle xenoliths (Yemen)

Detailed petrological and geochemical investigations of an extensive sampling of mantle xenoliths from the Neogene–Quaternary Bir Ali diatreme (southern Yemen) indicate that the underlying lithospheric mantle consists predominantly of medium- to fine-grained (often foliated) spinel-peridotites (85–90%) and spinel-pyroxenites (10–15%) showing thermobarometric estimates in the P–T range of 0.9–2.0GPa and 900–1150°C. Peridotites, including lherzolites, harzburgites and dunites delineate continuous chemical, modal and mineralogical variations compatible with large extractions of basic melts occurring since the late Proterozoic (~2Ga, according to Lu–Hf model ages). Pyroxenites may represent intrusions of subalkaline basic melts interacting and equilibrated with the host peridotite. Subsequent metasomatism has led to modal changes, with evidence of reaction patches and clinopyroxene and spinel destabilization, as well as formation of new phases (glass, amphibole and feldspar). These changes are accompanied by enrichment of the most incompatible elements and isotopic compositions. 143Nd/144Nd ranges from 0.51419 to 0.51209 (εNd from +30.3 to −10.5), 176Hf/177Hf from 0.28459 to 0.28239 (εHf from +64.4 to −13.6), and 208Pb/204Pb from 36.85 to 41.56, thus extending from the depleted mantle (DM) towards the enriched OIB mantle (EM and HIMU) components. 3He/4He (R/RA) ratios vary from 7.2 to 7.9 with He concentrations co-varying with the most incompatible element enrichment, in parallel with metasomatic effects. These metasomatic events, particularly effective in harzburgites and dunites, are attributable to the variable interaction with alkaline basic melts related to the general extensional and rifting regime affecting the East Africa–Arabian domain during the Cenozoic. In this respect, Bir Ali mantle xenoliths resemble those occurring along the Arabian margins and the East Africa Rift system, similarly affected by alkaline metasomatism, whereas they are distinctly different from xenoliths located within the Ethiopian–Yemen continental flood basalt province that are pervasively refertilized by plume-related subalkaline melts.

Alteration of mélange-hosted chromitites from Korydallos, Pindos ophiolite complex, Greece: evidence for modification by a residual high-T post-magmatic fluid

Abstract The peridotites from the area of Korydallos, in the Pindos ophiolitic massif, crop out as deformed slices of a rather dismembered sub-oceanic, lithospheric mantle section and are tectonically enclosed within the Avdella melange. The most sizeable block is a chromitite-bearing serpentinite showing a mesh texture. Accessory, subhedral to euhedral Cr-spinels in the serpentinite display Cr# [Cr/(Cr + Al)] values that range from 0.36 to 0.42 and Mg# [Mg/(Mg+ Fe2+ )] values that vary between 0.57 and 0.62, whereas the TiO2 content may be up to 0.47 wt.%. The serpentinite fragment is characterized by low abundances of magmaphile elements (Al2 O3 : 0.66 wt.%, CaO: 0.12 wt.%, Na2 O: 0.08 wt.%, TiO2 : 0.007 wt.%, Sc: 4 ppm) and enrichment in compatible elements (Cr: 2780 ppm and Ni: 2110 ppm). Overall data are in accordance with derivation of the serpentinite exotic block from a dunite that was formed in the mantle region underneath a back-arc basin before tectonic incorporation in the Korydallos melange. Two compositionally different chromitite pods are recognized in the studied serpentinite fragment, a Cr-rich chromitite and a high-Al chromitite, which have been ascribed to crystallization from a single, progressively differentiating MORB/IAT melt. Although both pods are fully serpentinized only the Al-rich one shows signs of limited Cr-spinel replacement by an opaque spinel phase and clinochlore across grain boundaries and fractures. Modification of the ore-making Cr-spinel is uneven among the Al-rich chromitite specimens. Textural features such as olivine replacement by clinochlore and clinochlore disruption by serpentine indicate that Cr-spinel alteration is not apparently related to serpentinization. From the unaltered Cr-spinel cores to their reworked boundaries the Al2 O3 and MgO abundances decrease, being mainly compensated by FeOt and Cr2 O3 increases. Such compositional variations are suggestive of restricted ferrian chromite (and minor magnetite) substitution for Cr-spinel during a short-lived but relatively intense, low amphibolite facies metamorphic episode (temperature: 400-700 °C). The presence of tremolite and clinochlore in the interstitial groundmass of the high-Al chromitite and their absence from the Cr-rich chromitite matrix imply that after chromitite formation a small volume of a high temperature, post-magmatic fluid reacted with Cr-spinel, triggering its alteration.

Geochemistry of alkali and nepheline syenites of the Ukrainian Shield: ICP-MS data

We present new geochemical data on alkali and nepheline syenites from various complexes of different age within the Ukrainian Shield. The results reveal a correlation between the content of trace elements in the syenites, their assignment to a particular rock complex, the chemistry of primary melts, and the degree of their differentiation. The data also suggest regional geochemical heterogeneity in the ultramafic-alkaline complexes of the Ukrainian Shield. The alkali and nepheline syenites in the ultramafic-alkaline massifs from the eastern and western parts of the region exhibit similar REE contents and Eu/Eu* ratios but are markedly different in Nb, Ta, Zr, and Hf content and are of the miaskitic type. These rocks have lower REE, Nb, and Zr and higher Sr and Ba compared with early foidolites. The rocks of the gabbro-syenite complexes define a distinct Fe-enrichment fractionation trend from early syenitic intrusions to more differentiated varieties; they are also characterized by lower Sr, Ba, and Eu/Eu* and significantly lower contents of some major elements, e.g., Ti, Mg, and P. The agpaitic index and concentrations of Zr, Nb, Y, and REE increase in the same direction. A similar geochemical feature is observed in the alkali syenites genetically associated with anorthositerapakivi-granite plutons, which show incompatible-element enrichment and strong depletion in Sr and Ba. The distinctive evolutionary trends of alkali and nepheline syenites from different rock complexes of the Ukrainian Shield can be explained by different mechanisms of their formation. The main petrogenetic mechanism controlling the distribution of trace elements in the rocks of ultramafic-alkaline complexes was the separation of parent melts of melanephelinite and melilitite types into immiscible phonolite and carbonatite liquids. The gabbro-syenite complexes and alkali syenites from anorthosite-rapakivi granite plutons evolved via crystallization differentiation, which involved extensive feldspar fractionation.

Central Tibetan Meso-Tethyan oceanic plateau

We report the occurrences of the remnants of a Meso-Tethyan oceanic plateau, encompassing an area of ~ 2 × 10 5 km 2 in central Tibet. The plateau remnants include large volumes of pillow basalt formed largely by emergent to subaerial eruption, minor ultramafic intrusives and cumulates, exotic blocks of limestone, radiolarian chert, graywacke, and shale. Isotopic and paleontological dating suggest two major plateau eruptive events at 193–173 Ma and at 128–104 Ma, respectively. The basalts are characterized by enrichment of incompatible elements and a wide range of Sr–Nd isotope composition (initial ε Nd from –3.71 to + 7.9, initial 87 Sr/ 86 Sr from 0.703927 to 0.707618). The trace element and Sr–Nd isotopic data suggest that these basalts are of affinity with those from the Kerguelen and Tethyan plumes, indicative of a plume mantle upwelling origin with involvement of continental material. The wholesale obduction of the Meso-Tethyan oceanic plateau, along with the dismembered normal oceanic crustal fragments, over the Tibetan continental crust could have given rise to perhaps 2 km elevation of central Tibet during the Late Cretaceous. • Remnants of Meso-Tethyan oceanic plateau in central Tibet covers an area of ~ 2 × 10 5 km 2 . • Plateau remnants are dominated by basalt sections with a thickness of at least 13 km. • Twohree major plateau eruptive events occurred at 193–173 Ma, at 167–162 Ma, and at 128–104 Ma. • Basalts are enriched in incompatible elements, with a wide range of and heterogeneous in Sr–Nd isotopes. • Obduction of the oceanic plateau likely triggered a 2-km elevation of central Tibet.

10Be, 18O and radiogenic isotopic constraints on the origin of adakitic signatures: a case study from Solander and Little Solander Islands, New Zealand

Subduction-related Quaternary volcanic rocks from Solander and Little Solander Islands, south of mainland New Zealand, are porphyritic trachyandesites and andesites (58.20–62.19 wt% SiO2) with phenocrysts of amphibole, plagioclase and biotite. The Solander and Little Solander rocks are incompatible element enriched (e.g. Sr ~931–2,270 ppm, Ba ~619–798 ppm, Th ~8.7–21.4 ppm and La ~24.3–97.2 ppm) with MORB-like Sr and Nd isotopic signatures. Isotopically similar quench-textured enclaves reflect mixing with intermediate (basaltic-andesite) magmas. The Solander rocks have geochemical affinities with adakites (e.g. high Sr/Y and low Y), whose origin is often attributed to partial melting of subducted oceanic crust. Solander sits on isotopically distinct continental crust, thus excluding partial melting of the lower crust in the genesis of the magmas. Furthermore, the incompatible element enrichments of the Solander rocks are inconsistent with partial melting of newly underplated mafic lower crust; reproduction of their major element compositions would require unrealistically high degrees of partial melting. A similar argument precludes partial melting of the subducting oceanic crust and the inability to match the observed trace element patterns in the presence of residual garnet or plagioclase. Alternatively, an enriched end member of depleted MORB mantle source is inferred from Sr, Nd and Pb isotopic compositions, trace element enrichments and eHf ≫ 0 CHUR in detrital zircons, sourced from the volcanics. 10Be and Sr, Nd and Pb isotopic systematics are inconsistent with significant sediment involvement in the source region. The trace element enrichments and MORB-like Sr and Nd isotopic characteristics of the Solander rocks require a strong fractionation mechanism to impart the high incompatible element concentrations and subduction-related (e.g. high LILE/HFSE) geochemical signatures of the Solander magmas. Trace element modelling shows that this can be achieved by very low degrees of melting of a peridotitic source enriched by the addition of a slab-derived melt. Subsequent open-system fractionation, involving a key role for mafic magma recharge, resulted in the evolved andesitic adakites.

Geochemical fingerprint of the primary magma composition in the marine tephras originated from the Baegdusan and Ulleung volcanoes

The intraplate Baegdusan (Changbai) and Ulleung volcanoes located on the border of China, North Korea, and East/Japan Sea, respectively, have been explained by appeals to both hotspots and asthenospheric mantle upwelling (wet plume) caused by the stagnant Pacific plate. To understand the origin of the Baegdusan and Ulleung volcanism, we performed geochemical analyses on the tephra deposits in the East/Japan Sea basins originating from the Baegdusan and Ulleung volcanoes. The volcanic glass in the tephra from the Baegdusan and Ulleung volcanoes ranged from alkaline trachyte to peralkaline rhyolite and from phonolite to trachyte, respectively. The tephra from the two intraplate volcanoes showed highly enriched incompatible elements, such as Tb, Nb, Hf, and Ta, distinct from those of the ordinary arc volcanoes of the Japanese islands. The straddle distribution of the Th/Yb and Ta/Yb ratios of the tephra deposits from the Baegdusan volcano may originate from the alkali basaltic magma resulting from mixing between the wet plume from the stagnant Pacific plate in the transition zone and the overlying shallow asthenospheric mantle. In contrast, the deposits from the Ulleung volcano show a minor contribution of the stagnant slab to the basaltic magma, implying either partial melting of a more enriched mantle, smaller degrees of partial melting of a garnet-bearing mantle source, or a combination of both processes as the magma genesis. Our study indicated that the Baegdusan and Ulleung volcanoes have different magma sources and evolutionary histories.

Lithospheric origin for Neogene–Quaternary Middle Atlas lavas (Morocco): Clues from trace elements and Sr–Nd–Pb–Hf isotopes

This study presents new geochemical data on 26 mafic lavas from the Middle Atlas and Central Morocco volcanic provinces, including Miocene nephelinites and Pliocene–Quaternary (3.9–0.6 Ma) nephelinites, basanites, alkali and subalkaline basalts. Most of them represent near-primary magmas, although some alkali basalts were derived from the minor fractionation of olivine and diopside phenocrysts. These evolved samples and the subalkaline basalt display higher 207Pb/204Pb and Zr/Nb ratios and lower εNd consistent with their contamination by lower crustal granulites during an open fractionation process. The progressive enrichment in incompatible elements observed from alkali basalts to nephelinites suggests their derivation from decreasing partial melting degrees of an enriched mantle source located at the garnet–spinel transition zone. The strong negative spikes observed for K in multielement patterns indicate that this source contained a residual pargasitic amphibole. We propose that partial melting occurred at around 2 GPa, i.e. near the lithosphere–asthenosphere boundary beneath the Middle Atlas (60–80 km). The trace element and isotopic Sr–Nd–Pb–Hf signature of the uncontaminated lavas displays a geochemical flavour intermediate between those of high μ (HIMU), “C”, and enriched mantle components. It is very similar to that of abundant metasomatic amphibole- and clinopyroxene-rich lithospheric peridotites and pyroxenites carried by Middle Atlas lavas, which likely represent an analog of the source of these lavas. It is therefore not necessary to postulate the contribution of a “fresh” asthenospheric mantle to their genesis. We propose that they resulted from the partial melting of the base of a veined lithospheric mantle metasomatised during the late Cretaceous by alkaline melts from the Central Atlantic plume, the ancestor of the Canary plume. Melting was probably triggered by the flux of a hot mantle within a regional SW–NE sub-lithospheric channel, in response to either the Alboran slab retreat or edge-driven convection around the West African craton.

Erratum to: Mineralogical and geochemical aspects of the petrogenesis of Pan African Dokhan Volcanics at Esh El Mellaha Area—NE Desert, Egypt

The volcanic activities in the Eastern Desert of Egypt define two major magmatic episodes separated in time. The Dokhan Volcanics is the main representative of the later episode which commenced about 600 Ma and continued for about 25 Ma. These volcanics have been found to vary lithologically from mafic to felsic rocks. Mineralogical and geochemical signatures were used to examine a suite of Dokhan lithology from the Esh El Mellaha area of Egypt Eastern Desert with the aim of clarifying their petrogenesis and tectonic significance. The primary phases (e.g. pyroxene, amphibole, and plagioclase) of the Dokhan volcanics illustrate a progression from basalt to andesite to dacite. Enstatite component (En) of pyroxenes and anorthite (An) component of plagioclase decrease in modes from basalts to andesites to dacites. Whole rock geochemistry records similar trends. There is a wide range of SiO2 (43.62–63.91 wt.%), CaO (2.34–10.56 wt.%), Sr (110–908 ppm), and Zr (120–296 ppm) contents, and a moderate enrichment in incompatible elements. The fractionation index (FeOtotal/MgO) increases gradually from basalts through andesites to dacites (2.72, 2.89, and 4.03, respectively). These chemical variations support a model of fractional crystallization playing an essential role during the evolution of the Dokhan volcanic magma series. The enrichment of LILE (e.g. Rb, Ba, K, and Sr) and the relative depletion of HFSE (e.g. Nb, Zr, Y, and Ti) appear to be inherited from a mantle source. Compiling field relationships with mineralogical and geochemical data confirm three magmatic assemblages: tholeiitic basalts, calc-alkaline andesites, and dacites. The data is interpreted to indicate an island arc tectonic setting that may have been transitional to an active continental margin in a subduction-related environment.

Ka'ena Volcano--A precursor volcano of the island of O'ahu, Hawai'i

Ka‘ena and Wai‘alu Ridges form prominent submarine ridges NW of the island of O‘ahu, Hawai‘i. We evaluate whether or not either one of these ridges represents a submarine extension of Wai‘anae Volcano on O‘ahu using new bottom observations, geophysical surveys, and geochemical data acquired on new samples from the region. Wai‘alu Ridge has the morphology of a submarine rift zone but is too shallow for its distance from the O‘ahu shoreline; Ka‘ena Ridge also is unusually shallow and is surmounted by two topographic shields. Ka‘ena and Wai‘alu Ridges have similar magmatic and volcanic evolutionary histories, beginning ca. 5 Ma with a submarine, shield phase of volcanism that produced high-SiO 2 , low-FeO* tholeiites with higher 208 Pb/ 204 Pb than in the adjacent Wai‘anae Volcano. Late-shield volcanism included transitional and alkalic rock types, with lower SiO 2 and enrichment in incompatible elements, especially P 2 O 5 , Nb, Zr, Ti, and light rare earth elements. The transition from shield to late-shield stage occurred as the edifice was beginning to emerge from the sea. Geological observations and K/Ar ages indicate that Ka‘ena emerged above sea level ca. 3.5 Ma, reaching a maximum height of ∼4000 m above the abyssal ocean floor and 1000 m above sea level. Relatively weak gravity anomalies, topographic lineaments, and the orientation of dike complexes indicate a volcanic structure that is independent of Wai‘anae Volcano. Thus, volcanic structure, geochemistry, and age all indicate a precursor volcano to the island of O‘ahu, which we call Ka‘ena Volcano. After emergence, Ka‘ena Volcano tilted ∼2° to the south. We estimate a total volume of 20–27 × 10 3 km 3 for Ka‘ena Volcano, taking into account overlapping geometry of concurrently active volcanoes. Sample compositions from the Ka‘ena landslide deposit are entirely consistent with derivation from Ka‘ena, whereas most samples from the Wai‘anae slump are likely derived from Wai‘anae Volcano. Uniformly oriented dikes in the Wai‘anae NW rift zone likely reflect buttressing by a preexisting Ka‘ena Volcano. Unusual isotopic compositions of some Wai‘anae samples, including unique hydrous silicic lavas, probably reflect interaction with underlying Ka‘ena crust. A newly recognized lava flow field on the southern flank of Ka‘ena Ridge extends the previously known distribution of secondary volcanism in the Kaua‘i Channel. Putative submarine volcanic activity in the region in 1956 cannot have built a large edifice and is unlikely to have produced pumice that was found on O‘ahu shores. This eruptive activity therefore remains unconfirmed.

Carbonate- and silicate-rich globules in the kimberlitic rocks of northwestern Tarim large igneous province, NW China: Evidence for carbonated mantle source

We report carbonate- and silicate-rich globules and andradite from the Wajilitage kimberlitic rocks in the northwestern Tarim large igneous province, NW China. The carbonate-rich globules vary in size from 1 to 3mm, and most have ellipsoidal or round shape, and are composed of nearly pure calcite. The silicate-rich globules are elliptical to round in shape and are typically larger than the carbonate-rich globules ranging from 2 to several centimeters in diameter. They are characterized by clear reaction rims and contain several silicate minerals such as garnet, diopside and phlogopite. The silicate-rich globules, reported here for the first time, are suggested to be related to the origin of andradite within the kimberlitic rocks. Our results show that calcite in the carbonate-rich globules has a high XCa (>0.97) and is characterized by extremely high concentrations of the total rare earth elements (up to 1500ppm), enrichment in Sr (8521–10,645ppm) and LREE, and remarkable depletion in Nd, Ta, Zr, Hf and Ti. The calcite in the silicate-rich globules is geochemically similar to those in the carbonate-rich globules except the lower trace element contents. Garnet is dominantly andradite (And59.56–92.32Grs5.67–36.03Pyr0.36–4.61Spe0–0.33) and is enriched in light rare earth elements (LREEs) and relatively depleted in Rb, Ba, Th, Pb, Sr, Zr and Hf. Phlogopite in the silicate-rich globules has a high Mg# ranging from 0.93 to 0.97. The composition of the diopside is Wo45.82–51.39En39.81–49.09Fs0.88–0.95 with a high Mg# ranging from 0.88 to 0.95. Diopside in the silicate-rich globules has low total rare earth element (REE) contents (14–31ppm) and shows middle REE- (Eu to Gd), slight light REE- and heavy REE-enrichment with elevated Zr, Hf and Sr contents and a negative Nb anomaly in the normalized diagram. The matrix of the kimberlitic rocks are silica undersaturated (27.92–29.31wt.% SiO2) with low Al2O3 (4.51–5.15wt.%) and high CaO (17.29–17.77wt.%) contents. The samples are characterized by incompatible element enrichment with high (La/Yb)N values (41–58) and remarkable negative anomalies in HFSEs (e.g. Ta, Zr, Hf). Our new data suggest that the carbonate-rich globule most likely crystallized at high-temperature and does not represent immiscible liquids, whereas the silicate-rich globules are related to carbonate-rich deuteric hydrothermal fluids during the later-stage of melt evolution. The fluids reacted with the surrounding silicate melts resulting in the formation of skarn minerals such as phlogopite, diopside and andradite. The presence of the carbonate-bearing globules indicates that the Wajilitage kimberlitic rocks are carbonate-rich and most likely derived from an enriched mantle with abundant carbonate. We correlate the carbonated mantle to metasomatism by the migration of deep-seated fluids (carbonate-rich) in response to the impingement of the early Permian mantle plume.

Uranium, rare metals, and granulite-facies metamorphism

During granulite-facies metamorphism of metasedimentary rocks by the infiltration of carbonic fluids, the disappearance of hydrated minerals leads to the liberation of aqueous fluids. These fluids are strongly enriched in F and Cl, and a series of Large-Ion-Lithophile (LIL) elements and rare metals, resulting in their depletion in granulites. To sum up the fate of these elements, we focus on three domains representing different crustal levels and showing distinct behaviours with respect to these elements. The Lapland metasedimentary granulites illustrate the behaviour of the LILE and rare metals during lower crustal metamorphism. There is no change in Ba, moderate loss in Rb, and extreme depletion in Cs, Li, and Sn. F and Cl contents are also very low compared to the protoliths or average upper continental crust. Biotite and amphibole breakdown leads to the incorporation of their partitioning into a fluid or a melt.The Tranomaro metasomatized marbles recrystallizing under granulite-facies conditions represent a demonstrative example of fluid transfer from granulite-facies supracrustals to traps represented by regional scale skarns. Such fluids may be at the origin of the incompatible element enrichment detected in leucosomes of migmatites from St Malo in Brittany (France) and Black Hills in South Dakota. The northern French Massif Central provides us with an example of a potential association between incompatible element enrichment of granitic melts and granulite-facies metamorphism. U- and F-enriched fine-grained granites are emplaced along a crustal scale shear zone active during the emplacement within the St Sylvestre peraluminous leucogranitic complex. We propose that during granulite-facies metamorphism dominated by carbonic waves in a deep segment of the continental crust, these shear zones control: (i) the percolation of F-, LILE-, rare metal-rich fluids liberated primarily by the breakdown of biotite; (ii) the enhancement of partial melting by F-rich fluids at intermediate crustal levels with the generation of F-, LILE-, rare metal-rich granitic melts; (iii) their transfer through the crust with protracted fractionation facilitated by their low viscosity due to high F-Li contents; and finally (iv) their emplacement as rare metal intrusions at shallow crust levels.

GEOCHEMISTRY, MINERALOGY, AND EVOLUTION OF Li-Al MICAS AND FELDSPARS FROM THE MOUNT MICA PEGMATITE, MAINE, USA

Mount Mica is a poorly zoned, sodic LCT-type pegmatite consisting dominantly of quartz, albite, and muscovite in the outer portion of the pegmatite. Micas are the principal K minerals throughout the pegmatite. Potassium feldspar and rare-element minerals such as lepidolite, elbaite, Cs-rich beryl, fluorapatite, and pollucite are restricted to the core zone of the pegmatite. The dearth of rare element (Li, F, Cs, and Rb) substitution in minerals of the outer portion of the pegmatite and the relatively low K/Rb ratio of K-feldspar in the core zone indicate that the overall degree of fractionation of the pegmatite is moderate. Aluminum-micas belong to the muscovite–polylithionite chemical trend, with a compositional gap between muscovite and trilithionite. Lithium is incorporated into the micas mainly via the Li 3 Al −1 □ −2 substitution mechanism. Lithium-Al micas in the wall zone are chemically homogeneous, but abruptly evolve into higher Cs + Rb bearing Li-rich muscovite and lepidolite in the core zone. An abrupt change in grain size, texture, and chemical composition is evident in the micas from the core zone. Pods of fine- to coarse-grained lepidolite occur sporadically throughout the core zone. Muscovite crystals located adjacent to lepidolite pods or adjacent to or within miarolitic cavities may be overgrown by a coarse-grained mosaic of lepidolite crystals. Some of the overgrown muscovite crystals display interlayering on a microscopic μm scale. The interlayering suggests late-stage rapid crystallization along a diffusion-controlled crystal-liquid interface. The abrupt increase of the Cs, Rb, and F in K-feldspar, muscovite, and lepidolite and the occurrence of such highly evolved species as F-rich lepidolite, pollucite pods, elbaite tourmaline, Cs-rich beryl, and spodumene in miarolitic cavities in the core zone suggest that incompatible elements were retained in the residual fluid until their concentration was high enough to initiate crystallization of incompatible-rich mineral phases. The relatively low abundance of incompatible elements in the hanging-wall zone (HWZ) and footwall zone (FWZ) suggest that the fractionation process was very efficient in sweeping the incompatibles into the core zone of the pegmatite, producing proportionally small volumes inside the pegmatite with very high enrichment in incompatible elements.

Whole-rock geochemistry of basic and intermediate intrusive rocks in the Ishiagu area: further evidence of anorogenic setting of the Lower Benue rift, southeastern Nigeria

Petrographic studies on the intrusive rocks from the Ishiagu area show that they are gabbro, dolerites, and diorite. The gabbro and diorite occur as stocks while the dolerites occur as sills in folded sedimentary sequence predominated by shale. Geochemical data confirmed the rocks as basic (gabbro and dolerites) and intermediate (diorite) rocks with silica contents ranging from 42.45 to 50.75 wt.% and 55.03 to 60.24 wt.%, respectively. They are predominantly alkaline (gabbro, dolerites, and diorites) with sparse tholeiites (few gabbro). The basic rocks are made up of calcic plagioclase (An49-54), clinopyroxene, olivine (altered), nepheline, and opaques, while the intermediate rocks consist of plagioclase (An41-49), hornblende, and clinopyroxene. Calcite occurs as a secondary mineral in both groups. Although many samples are moderately to heavily altered (loss on ignition: 2.12–10.46 wt.%), a consistent decrease in magnesium number (Mg#) (gabbro, 0.47; dolerites, 0.37; dolerites, 0.27) and immobile elements (Y, Zr, Hf, Ti, Nb, and Ta), which are more enriched in the intermediate than the basic rocks and similar patterns of spidergrams and rare earth elements (REEs), show that the rocks (gabbro, dolerites, and diorites) are genetically related. The rocks show stronger enrichment in incompatible elements and REEs [(La/Yb)n, 4.83–8.15 for the gabbro, 7.01–7.79 for the dolerites, and 8.85–9.63 for the diorites]. Primitive-mantle normalized trace-element patterns and trace-element ratios of both basic and intermediate rocks indicate similarity to ocean island basalts, which suggests a garnet-lherzolite mantle source. The ratios of La/Nb, Th/La, and Th/Nb and the high ratio of Nb/La (1.18–1.50 for gabbro, 1.37–1.95 for dolerites, and 1.21–1.32 for diorites) indicate a high 238U/204Pb (HIMU) mantle source region. There is no evidence of significant crustal contamination on the basic and intermediate rocks, which may be related to the rapid ascent of the magmas in an intracontinental rift setting similar to the East African rift.

Paleoclimatic conditions and paleoweathering processes on Mesozoic continental redbeds from Western-Central Mediterranean Alpine Chains

Chemical and mineralogical analyses of the Triassic to lowermost Jurassic mudstones from continental redbeds outcropping in the Internal Domains of the Betic–Rifian and Calabria–Peloritani chains have been used to infer the relationships between paleoclimatic conditions and paleoweathering processes during rifting of a continental crust block that finally detached from adjoining western Tethyan realms to form an independent microplate (Mesomediterranean Microplate) from Jurassic to lower Miocene time. The studied mudstone samples come from Middle Triassic and Upper Triassic beds of the Saladilla Formation (both in the Betic Cordillera and in the Rif), whereas the Calabria–Peloritani Arc studied mudstones come from Upper Triassic to lowermost Jurassic beds (both in the Sila and Longi Taormina Units). Major and trace element concentrations, based on the mass-balance calculation relative to the upper continental crust, show negative values both in Gibraltar and Calabria–Peloritani Arcs, implying that mudstone formation in the Early Mesozoic involved moderate to intense continental paleoweathering of the crust. In particular, CaO, Na2O, MgO, Sr, Ba, Fe2O3, MnO and transition metal elements (V, Cr, Co and Ni) are more depleted in the Triassic to Upper Jurassic samples of the Calabria–Peloritani samples than in the Middle to Upper Triassic Betic–Rifian samples, and suggest an increase of continental paleoweathering in the Mediterranean region from the Triassic to the Jurassic. In addition enrichment in SiO2, TiO2, Al2O3, K2O and incompatible elements in the Calabria–Peloritani Arc mudstones indicates sediment recycling effects that gradually increase from the Triassic to Jurassic time. The hinterland paleoweathering and sediment recycling effects have been mathematically distinguished using principal component analysis (PC1 is a measure of paleoweathering rate mainly due to humidity (positive values) against aridity (negative values), whereas PC2 corresponds to the extent of sediment recycling). The results strongly indicate that humidity had increased from the Triassic to the Jurassic and that the depositional environments in Calabria–Peloritani Arc were probably more suitable for sediment recycling. These seasonal climate alternations corresponding to an increase in paleoclimatic humidity that favored paleoweathering conditions and recycling processes. These results are also confirmed by the mineralogical data, which show a higher abundance of kaolinite, typical of warm–humid conditions, in the Calabria-Peloritani mudstones than in those of the Betic Cordillera and the Rif. Furthermore, the comparison among geochemical weathering index values of the studied samples and of recent soils from different climatic zones likely suggests a tropical rainforest climate in the studied area during the Triassic to the lowermost Jurassic.

Sr, Nd, Pb and Os Isotope Systematics of CAMP Tholeiites from Eastern North America (ENA): Evidence of a Subduction-enriched Mantle Source

The Central Atlantic Magmatic Province (CAMP) is one of the largest igneous provinces on Earth, with an areal extent exceeding 10e7km2. Here we document the geochemical characteristics of CAMP basalts from Triassic-Jurassic basins in northeastern USA and Nova Scotia (Canada). The CAMP rocks occur as lava flows, sills and dykes. All of our analysed samples show chemical characteristics typical of CAMP basalts with low titanium content, which include enrichment in the most incompatible elements and negative Nb anomalies. All the basalts also show enriched Sr-Nd-Pb initial (t=201Ma) isotopic compositions (206Pb/204Pbini. = 18·155-18·691, 207Pb/204Pbini. = 15·616-15·668, 208Pb/204Pbini. = 38·160-38·616, 143Nd/144Ndini. = 0·512169-0·512499). On the basis of stratigraphy, rare earth element (REE) chemistry and Sr-Nd-Pb isotope composition, three chemical groups are defined. The Hook Mountain group, with the lowest La/Yb ratios, initial 206Pb/204Pbini. >18·5 and 143Nd/144Ndini.>0·51238, comprises all the latest and upper stratigraphic units. The Preakness group, with intermediate La/Yb ratios, 206Pb/204Pbini.>18·5 and 0·51233>143Nd/144Ndini.>0·51225, comprises the intermediate units. The Orange Mountain group has the highest La/Yb ratios and 143Nd/144Ndini.<0·51235 and involves all the earliest and stratigraphically lowest units, including the entire North Mountain basalts from Nova Scotia. In this last group, three sub-groups may be distinguished: the Rapidan sill, which has 206Pb/204Pbini. higher than 18·5, the Shelburne sub-group, which has 143Nd/144Ndini.<0·51225, and the remaining Orange Mt samples. With the exception of one sample, the Eastern North America (ENA) CAMP basalts display initial 187Os/188Os ratios in the range of mantle-derived magmas (<0·15). Simple modelling shows that the composition of the ENA CAMP basalts cannot plausibly be explained solely by crustal contamination of oceanic island basalt (OIB), mid-ocean ridge basalt (MORB) or oceanic plateau basalt (OPB) magmas. Mixing of such magma compositions with sub- continental lithospheric mantle (SCLM)-derived melts followed by crustal contamination, by either assimilation-fractional crystallization (AFC) or assimilation through turbulent ascent (ATA) pro- cesses is somewhat more successful. However, this latter scenario does not reproduce the REE and isotopic composition of the ENA CAMP in a fully satisfactory manner. Alternatively, we propose a model in which asthenospheric mantle overlying a subducted slab (i.e. mantle wedge) was enriched during Cambrian to Devonian subduction by sedimentary material, isotopically equivalent to Proterozoic-Lower Paleozoic crustal rocks. Subsequently, after subduction ceased, the isotopic composition of this mantle evolved by radioactive decay for another 170 Myr until the CAMP magmatic event. Varying amounts and compositions of the incorporated sedimentary component coupled with radiogenic ingrowth over time can account for the main geochemical characteristics of the ENA CAMP (enriched incompatible element patterns, negative Nb anomalies, enriched Sr-Nd-Pb isotopic composition) and the differences between the three chemical groups.